TY - JOUR A1 - Knox-Brown, Patrick A1 - Rindfleisch, Tobias A1 - Günther, Anne A1 - Balow, Kim A1 - Bremer, Anne A1 - Walther, Dirk A1 - Miettinen, Markus S. A1 - Hincha, Dirk K. A1 - Thalhammer, Anja T1 - Similar Yet Different BT - Structural and Functional Diversity among Arabidopsis thaliana LEA_4 Proteins JF - International Journal of Molecular Sciences N2 - The importance of intrinsically disordered late embryogenesis abundant (LEA) proteins in the tolerance to abiotic stresses involving cellular dehydration is undisputed. While structural transitions of LEA proteins in response to changes in water availability are commonly observed and several molecular functions have been suggested, a systematic, comprehensive and comparative study of possible underlying sequence-structure-function relationships is still lacking. We performed molecular dynamics (MD) simulations as well as spectroscopic and light scattering experiments to characterize six members of two distinct, lowly homologous clades of LEA_4 family proteins from Arabidopsis thaliana. We compared structural and functional characteristics to elucidate to what degree structure and function are encoded in LEA protein sequences and complemented these findings with physicochemical properties identified in a systematic bioinformatics study of the entire Arabidopsis thaliana LEA_4 family. Our results demonstrate that although the six experimentally characterized LEA_4 proteins have similar structural and functional characteristics, differences concerning their folding propensity and membrane stabilization capacity during a freeze/thaw cycle are obvious. These differences cannot be easily attributed to sequence conservation, simple physicochemical characteristics or the abundance of sequence motifs. Moreover, the folding propensity does not appear to be correlated with membrane stabilization capacity. Therefore, the refinement of LEA_4 structural and functional properties is likely encoded in specific patterns of their physicochemical characteristics. KW - IDP KW - LEA protein KW - abiotic stress KW - dehydration KW - conformational rearrangement KW - membrane stabilization KW - sequence-structure-function relationship Y1 - 2020 U6 - https://doi.org/10.3390/ijms21082794 SN - 1422-0067 VL - 21 IS - 8 PB - Molecular Diversity Preservation International CY - Basel ER - TY - JOUR A1 - Maares, Maria A1 - Keil, Claudia A1 - Koza, Jenny A1 - Straubing, Sophia A1 - Schwerdtle, Tanja A1 - Haase, Hajo T1 - In Vitro Studies on Zinc Binding and Buffering by Intestinal Mucins JF - International Journal of Molecular Sciences N2 - The investigation of luminal factors influencing zinc availability and accessibility in the intestine is of great interest when analyzing parameters regulating intestinal zinc resorption. Of note, intestinal mucins were suggested to play a beneficial role in the luminal availability of zinc. Their exact zinc binding properties, however, remain unknown and the impact of these glycoproteins on human intestinal zinc resorption has not been investigated in detail. Thus, the aim of this study is to elucidate the impact of intestinal mucins on luminal uptake of zinc into enterocytes and its transfer into the blood. In the present study, in vitro zinc binding properties of mucins were analyzed using commercially available porcine mucins and secreted mucins of the goblet cell line HT-29-MTX. The molecular zinc binding capacity and average zinc binding affinity of these glycoproteins demonstrates that mucins contain multiple zinc-binding sites with biologically relevant affinity within one mucin molecule. Zinc uptake into the enterocyte cell line Caco-2 was impaired by zinc-depleted mucins. Yet this does not represent their form in the intestinal lumen in vivo under zinc adequate conditions. In fact, zinc-uptake studies into enterocytes in the presence of mucins with differing degree of zinc saturation revealed zinc buffering by these glycoproteins, indicating that mucin-bound zinc is still available for the cells. Finally, the impact of mucins on zinc resorption using three-dimensional cultures was studied comparing the zinc transfer of a Caco-2/HT-29-MTX co-culture and conventional Caco-2 monoculture. Here, the mucin secreting co-cultures yielded higher fractional zinc resorption and elevated zinc transport rates, suggesting that intestinal mucins facilitate the zinc uptake into enterocytes and act as a zinc delivery system for the intestinal epithelium. KW - intestinal zinc resorption KW - zinc binding KW - mucus layer KW - intestinal mucins KW - in vitro intestinal model KW - goblet cells KW - Caco-2/HT-29-MTX-model Y1 - 2018 U6 - https://doi.org/10.3390/ijms19092662 SN - 1422-0067 VL - 19 IS - 9 ER - TY - JOUR A1 - Kath, Nadja J. A1 - Boit, Alice A1 - Guill, Christian A1 - Gaedke, Ursula T1 - Accounting for activity respiration results in realistic trophic transfer efficiencies in allometric trophic network (ATN) models JF - Theoretical ecology N2 - Allometric trophic network (ATN) models offer high flexibility and scalability while minimizing the number of parameters and have been successfully applied to investigate complex food web dynamics and their influence on food web diversity and stability. However, the realism of ATN model energetics has never been assessed in detail, despite their critical influence on dynamic biomass and production patterns. Here, we compare the energetics of the currently established original ATN model, considering only biomass-dependent basal respiration, to an extended ATN model version, considering both basal and assimilation-dependent activity respiration. The latter is crucial in particular for unicellular and invertebrate organisms which dominate the metabolism of pelagic and soil food webs. Based on metabolic scaling laws, we show that the extended ATN version reflects the energy transfer through a chain of four trophic levels of unicellular and invertebrate organisms more realistically than the original ATN version. Depending on the strength of top-down control, the original ATN model yields trophic transfer efficiencies up to 71% at either the third or the fourth trophic level, which considerably exceeds any realistic values. In contrast, the extended ATN version yields realistic trophic transfer efficiencies 30% at all trophic levels, in accordance with both physiological considerations and empirical evidence from pelagic systems. Our results imply that accounting for activity respiration is essential for consistently implementing the metabolic theory of ecology in ATN models and for improving their quantitative predictions, which makes them more powerful tools for investigating the dynamics of complex natural communities. KW - Food web KW - Trophic transfer efficiency KW - Allometric trophic network model KW - Allometry KW - Energy transfer KW - Activity respiration Y1 - 2018 U6 - https://doi.org/10.1007/s12080-018-0378-z SN - 1874-1738 SN - 1874-1746 VL - 11 IS - 4 SP - 453 EP - 463 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Traxler, Juliane A1 - Hanssen, Marjolein M. A1 - Lautenbacher, Stefan A1 - Ottawa, Fabian A1 - Peters, Madelon L. T1 - General versus pain-specific cognitions BT - Pain catastrophizing but not optimism influences conditioned pain modulation JF - European journal of pain N2 - Background Previous studies found evidence that dispositional optimism is related to lower pain sensitivity. Recent findings suggest that temporarily increasing optimism by means of imagining a positive future may also have pain-alleviating effects. Objectives The present experiment was designed to investigate conditioned pain modulation (CPM) as a potential underlying mechanism of this pain-alleviating effect of induced optimism. Methods For this purpose, 45 healthy participants were randomized into an optimistic or neutral imagery condition. Additionally, participants completed questionnaires on dispositional optimism, pain catastrophizing and pain expectations. CPM was assessed by delivering a series of five heat pain stimuli on the nondominant hand before and during immersion of the dominant hand in water of 5 degrees C for 70 s. Results A clear CPM effect was found, that is heat pain reports were lower during simultaneous cold water stimulation. Although the optimism manipulation successfully increased optimism, it did not affect pain ratings or CPM. Post hoc analyses indicated that dispositional optimism was not associated with the magnitude of CPM, but pain catastrophizing and pain expectations did significantly correlate with the CPM effect. Conclusion Pain-specific but not general cognitions appear to influence endogenous pain modulation. Significance Conditioned pain modulation is not the underlying mechanism of the pain-alleviating effects of induced optimism. However, pain-specific cognitions including pain catastrophizing and pain expectations affect endogenous pain modulation which should be taken into account in treatment and CPM research. Y1 - 2018 U6 - https://doi.org/10.1002/ejp.1294 SN - 1090-3801 SN - 1532-2149 VL - 23 IS - 1 SP - 150 EP - 159 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Jia, He A1 - Friebe, Christian A1 - Schubert, Ulrich S. A1 - Zhang, Xiaozhe A1 - Quan, Ting A1 - Lu, Yan A1 - Gohy, Jean-Francois T1 - Core-Shell Nanoparticles with a Redox Polymer Core and a Silica Porous Shell as High-Performance Cathode Material for Lithium-Ion Batteries JF - Energy technology : generation, conversion, storage, distribution N2 - A facile and novel method for the fabrication of core-shell nanoparticles (PTMA@SiO2) based on a poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) core and a porous SiO2 shell is reported. The core-shell nanoparticles are further self-assembled with negatively charged multi-walled carbon nanotubes (MWCNTs), which results in the formation of a free-standing cathode electrode. The porous SiO2 shell not only effectively improves the stability of the linear PTMA redox polymer with low molar mass in organic electrolytes but also leads to the uniform dispersion of PTMA active units in the MWCNTs conductive network. The PTMA@SiO2@MWCNT composite electrode exhibits a specific capacity as high as 73.8 mAh g at 1 C and only 0.11% capacity loss per cycle at a rate of 2 C. KW - composite electrodes KW - core-shell nanoparticles KW - energy storage KW - lithium-ion batteries KW - redox polymers Y1 - 2019 U6 - https://doi.org/10.1002/ente.201901040 SN - 2194-4288 SN - 2194-4296 VL - 8 IS - 3 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Kleuser, Burkhard T1 - The enigma of sphingolipids in health and disease T2 - International journal of molecular sciences Y1 - 2018 U6 - https://doi.org/10.3390/ijms19103126 SN - 1422-0067 VL - 19 IS - 10 PB - MDPI CY - Basel ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Frischmann, Peter D. A1 - Schulze, Marcus A1 - Bohn, Bernhard J. A1 - Wein, Robin A1 - Livadas, Panajotis A1 - Carlson, Michael T. A1 - Jäckel, Frank A1 - Feldmann, Jochen A1 - Würthner, Frank A1 - Stolarczyk, Jacek K. T1 - All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods JF - Nature Energy N2 - Full water splitting into hydrogen and oxygen on semiconductor nanocrystals is a challenging task; overpotentials must be overcome for both half-reactions and different catalytic sites are needed to facilitate them. Additionally, efficient charge separation and prevention of back reactions are necessary. Here, we report simultaneous H-2 and O-2 evolution by CdS nanorods decorated with nanoparticulate reduction and molecular oxidation co-catalysts. The process proceeds entirely without sacrificial agents and relies on the nanorod morphology of CdS to spatially separate the reduction and oxidation sites. Hydrogen is generated on Pt nanoparticles grown at the nanorod tips, while Ru(tpy)(bpy)Cl-2-based oxidation catalysts are anchored through dithiocarbamate bonds onto the sides of the nanorod. O-2 generation from water was verified by O-18 isotope labelling experiments, and time-resolved spectroscopic results confirmed efficient charge separation and ultrafast electron and hole transfer to the reaction sites. The system demonstrates that combining nanoparticulate and molecular catalysts on anisotropic nanocrystals provides an effective pathway for visible-light-driven photocatalytic water splitting. Y1 - 2018 U6 - https://doi.org/10.1038/s41560-018-0229-6 SN - 2058-7546 VL - 3 IS - 10 SP - 862 EP - 869 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Cherstvy, Andrey G. A1 - Nagel, Oliver A1 - Beta, Carsten A1 - Metzler, Ralf T1 - Non-Gaussianity, population heterogeneity, and transient superdiffusion in the spreading dynamics of amoeboid cells JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - What is the underlying diffusion process governing the spreading dynamics and search strategies employed by amoeboid cells? Based on the statistical analysis of experimental single-cell tracking data of the two-dimensional motion of the Dictyostelium discoideum amoeboid cells, we quantify their diffusive behaviour based on a number of standard and complementary statistical indicators. We compute the ensemble- and time-averaged mean-squared displacements (MSDs) of the diffusing amoebae cells and observe a pronounced spread of short-time diffusion coefficients and anomalous MSD-scaling exponents for individual cells. The distribution functions of the cell displacements, the long-tailed distribution of instantaneous speeds, and the velocity autocorrelations are also computed. In particular, we observe a systematic superdiffusive short-time behaviour for the ensemble- and time-averaged MSDs of the amoeboid cells. Also, a clear anti-correlation of scaling exponents and generalised diffusivity values for different cells is detected. Most significantly, we demonstrate that the distribution function of the cell displacements has a strongly non-Gaussian shape andusing a rescaled spatio-temporal variablethe cell-displacement data collapse onto a universal master curve. The current analysis of single-cell motions can be implemented for quantifying diffusive behaviours in other living-matter systems, in particular, when effects of active transport, non-Gaussian displacements, and heterogeneity of the population are involved in the dynamics. Y1 - 2018 U6 - https://doi.org/10.1039/c8cp04254c SN - 1463-9076 SN - 1463-9084 VL - 20 IS - 35 SP - 23034 EP - 23054 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Brügger, Sandra Olivia A1 - Gobet, Erika A1 - Sigl, Michael A1 - Osmont, Dimitri A1 - Papina, Tatyana A1 - Rudaya, Natalia A1 - Schwikowski-Gigar, Margit A1 - Tinner, Willy T1 - Ice records provide new insights into climatic vulnerability of Central Asian forest and steppe communities JF - Global and planetary change N2 - Forest and steppe communities in the Altai region of Central Asia are threatened by changing climate and anthropogenic pressure. Specifically, increasing drought and grazing pressure may cause collapses of moisture-demanding plant communities, particularly forests. Knowledge about past vegetation and fire responses to climate and land use changes may help anticipating future ecosystem risks, given that it has the potential to disclose mechanisms and processes that govern ecosystem vulnerability. We present a unique paleoecological record from the high-alpine Tsambagarav glacier in the Mongolian Altai that provides novel large-scale information on vegetation, fire and pollution with an exceptional temporal resolution and precision. Our palynological record identifies several late-Holocene boreal forest expansions, contractions and subsequent recoveries. Maximum forest expansions occurred at 3000-2800 BC, 2400-2100 BC, and 1900-1800 BC. After 1800 BC mixed boreal forest communities irrecoverably declined. Fires reached a maximum at 1600 BC, 200 years after the final forest collapse. Our multiproxy data suggest that burning peaked in response to dead biomass accumulation resulting from forest diebacks. Vegetation and fire regimes partly decoupled from climate after 1700 AD, when atmospheric industrial pollution began, and land use intensified. We conclude that moisture availability was more important than temperature for past vegetation dynamics, in particular for forest loss and steppe expansion. The past Mongolian Altai evidence implies that in the future forests of the Russian Altai may collapse in response to reduced moisture availability. KW - Boreal forest diebacks KW - Climatic tipping points KW - Diversity KW - Ice core KW - Moisture change KW - Pollen KW - Microscopic charcoal KW - SCP Y1 - 2018 U6 - https://doi.org/10.1016/j.gloplacha.2018.07.010 SN - 0921-8181 SN - 1872-6364 VL - 169 SP - 188 EP - 201 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Fudickar, Werner A1 - Linker, Torsten T1 - Release of Singlet Oxygen from Aromatic Endoperoxides by Chemical Triggers JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - The generation of reactive singlet oxygen under mild conditions is of current interest in chemistry, biology, and medicine. We were able to release oxygen from dipyridylanthracene endoperoxides (EPOs) by using a simple chemical trigger at low temperature. Protonation and methylation of such EPOs strongly accelerated these reactions. Furthermore, the methyl pyridinium derivatives are water soluble and therefore serve as oxygen carriers in aqueous media. Methylation of the EPO of the ortho isomer affords the parent form directly without increasing the temperature under very mild conditions. This exceptional behavior is ascribed to the close contact between the nitrogen atom and the peroxo group. Singlet oxygen is released upon this reaction, and can be used to oxygenate an acceptor such as tetramethylethylene in the dark with no heating. Thus, a new chemical source of singlet oxygen has been found, which is triggered by a simple stimulus. KW - anthracenes KW - donor-acceptor systems KW - mild reaction conditions KW - selective oxidations KW - singlet oxygen Y1 - 2018 U6 - https://doi.org/10.1002/anie.201806881 SN - 1433-7851 SN - 1521-3773 VL - 57 IS - 39 SP - 12971 EP - 12975 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Koc, Julian A1 - Simovich, Tomer A1 - Schönemann, Eric A1 - Chilkoti, Ashutosh A1 - Gardner, Harrison A1 - Swain, Geoffrey W. A1 - Hunsucker, Kelli A1 - Laschewsky, André A1 - Rosenhahn, Axel T1 - Sediment challenge to promising ultra-low fouling hydrophilic surfaces in the marine environment JF - Biofouling : the journal of bioadhesion and biofilm research N2 - Hydrophilic coatings exhibit ultra-low fouling properties in numerous laboratory experiments. In stark contrast, the antifouling effect of such coatings in vitro failed when performing field tests in the marine environment. The fouling release performance of nonionic and zwitterionic hydrophilic polymers was substantially reduced compared to the controlled laboratory environment. Microscopy and spectroscopy revealed that a large proportion of the accumulated material in field tests contains inorganic compounds and diatomaceous soil. Diatoms adhered to the accumulated material on the coating, but not to the pristine polymer. Simulating field tests in the laboratory using sediment samples collected from the test sites showed that incorporated sand and diatomaceous earth impairs the fouling release characteristics of the coatings. When exposed to marine sediment from multiple locations, particulate matter accumulated on these coatings and served as attachment points for diatom adhesion and enhanced fouling. Future developments of hydrophilic coatings should consider accumulated sediment and its potential impact on the antifouling performance. KW - hydrogel KW - field test KW - fouling release KW - marine biofouling KW - sediment Y1 - 2019 U6 - https://doi.org/10.1080/08927014.2019.1611790 SN - 0892-7014 SN - 1029-2454 VL - 35 IS - 4 SP - 454 EP - 462 PB - Taylor & Francis CY - London ER - TY - JOUR A1 - Schuck, Götz A1 - Lehmann, Frederike A1 - Ollivier, Jacques A1 - Mutka, Hannu A1 - Schorr, Susan T1 - Influence of chloride substitution on the rotational dynamics of methylammonium in MAPbI(3-x)Cl(x) perovskites JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Hybrid halide perovskites, MAPbI(3), MAPbI(2.94)Cl(0.0)6, and MAPbCl(3) (MA, methylammonium), were investigated using inelastic and quasielastic neutron scattering (QENS) with the aim of elucidating the impact of chloride substitution on the rotational dynamics of MA. In this context, we discuss the influence of the inelastic neutron scattering caused by low-energy phonons on QENS, resulting from the MA rotational dynamics in MAPbI(3-x)Cl(x). Through a comparative temperature-dependent QENS investigation with different energy resolutions, which allow a wide Fourier time window, we achieved a consistent description of the influence of chlorine substitution in MAPbI(3) on the MA dynamics. Our results showed that chlorine substitution in the low-temperature orthorhombic phase leads to a weakening of the hydrogen bridge bonds, since the characteristic relaxation times of C-3 rotation at 70 K in MAPbCl(3) (135 ps) and MAPbI(2.94)Cl(0.06) (485 ps) are much shorter than that in MAPbI(3) (1635 ps). For the orthorhombic phase, we obtained the activitin energies from the temperature-dependent characteristic relaxation times tau (c3). by Arrhenius fits, indicating lower values of E-a for MAPbCl(3) and MAPbI(2.94)Cl(0.06) compared to that of MAPbI(3). We also performed QENS analyses at 190 K for all three samples. Here, we observed that MAPbCI(3) shows slower MA rotational dynamics than MAPbI(3) in the disordered structure. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpcc.9b01238 SN - 1932-7447 VL - 123 IS - 18 SP - 11436 EP - 11446 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Yu, Hongtao A1 - Quan, Ting A1 - Mei, Shilin A1 - Kochovski, Zdravko A1 - Huang, Wei A1 - Meng, Hong A1 - Lu, Yan T1 - Prompt Electrodeposition of Ni Nanodots on Ni Foam to Construct a High-Performance Water-Splitting Electrode BT - Efficient, Scalable, and Recyclable JF - Nano-Micro Letters N2 - HighlightsFacile electrodeposition for fabricating active Ni nanodots (NiNDs) on Ni foam (NF) is shown.Binder- and heteroatom-free recyclable NiO/NiNDs@NF electrodes are efficiently made.NiO/NiNDs@NF bifunctional catalytic electrodes are used for water splitting. AbstractIn past decades, Ni-based catalytic materials and electrodes have been intensively explored as low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysts for water splitting. With increasing demands for Ni worldwide, simplifying the fabrication process, increasing Ni recycling, and reducing waste are tangible sustainability goals. Here, binder-free, heteroatom-free, and recyclable Ni-based bifunctional catalytic electrodes were fabricated via a one-step quick electrodeposition method. Typically, active Ni nanodot (NiND) clusters are electrodeposited on Ni foam (NF) in Ni(NO3)(2) acetonitrile solution. After drying in air, NiO/NiND composites are obtained, leading to a binder-free and heteroatom-free NiO/NiNDs@NF catalytic electrode. The electrode shows high efficiency and long-term stability for catalyzing hydrogen and oxygen evolution reactions at low overpotentials ((10)(HER)=119mV and (50)(OER)=360mV) and can promote water catalysis at 1.70V@10mAcm(-2). More importantly, the recovery of raw materials (NF and Ni(NO3)(2)) is quite easy because of the solubility of NiO/NiNDs composites in acid solution for recycling the electrodes. Additionally, a large-sized (S similar to 70cm(2)) NiO/NiNDs@NF catalytic electrode with high durability has also been constructed. This method provides a simple and fast technology to construct high-performance, low-cost, and environmentally friendly Ni-based bifunctional electrocatalytic electrodes for water splitting. KW - Electrodeposition KW - Ni nanodots KW - Bifunctional catalysts KW - Water splitting KW - Large-size Y1 - 2019 U6 - https://doi.org/10.1007/s40820-019-0269-x SN - 2311-6706 SN - 2150-5551 VL - 11 IS - 41 PB - Shanghai JIAO TONG univ press CY - Shanghai ER - TY - JOUR A1 - Utecht, Manuel Martin A1 - Gaebel, Tina A1 - Klamroth, Tillmann T1 - Desorption induced by low energy charge carriers on Si(111)-7 x 7 BT - first principles molecular dynamics for benzene derivates JF - Journal of computational chemistry : organic, inorganic, physical, biological N2 - We use clusters for the modeling of local ion resonances caused by low energy charge carriers in STM-induced desorption of benzene derivates from Si(111)-7 x 7. We perform Born-Oppenheimer molecular dynamics for the charged systems assuming vertical transitions to the charged states at zero temperature, to rationalize the low temperature activation energies, which are found in experiment for chlorobenzene. Our calculations suggest very similar low temperature activation energies for toluene and benzene. For the cationic resonance transitions to physisorption are found even at 0 K, while the anion remains chemisorbed during the propagations. Further, we also extend our previous static quantum chemical investigations to toluene and benzene. In addition, an in depth analysis of the ionization potentials and electron affinities, which are used to estimate resonance energies, is given. KW - Born-Oppenheimer MD KW - STM-induced reactions KW - cluster models KW - Si(111)-7x7 Y1 - 2018 U6 - https://doi.org/10.1002/jcc.25607 SN - 0192-8651 SN - 1096-987X VL - 39 IS - 30 SP - 2517 EP - 2525 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Werno, Martin Witold A1 - Wilhelmi, Ilka A1 - Kuropka, Benno A1 - Ebert, Franziska A1 - Freund, Christian A1 - Schürmann, Annette T1 - The GTPase ARFRP1 affects lipid droplet protein composition and triglyceride release from intracellular storage of intestinal Caco-2 cells JF - Biochemical and biophysical research communications N2 - Intestinal release of dietary triglycerides via chylomicrons is the major contributor to elevated postprandial triglyceride levels. Dietary lipids can be transiently stored in cytosolic lipid droplets (LDs) located in intestinal enterocytes for later release. ADP ribosylation factor-related protein 1 (ARFRP1) participates in processes of LD growth in adipocytes and in lipidation of lipoproteins in liver and intestine. This study aims to explore the impact of ARFRP1 on LD organization and its interplay with chylomicron-mediated triglyceride release in intestinal-like Caco-2 cells. Suppression of Arfrp1 reduced release of intracellularly derived triglycerides (0.69-fold) and increased the abundance of transitional endoplasmic reticulum ATPase TERA/VCP, fatty acid synthase-associated factor 2 (FAF2) and perilipin 2 (Plin2) at the LD surface. Furthermore, TERA/VCP and FAF2 co-occurred more frequently with ATGL at LDs, suggesting a reduced adipocyte triglyceride lipase (ATGL)-mediated lipolysis. Accordingly, inhibition of lipolysis reduced lipid release from intracellular storage pools by the same magnitude as Arfrp1 depletion. Thus, the lack of Arfrp1 increases the abundance of lipolysis-modulating enzymes TERA/VCP, FAF2 and Plin2 at LDs, which might decrease lipolysis and reduce availability of fatty acids for triglyceride synthesis and their release via chylomicrons. (C) 2018 The Authors. Published by Elsevier Inc. KW - Chylomicron KW - Lipid droplet proteome KW - Triglyceride secretion KW - Lipolysis Y1 - 2018 U6 - https://doi.org/10.1016/j.bbrc.2018.10.092 SN - 0006-291X SN - 1090-2104 VL - 506 IS - 1 SP - 259 EP - 265 PB - Elsevier CY - San Diego ER - TY - JOUR A1 - Duydu, Yalcin A1 - Basaran, Nursen A1 - Aydin, Sevtap A1 - Ustundag, Aylin A1 - Yalcin, Can Özgür A1 - Anlar, Hatice Gul A1 - Bacanli, Merve A1 - Aydos, Kaan A1 - Atabekoglu, Cem Somer A1 - Golka, Klaus A1 - Ickstadt, Katja A1 - Schwerdtle, Tanja A1 - Werner, Matthias A1 - Meyer, Sören A1 - Bolt, Hermann M. T1 - Evaluation of FSH, LH, testosterone levels and semen parameters in male boron workers under extreme exposure conditions JF - Archives of toxicology : official journal of EUROTOX N2 - Boric acid and sodium borates are currently classified in the EU-CLP regulation as "toxic to reproduction" under "Category 1B", with hazard statement of H360FD. However, so far field studies on male reproduction in China and in Turkey could not confirm such boron-associated toxic effects. As validation by another independent study is still required, the present study has investigated possible boron-associated effects on male reproduction in workers (n = 212) under different boron exposure conditions. The mean daily boron exposure (DBE) and blood boron concentration of workers in the extreme exposure group (n = 98) were 47.17 +/- 17.47 (7.95-106.8) mg B/day and 570.6 +/- 160.1 (402.6-1100) ng B/g blood, respectively. Nevertheless, boron-associated adverse effects on semen parameters, as well as on FSH, LH and total testosterone levels were not seen, even within the extreme exposure group. With this study, a total body of evidence has accumulated that allows to conclude that male reproductive effects are not relevant to humans, under any feasible and realistic conditions of exposure to inorganic boron compounds. KW - Boron exposure KW - Boric acid KW - Reproductive toxicity KW - FSH KW - LH KW - Testosterone KW - Semen parameters Y1 - 2018 U6 - https://doi.org/10.1007/s00204-018-2296-7 SN - 0340-5761 SN - 1432-0738 VL - 92 IS - 10 SP - 3051 EP - 3059 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Goychuk, Igor T1 - Viscoelastic subdiffusion in a random Gaussian environment JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Viscoelastic subdiffusion governed by a fractional Langevin equation is studied numerically in a random Gaussian environment modeled by stationary Gaussian potentials with decaying spatial correlations. This anomalous diffusion is archetypal for living cells, where cytoplasm is known to be viscoelastic and a spatial disorder also naturally emerges. We obtain some first important insights into it within a model one-dimensional study. Two basic types of potential correlations are studied: short-range exponentially decaying and algebraically slow decaying with an infinite correlation length, both for a moderate (several kBT, in the units of thermal energy), and strong (5–10kBT) disorder. For a moderate disorder, it is shown that on the ensemble level viscoelastic subdiffusion can easily overcome the medium's disorder. Asymptotically, it is not distinguishable from the disorder-free subdiffusion. However, a strong scatter in single-trajectory averages is nevertheless seen even for a moderate disorder. It features a weak ergodicity breaking, which occurs on a very long yet transient time scale. Furthermore, for a strong disorder, a very long transient regime of logarithmic, Sinai-type diffusion emerges. It can last longer and be faster in the absolute terms for weakly decaying correlations as compared with the short-range correlations. Residence time distributions in a finite spatial domain are of a generalized log-normal type and are reminiscent also of a stretched exponential distribution. They can be easily confused for power-law distributions in view of the observed weak ergodicity breaking. This suggests a revision of some experimental data and their interpretation. Y1 - 2018 U6 - https://doi.org/10.1039/c8cp05238g SN - 1463-9076 SN - 1463-9084 VL - 20 IS - 37 SP - 24140 EP - 24155 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Yalcinkaya, Hacer A1 - Bressel, Katharina A1 - Lindner, Peter A1 - Gradzielski, Michael T1 - Controlled formation of vesicles with added styrene and their fixation by polymerization JF - Journal of colloid and interface science N2 - Hypothesis: An effective way for fixating vesicle structures is the insertion of monomers and cross-linking agents into their bilayer, and their subsequent polymerization can lead to the formation of polymeric nanocapsules. Particularly attractive here are vesicle systems that form spontaneously well-defined small vesicles, as obtaining such small nanocapsules with sizes below 100 nm is still challenging. Experiments: A spontaneously forming well-defined vesicle system composed of the surfactants TDMAO (tetradecyldimethylamine oxide), Pluronic L35, and LiPFOS (lithium perfluorooctylsulfonate) mixture was used as template for fixation by polymerization. Therefore, styrene monomer was incorporated into the vesicle bilayer and ultimately these structures were fixated by UV induced radical polymerization. Structural alteration of the vesicles upon loading with monomer and the cross-linker as well as the effect of subsequent polymerization in the membrane were investigated in detail by turbidity measurements, dynamic and static light scattering, (DLS, SLS), and small angle neutron scattering (SANS). Findings: The analysis showed the changes on vesicle structures due to the monomer loading, and that these structures can become permanently fixed by the polymerization process. The potential of this approach to produce well-defined nanocapsules starting from a self-assembled system and following polymerization is critically evaluated. (C) 2018 Elsevier Inc. All rights reserved. KW - Template reaction KW - Zwitterionic surfactant KW - Anionic surfactant KW - Styrene KW - Vesicle KW - Small angle neutron scattering KW - Polymerization Y1 - 2018 U6 - https://doi.org/10.1016/j.jcis.2018.07.097 SN - 0021-9797 SN - 1095-7103 VL - 531 SP - 672 EP - 680 PB - Elsevier CY - San Diego ER - TY - JOUR A1 - Koetz, Joachim T1 - The Effect of Surface Modification of Gold Nanotriangles for Surface-Enhanced Raman Scattering Performance JF - Nanomaterials N2 - A surface modification of ultraflat gold nanotriangles (AuNTs) with different shaped nanoparticles is of special relevance for surface-enhanced Raman scattering (SERS) and the photo-catalytic activity of plasmonic substrates. Therefore, different approaches are used to verify the flat platelet morphology of the AuNTs by oriented overgrowth with metal nanoparticles. The most important part for the morphological transformation of the AuNTs is the coating layer, containing surfactants or polymers. By using well established AuNTs stabilized by a dioctyl sodium sulfosuccinate (AOT) bilayer, different strategies of surface modification with noble metal nanoparticles are possible. On the one hand undulated superstructures were synthesized by in situ growth of hemispherical gold nanoparticles in the polyethyleneimine (PEI)-coated AOT bilayer of the AuNTs. On the other hand spiked AuNTs were obtained by a direct reduction of Au³⁺ ions in the AOT double layer in presence of silver ions and ascorbic acid as reducing agent. Additionally, crumble topping of the smooth AuNTs can be realized after an exchange of the AOT bilayer by hyaluronic acid, followed by a silver-ion mediated reduction with ascorbic acid. Furthermore, a decoration with silver nanoparticles after coating the AOT bilayer with the cationic surfactant benzylhexadecyldimethylammonium chloride (BDAC) can be realized. In that case the ultraviolet (UV)-absorption of the undulated Au@Ag nanoplatelets can be tuned depending on the degree of decoration with silver nanoparticles. Comparing the Raman scattering data for the plasmon driven dimerization of 4-nitrothiophenol (4-NTP) to 4,4′-dimercaptoazobenzene (DMAB) one can conclude that the most important effect of surface modification with a 75 times higher enhancement factor in SERS experiments becomes available by decoration with gold spikes. KW - undulated KW - spiked and crumble gold nanotriangles KW - SERS enhancement factor KW - dimerization of 4-nitrothiophenol KW - AOT bilayer KW - PEI coating Y1 - 2020 U6 - https://doi.org/10.3390/nano10112187 SN - 2079-4991 VL - 10 IS - 11 PB - MDPI CY - Basel ER - TY - JOUR A1 - Schultze, Christiane A1 - Schmidt, Bernd T1 - Functionalized Benzofurans via Microwave-Promoted Tandem Claisen-Rearrangement/5-endo-dig Cyclization JF - Journal of heterocyclic chemistry N2 - Ortho-allyloxy alkinyl benzenes undergo, upon microwave irradiation in dimethylformamide, a tandem sequence of Claisen-rearrangement and 5-endo-dig cyclization to furnish 7-allyl-substituted benzofurans. With terminal alkynes, chroman-4-ones and enaminoketones become the main products. A mechanistic proposal for this observation relies on a reaction of the starting material with the solvent dimethylformamide under the microwave conditions. Y1 - 2019 U6 - https://doi.org/10.1002/jhet.3671 SN - 0022-152X SN - 1943-5193 VL - 56 IS - 9 SP - 2619 EP - 2629 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Benzyne - an acetylene- or cumulene-like electronic structure? JF - Tetrahedron N2 - The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of benzyne 1 and analogues (benzene 2, 1,2,3-cyclohexatriene 3, cyclohexen-3-yne 4, cyclohexen-4-yne 5, cyclohexyne 6) have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values could be employed to compare the diatropic ring current effects of benzene and benzyne, and, when compared with the spatial magnetic properties of the analogues, to answer the question whether the benzyne electronic structure is more acetylene- or cumulene-like, supported by structural data and delta(C-13)/ppm values. (C) 2019 Published by Elsevier Ltd. KW - Benzyne-allene or cumulene-like structure KW - Trough-space NMR shieldings (TSNMRS) KW - NICS KW - Iso-chemical shielding surfaces (ICSS) KW - Ring current effect Y1 - 2019 U6 - https://doi.org/10.1016/j.tet.2019.07.011 SN - 0040-4020 VL - 75 IS - 33 SP - 4663 EP - 4668 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Note, Carine A1 - Koetz, Joachim A1 - Kosmella, Sabine T1 - Structural changes in poly(ethyleneimine) modified microemulsion JF - Journal of colloid and interface science N2 - The influence of branched poly(ethyleneimine) on the phase behavior of the system sodium dodecylsulfate/toluene-pentanol (1:1)/water has been studied. The isotropic microemulsions still exist when water is replaced with aqueous solutions of PEI (up to 30% in weight), but their stability is significantly influenced. From a polymer concentration of 20 wt%, the polymer enhances the solubilization of water in oil, changes the sign of the spontaneous curvature of the surfactant film, and induces an inversion of the microemulsion type from water-in-oil (L-2) to oil-in-water (L-1), by the formation of a bicontinuous channel. Further investigations show that the addition of polymer in the L-2 phase changes the droplet-droplet interactions as the conductivity drops and the percolation disappears. In the bicontinuous channel, higher viscosities can be detected, as well as a weak percolation followed by a steep increase of the conductivity, which can be related to evident structural changes in the system. DSC measurements allow then to follow the changes of the water properties in the system, from interfacial-water in the L-2 phase to free-water in the sponge-like phase. Finally, all the measurements performed permit to characterize the structural transitions in the system and to understand the role of the added polymer. KW - polyelectrolyte KW - microemulsion KW - bicontinuous phase Y1 - 2006 U6 - https://doi.org/10.1016/j.jcis.2006.06.071 SN - 0021-9797 VL - 302 SP - 662 EP - 668 PB - Elsevier CY - Amsterdam ER - TY - THES A1 - Ziemann, Vanessa T1 - Toxische Effekte von Arsenolipiden in humanen Kulturzellen und Caenorhabditis elegans Y1 - 2020 ER - TY - JOUR A1 - Lange, Birger A1 - Wagner, Jürgen A1 - Zentel, Rudolf T1 - Fabrication of robust high-quality ORMOCER (R) inverse opals JF - Macromolecular rapid communications N2 - The nanostructuring of ORMOCER (R) to form inverse opals is described. For this purpose a polymer opal is used as a template and infiltrated with liquid ORMOCER (R). After photopolymerization of the resin the host opal is dissolved in tetrahydrofuran and an ORMOCER (R) inverse opal is obtained. It shows excellent periodicity (by SEM) and optical properties to reveal a high degree of face centered cubic order. This replication process leads to a nanostructured photonic crystal with the outstanding mechanical properties of ORMOCER (R) and high temperature stability up to 350 degrees C. KW - colloids KW - inverse opals KW - ORMOCER (R) KW - photonic crystal KW - self-assembly Y1 - 2006 U6 - https://doi.org/10.1002/marc.200600429 SN - 1022-1336 VL - 27 SP - 1746 EP - 1751 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kapp, A. A1 - Beissenhirtz, Moritz Karl A1 - Geyer, F. A1 - Scheller, F. A1 - Viezzoli, Maria Silvia A1 - Lisdat, Fred T1 - Electrochemical and sensorial behavior of SOD mutants immobilized on gold electrodes in aqueous/organic solvent mixtures JF - Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis N2 - A cysteine mutant of a monomeric human Cu, Zn-SOD (Glycine 61, Serine 142) has been immobilized directly on gold electrodes using the thiol groups introduced. The electrochemical behavior of the surface confined protein was studied in mixtures of aqueous buffer and DMSO up to an organic solvent content of 60%. The formal potential was found to be rather independent of the DMSO content. However, half peak width increased and the redoxactive amount clearly decreased with raising DMSO content. In addition, the kinetics of the heterogeneous electron transfer became slower; but still a quasireversible electrochemical conversion of the mutant SOD was feasible. Thus, the electrodes were applied for sensorial superoxide detection. At a potential of +220 mV vs. Ag/AgCl advantage was taken of the partial oxidation reaction of the enzyme. A defined superoxide signal was obtained in solutions up to 40% DMSO. The sensitivity of the mutant electrodes decreased linearly with the organic solvent content in solution but was still higher compared to conventional cyt.c based sensors. At DMSO concentrations higher than 40% no sensor response was detected. KW - SOD KW - mutants KW - gold electrodes KW - DMSO KW - electrochemistry Y1 - 2006 U6 - https://doi.org/10.1002/elan.200603620 SN - 1040-0397 VL - 18 SP - 1909 EP - 1915 PB - Wiley CY - Weinheim ER - TY - JOUR A1 - He, Hai A1 - Noor, Elad A1 - Ramos-Parra, Perla A. A1 - García-Valencia, Liliana E. A1 - Patterson, Jenelle A. A1 - Díaz de la Garza, Rocío I. A1 - Hanson, Andrew D. A1 - Bar-Even, Arren T1 - In Vivo Rate of Formaldehyde Condensation with Tetrahydrofolate JF - Metabolites N2 - Formaldehyde is a highly reactive compound that participates in multiple spontaneous reactions, but these are mostly deleterious and damage cellular components. In contrast, the spontaneous condensation of formaldehyde with tetrahydrofolate (THF) has been proposed to contribute to the assimilation of this intermediate during growth on C1 carbon sources such as methanol. However, the in vivo rate of this condensation reaction is unknown and its possible contribution to growth remains elusive. Here, we used microbial platforms to assess the rate of this condensation in the cellular environment. We constructed Escherichia coli strains lacking the enzymes that naturally produce 5,10-methylene-THF. These strains were able to grow on minimal medium only when equipped with a sarcosine (N-methyl-glycine) oxidation pathway that sustained a high cellular concentration of formaldehyde, which spontaneously reacts with THF to produce 5,10-methylene-THF. We used flux balance analysis to derive the rate of the spontaneous condensation from the observed growth rate. According to this, we calculated that a microorganism obtaining its entire biomass via the spontaneous condensation of formaldehyde with THF would have a doubling time of more than three weeks. Hence, this spontaneous reaction is unlikely to serve as an effective route for formaldehyde assimilation. KW - one-carbon metabolism KW - spontaneous reaction KW - auxotrophy KW - serine cycle KW - phenotypic phase plane Y1 - 2019 U6 - https://doi.org/10.3390/metabo10020065 SN - 2218-1989 VL - 10 IS - 65 PB - MDPI CY - Basel ER - TY - JOUR A1 - Lai, Feili A1 - Feng, Jianrui A1 - Heil, Tobias A1 - Tian, Zhihong A1 - Schmidt, Johannes A1 - Wang, Gui-Chang A1 - Oschatz, Martin T1 - Partially delocalized charge in Fe-doped NiCo2S4 nanosheet-mesoporous carbon-composites for high-voltage supercapacitors JF - Journal of materials chemistry : A, Materials for energy and sustainability N2 - Unraveling the effect of transition-metal doping on the energy storage properties of bimetallic sulfides remains a grand challenge. Herein, we construct bimetallic sulfide nanosheets and hence deliberately introduce transition-metal doping domains on their surface. The resulting materials show not only an enhanced density of states near the Fermi level but also partially delocalized charge as shown by density functional theory (DFT) calculations. Fe-doped NiCo2S4 nanosheets wrapped on N,S-doped ordered mesoporous carbon (Fe-NiCo2S4@N,S-CMK-3) are prepared, which show an enhanced specific capacitance of 197.8 F g(-1) in ionic liquid-based supercapacitors at a scan rate of 2 mV s(-1). This is significantly higher as compared to the capacitance of 155.2 and 135.9 F g(-1) of non-iron-doped NiCo2S4@N,S-CMK and Fe-NiCo2S4@CMK-3 electrodes, respectively. This result arises from the enhanced ionic liquid polarization effect and transportation ability from the Fe-NiCo2S4 surface and N,S-CMK-3 structure. Furthermore, the importance of matching multi-dimensional structures and ionic liquid ion sizes in the fabrication of asymmetric supercapacitors (ASCs) is demonstrated. As a result, the ASC device exhibits a high energy density of 107.5 W h kg(-1) at a power density of 100 W kg(-1) in a working-voltage window of 4 V when using Fe-NiCo2S4@N,S-CMK-3 and N,S-CMK-3 as positive and negative electrodes, respectively. This work puts forward a new direction to design supercapacitor composite electrodes for efficient ionic liquid coupling. Y1 - 2019 U6 - https://doi.org/10.1039/c9ta06250e SN - 2050-7488 SN - 2050-7496 VL - 7 IS - 33 SP - 19342 EP - 19347 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Shou, Keyun A1 - Bremer, Anne A1 - Rindfleisch, Tobias A1 - Knox-Brown, Patrick A1 - Hirai, Mitsuhiro A1 - Rekas, Agata A1 - Garvey, Christopher J. A1 - Hincha, Dirk K. A1 - Stadler, Andreas M. A1 - Thalhammer, Anja T1 - Conformational selection of the intrinsically disordered plant stress protein COR15A in response to solution osmolarity - an X-ray and light scattering study JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The plant stress protein COR15A stabilizes chloroplast membranes during freezing. COR15A is an intrinsically disordered protein (IDP) in aqueous solution, but acquires an alpha-helical structure during dehydration or the increase of solution osmolarity. We have used small- and wide-angle X-ray scattering (SAXS/WAXS) combined with static and dynamic light scattering (SLS/DLS) to investigate the structural and hydrodynamic properties of COR15A in response to increasing solution osmolarity. Coarse-grained ensemble modelling allowed a structure-based interpretation of the SAXS data. Our results demonstrate that COR15A behaves as a biomacromolecule with polymer-like properties which strongly depend on solution osmolarity. Biomacromolecular self-assembly occurring at high solvent osmolarity is initiated by the occurrence of two specific structural subpopulations of the COR15A monomer. The osmolarity dependent structural selection mechanism is an elegant way for conformational regulation and assembly of COR15A. It highlights the importance of the polymer-like properties of IDPs for their associated biological function. Y1 - 2019 U6 - https://doi.org/10.1039/c9cp01768b SN - 1463-9076 SN - 1463-9084 VL - 21 IS - 34 SP - 18727 EP - 18740 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Jacques, Mauricio Tavares A1 - Bornhorst, Julia A1 - Soares, Marcell Valandro A1 - Schwerdtle, Tanja A1 - Garcia, Solange A1 - Avila, Daiana Silva T1 - Reprotoxicity of glyphosate-based formulation in Caenorhabditis elegans is not due to the active ingredient only JF - Environmental pollution N2 - Pesticides guarantee us high productivity in agriculture, but the long-term costs have proved too high. Acute and chronic intoxication of humans and animals, contamination of soil, water and food are the consequences of the current demand and sales of these products. In addition, pesticides such as glyphosate are sold in commercial formulations which have inert ingredients, substances with unknown composition and proportion. Facing this scenario, toxicological studies that investigate the interaction between the active principle and the inert ingredients are necessary. The following work proposed comparative toxicology studies between glyphosate and its commercial formulation using the alternative model Caenorhabditis elegans. Worms were exposed to different concentrations of the active ingredient (glyphosate in monoisopropylamine salt) and its commercial formulation. Reproductive capacity was evaluated through brood size, morphological analysis of oocytes and through the MD701 strain (bcIs39), which allows the visualization of germ cells in apoptosis. In addition, the metal composition in the commercial formulation was analyzed by ICP-MS. Only the commercial formulation of glyphosate showed significant negative effects on brood size, body length, oocyte size, and the number of apoptotic cells. Metal analysis showed the presence of Hg, Fe, Mn, Cu, Zn, As, Cd and Pb in the commercial formulation, which did not cause reprotoxicity at the concentrations found. However, metals can bio-accumulate in soil and water and cause environmental impacts. Finally, we demonstrated that the addition of inert ingredients increased the toxic profile of the active ingredient glyphosate in C. elegans, which reinforces the need of components description in the product labels. (C) 2019 Elsevier Ltd. All rights reserved. KW - Glyphosate KW - Inert ingredients KW - Reproduction KW - Oocytes KW - Development KW - Metals Y1 - 2019 U6 - https://doi.org/10.1016/j.envpol.2019.06.099 SN - 0269-7491 SN - 1873-6424 VL - 252 SP - 1854 EP - 1862 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Garnier, Sebastien A1 - Laschewsky, Andre T1 - Non-ionic amphiphilic block copolymers by RAFT-polymerization and their self-organization JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - Water-soluble, amphiphilic diblock copolymers were synthesized by reversible addition fragmentation chain transfer polymerization. They consist of poly(butyl acrylate) as hydrophobic block with a low glass transition temperature and three different nonionic water-soluble blocks, namely, the classical hydrophilic block poly(dimethylacrylamide), the strongly hydrophilic poly(acryloyloxyethyl methylsulfoxide), and the thermally sensitive poly(N-acryloylpyrrolidine). Aqueous micellar solutions of the block copolymers were prepared and characterized by static and dynamic light scattering analysis (DLS and SLS). No critical micelle concentration could be detected. The micellization was thermodynamically favored, although kinetically slow, exhibiting a marked dependence on the preparation conditions. The polymers formed micelles with a hydrodynamic diameter from 20 to 100 nm, which were stable upon dilution. The micellar size was correlated with the composition of the block copolymers and their overall molar mass. The micelles formed with the two most hydrophilic blocks were particularly stable upon temperature cycles, whereas the thermally sensitive poly(N-acryloylpyrrolidine) block showed a temperature-induced precipitation. According to combined SLS and DLS analysis, the micelles exhibited an elongated shape such as rods or worms. It should be noted that the block copolymers with the most hydrophilic poly(sulfoxide) block formed inverse micelles in certain organic solvents. KW - macrosurfactants KW - block copolymers KW - micelles KW - inverse micelles KW - sulfoxide Y1 - 2006 U6 - https://doi.org/10.1007/s00396-006-1484-9 SN - 0303-402X VL - 284 SP - 1243 EP - 1254 PB - Springer CY - Berlin ER - TY - JOUR A1 - Schmidt, Bernd A1 - Nave, Stefan T1 - Stereoselective syntheses of enantiomerically pure 2,5-disubstituted dihydropyrans based on olefin metathesis JF - The journal of organic chemistry N2 - A short synthesis of 2,5-disubstituted dihydropyrans starting from D-mannitol as a chiral building block is described. Our synthetic approach combines ruthenium-catalyzed ring closing olefin metathesis and palladium-catalyzed nucleophilic substitution. Y1 - 2006 U6 - https://doi.org/10.1021/jo061190k SN - 0022-3263 VL - 71 IS - 19 SP - 7364 EP - 7369 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Lutz, Jean-Francois A1 - Kristen, Juliane A1 - Skrabania, Katja A1 - Laschewsky, Andre T1 - POLY 14-Synthetic strategies for preparing multicompartment micelles T2 - Abstracts of papers / American Chemical Society N2 - The fabrication of compartmented micellar systems is an exciting new area of research in the field of polymer self-assembly. Multicompartment micelles composed of a water-soluble shell and a segregated hydrophobic core can be obtained via direct aqueous self-assembly of preformed polymeric amphiphiles possessing one hydrophilic segment and two incompatible hydrophobic segments (e.g. hydrocarbon and fluorocarbon blocks). Such macromolecular building-blocks were prepared in the present work principally via reversible addition-fragmentation transfer polymerization (RAFT). Polysoaps or triblock macrosurfactants can be synthesized in high yields by RAFT under relatively straightforward experimental conditions. Y1 - 2006 SN - 0-8412-7426-6 SN - 0065-7727 VL - 232 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lendlein, Andreas A1 - Balk, Maria A1 - Tarazona, Natalia A. A1 - Gould, Oliver E. C. T1 - Bioperspectives for Shape-Memory Polymers as Shape Programmable, Active Materials JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - Within the natural world, organisms use information stored in their material structure to generate a physical response to a wide variety of environmental changes. The ability to program synthetic materials to intrinsically respond to environmental changes in a similar manner has the potential to revolutionize material science. By designing polymeric devices capable of responsively changing shape or behavior based on information encoded into their structure, we can create functional physical behavior, including a shape memory and an actuation capability. Here we highlight the stimuli-responsiveness and shape-changing ability of biological materials and biopolymer-based materials, plus their potential biomedical application, providing a bioperspective on shape-memory materials. We address strategies to incorporate a shape memory (actuation) function in polymeric materials, conceptualized in terms of its relationship with inputs (environmental stimuli) and outputs (shape change). Challenges and opportunities associated with the integration of several functions in a single material body to achieve multifunctionality are discussed. Finally, we describe how elements that sense, convert, and transmit stimuli have been used to create multisensitive materials. Y1 - 2019 U6 - https://doi.org/10.1021/acs.biomac.9b01074 SN - 1525-7797 SN - 1526-4602 VL - 20 IS - 10 SP - 3627 EP - 3640 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Jia, He A1 - Quan, Ting A1 - Liu, Xuelian A1 - Bai, Lu A1 - Wang, Jiande A1 - Boujioui, Fadoi A1 - Ye, Ran A1 - Vald, Alexandru A1 - Lu, Yan A1 - Gohy, Jean-Francois T1 - Core-shell nanostructured organic redox polymer cathodes with superior performance JF - Nano Energy N2 - Core-shell nanoparticles stabilized by a cationic surfactant are prepared from the poly(2,2,6,6-tetra-methylpiperidinyloxy-4-yl methacrylate) redox polymer. The nanoparticles are further self-assembled with negatively charged reduced graphene oxide nanosheets and negatively charged mull-walled carbon nanotubes. This results in the formation of a free-standing cathode with a layered nanostructure and a high content of redox polymer that exhibits 100% utilization of the active substance with a measured capacity as high as 105 mAh/g based on the whole weight of the electrode. KW - Nanostructured KW - Redox polymer KW - Organic electrode KW - Lithium ion battery KW - Energy storage Y1 - 2019 U6 - https://doi.org/10.1016/j.nanoen.2019.103949 SN - 2211-2855 SN - 2211-3282 VL - 64 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Kuroki, Agnes A1 - Tchoupa, Arnaud Kengmo A1 - Hartlieb, Matthias A1 - Peltier, Raoul A1 - Locock, Katherine E. S. A1 - Unnikrishnan, Meera A1 - Perrier, Sebastien T1 - Targeting intracellular, multi-drug resistant Staphylococcus aureus with guanidinium polymers by elucidating the structure-activity relationship JF - Biomaterials : biomaterials reviews online N2 - Intracellular persistence of bacteria represents a clinical challenge as bacteria can thrive in an environment protected from antibiotics and immune responses. Novel targeting strategies are critical in tackling antibiotic resistant infections. Synthetic antimicrobial peptides (SAMPs) are interesting candidates as they exhibit a very high antimicrobial activity. We first compared the activity of a library of ammonium and guanidinium polymers with different sequences (statistical, tetrablock and diblock) synthesized by RAFT polymerization against methicillin-resistant S. aureus (MRSA) and methicillin-sensitive strains (MSSA). As the guanidinium SAMPs were the most potent, they were used to treat intracellular S. aureus in keratinocytes. The diblock structure was the most active, reducing the amount of intracellular MSSA and MRSA by two-fold. We present here a potential treatment for intracellular, multi-drug resistant bacteria, using a simple and scalable strategy. KW - Antimicrobial KW - Intracellular bacteria KW - Block copolymers KW - RAFT polymerization Y1 - 2019 U6 - https://doi.org/10.1016/j.biomaterials.2019.119249 SN - 0142-9612 SN - 1878-5905 VL - 217 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Krüger, Tobias A1 - Linker, Torsten T1 - Synthesis of gamma-spirolactams by Birch reduction of arenes JF - European journal of organic chemistry N2 - A convenient method for the synthesis of gamma-spirolactams in only three steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of chloroacetonitrile affords nitriles in moderate to good yields. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and anthroic acid. Subsequent catalytic hydrogenation proceeds smoothly with PtO2 or Raney Ni as catalysts and lactams are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation at different pressures, affording products with 0, 1, or 2 double bonds. Overall, more than 15 new gamma-spirolactams have been synthesized in analytically pure form. KW - Arenes KW - Birch reduction KW - Hydrogenation KW - Lactams KW - Synthetic methods Y1 - 2021 U6 - https://doi.org/10.1002/ejoc.202100056 SN - 1099-0690 VL - 2021 IS - 10 SP - 1585 EP - 1591 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Fudickar, Werner A1 - Metz, Melanie A1 - Mai-Linde, Yasemin A1 - Krüger, Tobias A1 - Kelling, Alexandra A1 - Sperlich, Eric A1 - Linker, Torsten T1 - Influence of functional groups on the ene reaction of singlet oxygen with 1,4-cyclohexadienes JF - Photochemistry and photobiology : the official journal of the American Society for Photobiology N2 - The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions. Y1 - 2021 U6 - https://doi.org/10.1111/php.13422 SN - 0031-8655 SN - 1751-1097 VL - 97 IS - 6 SP - 1289 EP - 1297 PB - Wiley CY - Malden, Mass. ER - TY - JOUR A1 - Raju, Rajarshi Roy A1 - Liebig, Ferenc A1 - Klemke, Bastian A1 - Koetz, Joachim T1 - Ultralight magnetic aerogels from Janus emulsions JF - RSC Advances N2 - Magnetite containing aerogels were synthesized by freeze-drying olive oil/silicone oil-based Janus emulsion gels containing gelatin and sodium carboxymethylcellulose (NaCMC). The magnetite nanoparticles dispersed in olive oil are processed into the gel and remain in the macroporous aerogel after removing the oil components. The coexistence of macropores from the Janus droplets and mesopores from freeze-drying of the hydrogels in combination with the magnetic properties offer a special hierarchical pore structure, which is of relevance for smart supercapacitors, biosensors, and spilled oil sorption and separation. The morphology of the final structure was investigated in dependence on initial compositions. More hydrophobic aerogels with magnetic responsiveness were synthesized by bisacrylamide-crosslinking of the hydrogel. The crosslinked aerogels can be successfully used in magnetically responsive clean up experiments of the cationic dye methylene blue. Y1 - 2019 U6 - https://doi.org/10.1039/c9ra10247g SN - 2046-2069 VL - 10 IS - 13 SP - 7492 EP - 7499 PB - RSC Publishing CY - London ER - TY - JOUR A1 - Raju, Rajarshi Roy A1 - Liebig, Ferenc A1 - Klemke, Bastian A1 - Koetz, Joachim T1 - pH-responsive magnetic Pickering Janus emulsions JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - We report ultrasonically generated pH-responsive Pickering Janus emulsions of olive oil and silicone oil with controllable droplet size and engulfment. Chitosan was used as a pH-responsive emulsifier. The increase of pH from 2 to 6 leads to a transition from completely engulfed double emulsion droplets to dumbbell-shaped Janus droplets accompanied by a significant decrease of droplet diameter and a more homogeneous size distribution. The results can be elucidated by the conformational change of chitosan from a more extended form at pH 2 to a more flexible form at pH 4-5. Magnetic responsiveness to the emulsion was attributed by dispersing superparamagnetic nanoparticles (Fe3O4 with diameter of 13 +/- 2 nm) in the olive oil phase before preparing the Janus emulsion. Incorporation of magnetic nanoparticles leads to superior emulsion stability, drastically reduced droplet diameters, and opened the way to control movement and orientation of the Janus droplets according to an external magnetic field. KW - Janus emulsion KW - Chitosan KW - pH-responsive KW - Magnetic-responsive KW - Cryo-SEM KW - TEM Y1 - 2018 U6 - https://doi.org/10.1007/s00396-018-4321-z SN - 0303-402X SN - 1435-1536 VL - 296 IS - 6 SP - 1039 EP - 1046 PB - Springer CY - New York ER - TY - JOUR A1 - Huwer, Johannes A1 - Banerji, Amitabh T1 - Corona sei Dank?! BT - Digitalisierung im Chemieunterricht JF - Chemie konkret : CHEMKON ; Forum für Unterricht und Didaktik Y1 - 2020 U6 - https://doi.org/10.1002/ckon.202000037 SN - 0944-5846 SN - 1521-3730 VL - 27 IS - 3 SP - 105 EP - 106 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Hermanns, Jolanda A1 - Keller, David T1 - The development, use, and evaluation of digital games and quizzes in an introductory course on organic chemistry for preservice chemistry teachers JF - Journal of chemical education / Division of Chemical Education, Inc., American Chemical Society N2 - Due to the COVID pandemic, the introductory course on organic chemistry was developed and conducted as anonline course. To ensure methodical variety in this course,educational games and quizzes have been developed, used, and evaluated. The attendance of the course, and therefore also the use of the quizzes and games, was voluntary. The quizzes'main goalwas to give the students the opportunity to check whether they had memorized the knowledge needed in the course. Another goal was to make transparent which knowledge the students shouldmemorize by rote. The evaluation shows that the students hadnot internalized all knowledge which they should apply in severaltasks on organic chemistry. They answered multiselect questions in general less well than single-select questions. The games shouldcombine fun with learning. The evaluation of the games shows that the students rated them very well. The students used thosegames again for their exam preparation, as the monitoring of accessing the games showed. Students'experiences with usingelectronic devices in general or for quizzes and games have also been evaluated, because their experience could influence thestudents'assessment of the quizzes and games used in our study. However, the students used electronic devices regularly and shouldtherefore be technically competent to use our quizzes and games. The evaluation showed that the use of digital games for learningpurposes is not very common, neither at school nor at university, although the students had worked with such tools before. Thestudents are also very interested in using and developing such digital games not only for their own study, but also for their future work at school KW - Organic Chemistry KW - Second-Year Undergraduate KW - Humor KW - Puzzles KW - Games; KW - Internet KW - Web-Based Learning KW - Distance Learning KW - Self Instruction Y1 - 2022 U6 - https://doi.org/10.1021/acs.jchemed.2c00058 SN - 0021-9584 SN - 1938-1328 VL - 99 IS - 4 SP - 1715 EP - 1724 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Raju, Rajarshi Roy A1 - Koetz, Joachim T1 - Pickering Janus emulsions stabilized with gold nanoparticles JF - Langmuir : the ACS journal of surfaces and colloids / American Chemical Society N2 - We report a modified approach to the batch scale preparation of completely engulfed core-shell emulsions or partially engulfed Janus emulsions with colorful optical properties, containing water, olive oil, and silicone oil. The in situ reduction of gold chloride, forming gold nanoparticles (AuNPs) at the olive oil interface in the absence or presence of chitosan, leads to the formation of compartmentalized olive-silicone oil emulsion droplets in water. In the absence of additional reducing components, time-dependent morphological transformations from partial engulfment to complete engulfment were observed. Similar experiments in the presence of chitosan or presynthesized AuNPs show an opposite time-dependent trend of transformation of core-shell structures into partially engulfed ones. This behavior can be understood by a time-dependent rearrangement of the AuNPs at the interface and changes of the interfacial tension. The Pickering effect of AuNPs at oil-water and oil-oil interfaces brings not only color effects to individual microdroplets, which are of special relevance for the preparation of new optical elements, but also a surprising self-assembly of droplets. Y1 - 2022 U6 - https://doi.org/10.1021/acs.langmuir.1c02256 SN - 0743-7463 SN - 1520-5827 VL - 38 IS - 1 SP - 147 EP - 155 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schwarze, Thomas T1 - Determination of Pd2+ by fluorescence enhancement caused by an off-switching of an energy- and an electron transfer JF - ChemistrySelect N2 - In this paper, we introduce a fluorescent dye 1, which is able to detect selectively Pd2+ by a clear fluorescence enhancement (FE) in THF. In the presence of eight Pd2+ equivalents, we observed a fluorescence enhancement factor (FEF) of 28.3. The high Pd2+ induced FEF can be explained by an off switching of multiple quenching processes within 1 by Pd2+. In the free dye 1 a photoinduced electron transfer (PET) and energy transfer (ET) takes place and quenches the anthracenic fluorescence. The coordination of eight Pd2+ units by the alkylthio-substituted porphyrazine receptor suppresses the PET and ET quenching process and the anthracenic fluorescence is switched on. KW - Palladium ion KW - electron transfer KW - energy transfer KW - fluorescence KW - porphyrazine Y1 - 2021 U6 - https://doi.org/10.1002/slct.202003975 SN - 2365-6549 VL - 6 IS - 3 SP - 318 EP - 322 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Hwang, Jongkook A1 - Walczak, Ralf A1 - Oschatz, Martin A1 - Tarakina, Nadezda A1 - Schmidt, Bernhard V. K. J. T1 - Micro-Blooming: Hierarchically Porous Nitrogen-Doped Carbon Flowers Derived from Metal-Organic Mesocrystals JF - Small N2 - Synthesis of 3D flower-like zinc-nitrilotriacetic acid (ZnNTA) mesocrystals and their conformal transformation to hierarchically porous N-doped carbon superstructures is reported. During the solvothermal reaction, 2D nanosheet primary building blocks undergo oriented attachment and mesoscale assembly forming stacked layers. The secondary nucleation and growth preferentially occurs at the edges and defects of the layers, leading to formation of 3D flower-like mesocrystals comprised of interconnected 2D micropetals. By simply varying the pyrolysis temperature (550-1000 degrees C) and the removal method of in the situ-generated Zn species, nonporous parent mesocrystals are transformed to hierarchically porous carbon flowers with controllable surface area (970-1605 m(2) g(-1)), nitrogen content (3.4-14.1 at%), pore volume (0.95-2.19 cm(3) g(-1)), as well as pore diameter and structures. The carbon flowers prepared at 550 degrees C show high CO2/N-2 selectivity due to the high nitrogen content and the large fraction of (ultra)micropores, which can greatly increase the CO2 affinity. The results show that the physicochemical properties of carbons are highly dependent on the thermal transformation and associated pore formation process, rather than directly inherited from parent precursors. The present strategy demonstrates metal-organic mesocrystals as a facile and versatile means toward 3D hierarchical carbon superstructures that are attractive for a number of potential applications. KW - 3D flower superstructures KW - hierarchically porous carbon KW - metal-organic mesocrystals KW - thermal transformation mechanism Y1 - 2019 U6 - https://doi.org/10.1002/smll.201901986 SN - 1613-6810 SN - 1613-6829 VL - 15 IS - 37 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Prestel, Andreas A1 - Möller, Heiko Michael T1 - Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides N2 - The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 218 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89658 SP - 701 EP - 704 ER - TY - JOUR A1 - Abbas, Ioana M. A1 - Vranic, Marija A1 - Hoffmann, Holger A1 - El-Khatib, Ahmed H. A1 - Montes-Bayón, María A1 - Möller, Heiko Michael A1 - Weller, Michael G. T1 - Investigations of the Copper Peptide Hepcidin-25 by LC-MS/MS and NMR⁺ JF - International Journal of Molecular Sciences N2 - Hepcidin-25 was identified as themain iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II) binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandemmass spectrometry (MS/MS), high-resolutionmass spectrometry (HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or referencematerial comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others. KW - hepcidin-25 KW - copper KW - nickel KW - copper complex KW - ATCUN motif KW - metal complex KW - MS KW - NMR structure KW - metal peptide KW - metalloprotein KW - metallopeptide KW - isomerization KW - racemization KW - purity KW - reference material Y1 - 2018 U6 - https://doi.org/10.3390/ijms19082271 SN - 1422-0067 SN - 1661-6596 VL - 19 IS - 8 PB - Molecular Diversity Preservation International CY - Basel ER - TY - JOUR A1 - Prestel, Andreas A1 - Möller, Heiko Michael T1 - Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides JF - Chemical communications : ChemComm N2 - The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control. Y1 - 2015 U6 - https://doi.org/10.1039/C5CC06848G SN - 1364-548X IS - 52 SP - 701 EP - 704 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Abbas, Ioana M. A1 - Vranic, Marija A1 - Hoffmann, Holger A1 - El-Khatib, Ahmed H. A1 - Montes-Bayón, María A1 - Möller, Heiko Michael A1 - Weller, Michael G. T1 - Investigations of the Copper Peptide Hepcidin-25 by LC-MS/MS and NMR⁺ T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - Hepcidin-25 was identified as themain iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II) binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandemmass spectrometry (MS/MS), high-resolutionmass spectrometry (HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or referencematerial comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 701 KW - hepcidin-25 KW - copper KW - nickel KW - copper complex KW - ATCUN motif KW - metal complex KW - MS KW - NMR structure KW - metal peptide KW - metalloprotein KW - metallopeptide KW - isomerization KW - racemization KW - purity KW - reference material Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-427926 SN - 1866-8372 IS - 701 ER - TY - JOUR A1 - Krstic, Jelena A1 - Reinisch, Isabel A1 - Schupp, Michael A1 - Schulz, Tim Julius A1 - Prokesch, Andreas T1 - p53 functions in adipose tissue metabolism and homeostasis JF - International journal of molecular sciences N2 - As a tumor suppressor and the most frequently mutated gene in cancer, p53 is among the best-described molecules in medical research. As cancer is in most cases an age-related disease, it seems paradoxical that p53 is so strongly conserved from early multicellular organisms to humans. A function not directly related to tumor suppression, such as the regulation of metabolism in nontransformed cells, could explain this selective pressure. While this role of p53 in cellular metabolism is gradually emerging, it is imperative to dissect the tissue-and cell-specific actions of p53 and its downstream signaling pathways. In this review, we focus on studies reporting p53's impact on adipocyte development, function, and maintenance, as well as the causes and consequences of altered p53 levels in white and brown adipose tissue (AT) with respect to systemic energy homeostasis. While whole body p53 knockout mice gain less weight and fat mass under a high-fat diet owing to increased energy expenditure, modifying p53 expression specifically in adipocytes yields more refined insights: (1) p53 is a negative regulator of in vitro adipogenesis; (2) p53 levels in white AT are increased in diet-induced and genetic obesity mouse models and in obese humans; (3) functionally, elevated p53 in white AT increases senescence and chronic inflammation, aggravating systemic insulin resistance; (4) p53 is not required for normal development of brown AT; and (5) when p53 is activated in brown AT in mice fed a high-fat diet, it increases brown AT temperature and brown AT marker gene expression, thereby contributing to reduced fat mass accumulation. In addition, p53 is increasingly being recognized as crucial player in nutrient sensing pathways. Hence, despite existence of contradictory findings and a varying density of evidence, several functions of p53 in adipocytes and ATs have been emerging, positioning p53 as an essential regulatory hub in ATs. Future studies need to make use of more sophisticated in vivo model systems and should identify an AT-specific set of p53 target genes and downstream pathways upon different (nutrient) challenges to identify novel therapeutic targets to curb metabolic diseases KW - p53 KW - adipose tissue KW - metabolic syndrome KW - obesity KW - adipogenesis KW - insulin resistance Y1 - 2018 U6 - https://doi.org/10.3390/ijms19092622 SN - 1422-0067 VL - 19 IS - 9 PB - MDPI CY - Basel ER - TY - JOUR A1 - Schulze, Sven A1 - Wehrhold, Michel A1 - Hille, Carsten T1 - Femtosecond-Pulsed laser written and etched fiber bragg gratings for fiber-optical biosensing JF - Sensors N2 - We present the development of a label-free, highly sensitive fiber-optical biosensor for online detection and quantification of biomolecules. Here, the advantages of etched fiber Bragg gratings (eFBG) were used, since they induce a narrowband Bragg wavelength peak in the reflection operation mode. The gratings were fabricated point-by-point via a nonlinear absorption process of a highly focused femtosecond-pulsed laser, without the need of prior coating removal or specific fiber doping. The sensitivity of the Bragg wavelength peak to the surrounding refractive index (SRI), as needed for biochemical sensing, was realized by fiber cladding removal using hydrofluoric acid etching. For evaluation of biosensing capabilities, eFBG fibers were biofunctionalized with a single-stranded DNA aptamer specific for binding the C-reactive protein (CRP). Thus, the CRP-sensitive eFBG fiber-optical biosensor showed a very low limit of detection of 0.82 pg/L, with a dynamic range of CRP detection from approximately 0.8 pg/L to 1.2 mu g/L. The biosensor showed a high specificity to CRP even in the presence of interfering substances. These results suggest that the proposed biosensor is capable for quantification of CRP from trace amounts of clinical samples. In addition, the adaption of this eFBG fiber-optical biosensor for detection of other relevant analytes can be easily realized. KW - fiber Bragg gratings KW - ultra-fast laser inscription KW - fiber etching KW - nanostructure fabrication KW - fiber-optical sensors KW - aptamers KW - C-reactive protein KW - biomarker Y1 - 2018 U6 - https://doi.org/10.3390/s18092844 SN - 1424-8220 VL - 18 IS - 9 PB - MDPI CY - Basel ER - TY - JOUR A1 - Paz, Cristian A1 - Heydenreich, Matthias A1 - Schmidt, Bernd A1 - Vadra, Nahir A1 - Baggio, Ricardo T1 - Three new dihydro-beta-agarofuran sesquiterpenes from the seeds of Maytenus boaria JF - Acta Crystallographica Section C N2 - As part of a project studying the secondary metabolites extracted from the Chilean flora, we report herein three new beta-agarofuran sesquiterpenes, namely (1S,4S,5S,6R,7R,8R,9R,10S)-6-acetoxy-4,9-dihydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b] oxepine-5,10-diylbis(furan-3-carboxylate), C27H32O11, (II), (1S,4S,5S,6R,7R,9S,10S)-6-acetoxy-9-hydroxy-2,2,5a, 9-tetramethyloctahydro-2H-3,9a-methanobenzo[ b] oxepine-5,10-diyl bis(furan-3-carboxylate), C27H32O10, (III), and (1S,4S,5S,6R,7R,9S,10S)-6-acetoxy-10-(benzoyloxy)-9-hydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b]oxepin-5-yl furan-3-carboxylate, C29H34O9, (IV), obtained from the seeds of Maytenus boaria and closely associated with a recently published relative [Paz et al. (2017). Acta Cryst. C73, 451-457]. In the (isomorphic) structures of (II) and (III), the central decalin system is esterified with an acetate group at site 1 and furoate groups at sites 6 and 9, and differ at site 8, with an OH group in (II) and no substituent in (III). This position is also unsubstituted in (IV), with site 6 being occupied by a benzoate group. The chirality of the skeletons is described as 1S, 4S, 5S, 6R, 7R, 8R, 9R, 10S in (II) and 1S, 4S, 5S, 6R, 7R, 9S, 10S in (III) and (IV), matching the chirality suggested by NMR studies. This difference in the chirality sequence among the title structures (in spite of the fact that the three skeletons are absolutely isostructural) is due to the differences in the environment of site 8, i.e. OH in (II) and H in (III) and (IV). This diversity in substitution, in turn, is responsible for the differences in the hydrogen-bonding schemes, which is discussed. KW - Celastraceae KW - Maytenus boaria KW - sesquiterpene KW - dihydro-beta-agarofuran KW - crystal structure KW - NMR KW - DSC Y1 - 2018 U6 - https://doi.org/10.1107/S2053229618005429 SN - 2053-2296 VL - 74 SP - 564 EP - 570 PB - International Union of Crystallography CY - Chester ER - TY - JOUR A1 - Tian, Guang-Zong A1 - Hu, Jing A1 - Zhang, Heng-Xi A1 - Rademacher, Christoph A1 - Zou, Xiao-Peng A1 - Zheng, Hong-Ning A1 - Xu, Fei A1 - Wang, Xiao-Li A1 - Linker, Torsten A1 - Yin, Jian T1 - Synthesis and conformational analysis of linear homo- and heterooligomers from novel 2-C-branched sugar amino acids (SAAs) JF - Scientific reports N2 - Sugar amino acids (SAAs), as biologically interesting structures bearing both amino and carboxylic acid functional groups represent an important class of multifunctional building blocks. In this study, we develop an easy access to novel SAAs in only three steps starting from nitro compounds in high yields in analytically pure form, easily available by ceric (IV) mediated radical additions. Such novel SAAs have been applied in the assembly of total nine carbopeptoids with the form of linear homo-and heterooligomers for the structural investigations employing circular dichroism (CD) spectroscopy, which suggest that the carbopeptoids emerge a well-extended, left (or right)-handed conformation similar to polyproline II (PPII) helices. NMR studies also clearly demonstrated the presence of ordered secondary structural elements. 2D-ROESY spectra were acquired to identify i+1NH <-> (C1H)-C-i, (C2H)-C-i correlations which support the conformational analysis of tetramers by CD spectroscopy. These findings provide interesting information of SAAs and their oligomers as potential scaffolds for discovering new drugs and materials. Y1 - 2018 U6 - https://doi.org/10.1038/s41598-018-24927-6 SN - 2045-2322 VL - 8 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Wessig, Pablo A1 - John, Leonard A1 - Mertens, Monique T1 - Extending the Class of [1,3]-Dioxolo[4.5-f]benzodioxole (DBD) Fluorescent Dyes JF - European journal of organic chemistry N2 - Synthetic routes to a collection of new fluorescent dyes are described, which are based on the [1,3]-dioxolo[4.5-f]benzodioxole (DBD) core. By introducing different electron withdrawing groups in 4- and 8-position of the DBD moiety the emission wavelength could be adjusted over a large spectral range from blue to orange light. KW - Functional organic materials KW - Fluorescence KW - DBD dyes KW - Large Stokes shifts KW - Aryllithium compounds KW - Heterocycles Y1 - 2018 U6 - https://doi.org/10.1002/ejoc.201800002 SN - 1434-193X SN - 1099-0690 VL - 2018 IS - 14 SP - 1674 EP - 1681 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Liebig, Ferenc A1 - Sarhan, Radwan Mohamed A1 - Prietzel, Claudia Christina A1 - Thünemann, Andreas F. A1 - Bargheer, Matias A1 - Koetz, Joachim T1 - Undulated Gold Nanoplatelet Superstructures BT - In Situ Growth of Hemispherical Gold Nanoparticles onto the Surface of Gold Nanotriangles JF - Langmuir N2 - Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 degrees C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV-vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of similar to 6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor. Y1 - 2018 U6 - https://doi.org/10.1021/acs.langmuir.7b02898 SN - 0743-7463 VL - 34 IS - 15 SP - 4584 EP - 4594 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Fudickar, Werner A1 - Linker, Torsten T1 - Release of Singlet Oxygen from Organic Peroxides under Mild Conditions JF - ChemPhotoChem N2 - Singlet oxygen can be released in the dark in nearly quantitative yield from endoperoxides of naphthalenes, anthracenes and pyridones as an alternative to its generation by photosensitization. Recently, new donor systems have been designed which operate at very low temperatures but which are prepared from their parent forms at acceptable rates. Enhancement of the reactivity of donors is conveniently achieved by the design of the substitution pattern or through the use of plasmonic heating of nanoparticle-bound donors. The most important aim of these donor molecules is to transfer singlet oxygen in a controlled and directed manner to a target. Low temperatures and the linking between donors and acceptors reduce the random walk of oxygen and may force an attack at the desired position. By using chiral donor systems, new stereocenters might be introduced into prochiral acceptors. KW - donor-acceptor systems KW - oxygenation KW - peroxides KW - polycycles KW - retro reactions Y1 - 2018 U6 - https://doi.org/10.1002/cptc.201700235 SN - 2367-0932 VL - 2 IS - 7 SP - 548 EP - 558 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Zwickel, Theresa A1 - Kahl, Sandra M. A1 - Rychlik, Michael A1 - Müller, Marina E. H. T1 - Chemotaxonomy of Mycotoxigenic Small-Spored Alternaria Fungi BT - Do Multitoxin Mixtures Act as an Indicator for Species Differentiation? JF - Frontiers in microbiology N2 - Necrotrophic as well as saprophytic small-spored Altemaria (A.) species are annually responsible for major losses of agricultural products, such as cereal crops, associated with the contamination of food and feedstuff with potential health-endangering Altemaria toxins. Knowledge of the metabolic capabilities of different species-groups to form mycotoxins is of importance for a reliable risk assessment. 93 Altemaria strains belonging to the four species groups Alternaria tenuissima, A. arborescens, A. altemata, and A. infectoria were isolated from winter wheat kernels harvested from fields in Germany and Russia and incubated under equal conditions. Chemical analysis by means of an HPLC-MS/MS multi-Alternaria-toxin-method showed that 95% of all strains were able to form at least one of the targeted 17 non-host specific Altemaria toxins. Simultaneous production of up to 15 (modified) Altemaria toxins by members of the A. tenuissima, A. arborescens, A. altemata species-groups and up to seven toxins by A. infectoria strains was demonstrated. Overall tenuazonic acid was the most extensively formed mycotoxin followed by alternariol and alternariol mono methylether, whereas altertoxin I was the most frequently detected toxin. Sulfoconjugated modifications of alternariol, alternariol mono methylether, altenuisol and altenuene were frequently determined. Unknown perylene quinone derivatives were additionally detected. Strains of the species-group A. infectoria could be segregated from strains of the other three species-groups due to significantly lower toxin levels and the specific production of infectopyrone. Apart from infectopyrone, alterperylenol was also frequently produced by 95% of the A. infectoria strains. Neither by the concentration nor by the composition of the targeted Altemaria toxins a differentiation between the species-groups A. altemata, A. tenuissima and A. arborescens was possible. KW - small-spored Alternaria fungi KW - Alternaria species-groups KW - Alternaria mycotoxins KW - chemotaxonomy KW - secondary metabolite profiling KW - LC-MS/MS KW - wheat KW - perylene quinone derivatives Y1 - 2018 U6 - https://doi.org/10.3389/fmicb.2018.01368 SN - 1664-302X VL - 9 PB - Frontiers Research Foundation CY - Lausanne ER - TY - JOUR A1 - Hesse, Julia A1 - Klier, Dennis Tobias A1 - Sgarzi, Massimo A1 - Nsubuga, Anne A1 - Bauer, Christoph A1 - Grenzer, Joerg A1 - Hübner, Rene A1 - Wislicenus, Marcus A1 - Joshi, Tanmaya A1 - Kumke, Michael Uwe A1 - Stephan, Holger T1 - Rapid Synthesis of Sub-10nm Hexagonal NaYF4-Based Upconverting Nanoparticles using Therminol((R))66 JF - ChemistryOpen : including thesis treasury N2 - We report a simple one-pot method for the rapid preparation of sub-10nm pure hexagonal (-phase) NaYF4-based upconverting nanoparticles (UCNPs). Using Therminol((R))66 as a co-solvent, monodisperse UCNPs could be obtained in unusually short reaction times. By varying the reaction time and reaction temperature, it was possible to control precisely the particle size and crystalline phase of the UCNPs. The upconversion (UC) luminescence properties of the nanocrystals were tuned by varying the concentrations of the dopants (Nd3+ and Yb3+ sensitizer ions and Er3+ activator ions). The size and phase-purity of the as-synthesized core and core-shell nanocrystals were assessed by using complementary transmission electron microscopy, dynamic light scattering, X-ray diffraction, and small-angle X-ray scattering studies. In-depth photophysical evaluation of the UCNPs was pursued by using steady-state and time-resolved luminescence spectroscopy. An enhancement in the UC intensity was observed if the nanocrystals, doped with optimized concentrations of lanthanide sensitizer/activator ions, were further coated with an inert/active shell. This was attributed to the suppression of surface-related luminescence quenching effects. KW - core-shell materials KW - lanthanides KW - nanostructures KW - photoluminescence KW - upconversion Y1 - 2018 U6 - https://doi.org/10.1002/open.201700186 SN - 2191-1363 VL - 7 IS - 2 SP - 159 EP - 168 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Yaouba, Souaibou A1 - Koch, Andreas A1 - Guantai, Eric M. A1 - Derese, Solomon A1 - Irungu, Beatrice A1 - Heydenreich, Matthias A1 - Yenesew, Abiy T1 - Alkenyl cyclohexanone derivatives from Lannea rivae and Lannea schweinfurthii JF - Phytochemistry letters / Phytochemical Society of Europe N2 - Phytochemical investigation of the CH2Cl2/MeOH (1:1) extract of the roots of Lannea rivae (Chiov) Sacleux (Anacardiaceae) led to the isolation of a new alkenyl cyclohexenone derivative: (4R,6S)-4,6-dihydroxy-6-((Z)-nonadec-14′-en-1-yl)cyclohex-2-en-1-one (1), and a new alkenyl cyclohexanol derivative: (2S*,4R*,5S*)-2,4,5-trihydroxy-2-((Z)-nonadec-14′-en-1-yl)cyclohexanone (2) along with four known compounds, namely epicatechin gallate, taraxerol, taraxerone and β-sitosterol; while the stem bark afforded two known compounds, daucosterol and lupeol. Similar investigation of the roots of Lannea schweinfurthii (Engl.) Engl. led to the isolation of four known compounds: 3-((E)-nonadec-16′-enyl)phenol, 1-((E)-heptadec-14′-enyl)cyclohex-4-ene-1,3-diol, catechin, and 1-((E)-pentadec-12′-enyl)cyclohex-4-ene-1,3-diol. The structures of the isolated compounds were determined by NMR spectroscopy and mass spectrometry. The absolute configuration of compound 1 was established by quantum chemical ECD calculations. In an antibacterial activity assay using the microbroth kinetic method, compound 1 showed moderate activity against Escherichia coli while compound 2 exhibited moderate activity against Staphylococcus aureus. Compound 1 also showed moderate activity against E. coli using the disc diffusion method. The roots extract of L. rivae was notably cytotoxic against both the DU-145 prostate cancer cell line and the Vero mammalian cell line (CC50 = 5.24 and 5.20 μg/mL, respectively). Compound 1 was also strongly cytotoxic against the DU-145 cell line (CC50 = 0.55 μg/mL) but showed no observable cytotoxicity (CC50 > 100 μg/mL) against the Vero cell line. The roots extract of L. rivae and L. schweinfurthii, epicatechin gallate as well as compound 1 exhibited inhibition of carageenan-induced inflammation. KW - Lannea rivae KW - Lannea schweinfurthii KW - Alkenyl cyclohexenone KW - Alkenyl cyclohexanone KW - Anti-inflammatory KW - Cytotoxicity KW - Antimicrobial Y1 - 2017 U6 - https://doi.org/10.1016/j.phytol.2017.12.001 SN - 1874-3900 SN - 1876-7486 VL - 23 SP - 141 EP - 148 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Guo, Ranran A1 - Tian, Ye A1 - Yang, Yueqi A1 - Jiang, Qin A1 - Wang, Yajun A1 - Yang, Wuli T1 - A Yolk-Shell nanoplatform for gene-silencing-enhanced photolytic ablation of cancer JF - Advanced functional materials N2 - Noninvasive near-infrared (NIR) light responsive therapy is a promising cancer treatment modality; however, some inherent drawbacks of conventional phototherapy heavily restrict its application in clinic. Rather than producing heat or reactive oxygen species in conventional NIR treatment, here a multifunctional yolk-shell nanoplatform is proposed that is able to generate microbubbles to destruct cancer cells upon NIR laser irradiation. Besides, the therapeutic effect is highly improved through the coalition of small interfering RNA (siRNA), which is codelivered by the nanoplatform. In vitro experiments demonstrate that siRNA significantly inhibits expression of protective proteins and reduces the tolerance of cancer cells to bubble-induced environmental damage. In this way, higher cytotoxicity is achieved by utilizing the yolk-shell nanoparticles than treated with the same nanoparticles missing siRNA under NIR laser irradiation. After surface modification with polyethylene glycol and transferrin, the yolk-shell nanoparticles can target tumors selectively, as demonstrated from the photoacoustic and ultrasonic imaging in vivo. The yolk-shell nanoplatform shows outstanding tumor regression with minimal side effects under NIR laser irradiation. Therefore, the multifunctional nanoparticles that combining bubble-induced mechanical effect with RNA interference are expected to be an effective NIR light responsive oncotherapy. KW - cancer KW - gene silencing KW - near-infrared absorption KW - photolytic ablation KW - yolk-shell nanoparticles Y1 - 2018 U6 - https://doi.org/10.1002/adfm.201706398 SN - 1616-301X SN - 1616-3028 VL - 28 IS - 14 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Burek, Katja A1 - Eidner, Sascha A1 - Kuke, Stefanie A1 - Kumke, Michael Uwe T1 - Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight JF - Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy N2 - The luminescence of Lanthanide(Ill) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and.Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(Ill) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K <= T <= 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M <= 1 <= 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites. KW - Humic substance KW - Model ligand KW - Metal complexation KW - Benzoic acids KW - Intramolecular deactivation Y1 - 2018 U6 - https://doi.org/10.1016/j.saa.2017.09.012 SN - 1386-1425 VL - 191 SP - 36 EP - 49 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Schmidt, Bernd A1 - Petersen, Monib H. A1 - Braun, Diana T1 - Bidirectional Synthesis of 6-Acetoxy-5-hexadecanolide, the Mosquito Oviposition Pheromone of Culex quinquefasciatus, from a C-2-Symmetric Building Block Using Olefin Metathesis Reactions JF - The journal of organic chemistry N2 - (5R,6S)-6-Acetoxy-5-hexadecanolide (MOP) is the oviposition pheromone of the mosquito Cx. quinquefasciatus, a vector of pathogens causing a variety of tropical diseases. We describe and evaluate herein three syntheses of MOP starting from mannitol-derived (3R,4R)-hexa-1,5-diene-3,4-diol. This C-2-symmetric building block is elaborated through bidirectional olefin metathesis reactions into 6-epi-MOP, which was converted into MOP via Mitsunobu inversion. The shortest of the three routes makes use of two sequential cross-metathesis reactions and an assisted tandem catalytic olefin reduction, induced by an in situ conversion of a Ru-carbene to a Ru-hydride. Y1 - 2018 U6 - https://doi.org/10.1021/acs.joc.7b02944 SN - 0022-3263 VL - 83 IS - 3 SP - 1627 EP - 1633 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Sun, Fu A1 - Osenberg, Markus A1 - Dong, Kang A1 - Zhou, Dong A1 - Hilger, Andre A1 - Jafta, Charl J. A1 - Risse, Sebastian A1 - Lu, Yan A1 - Markoetter, Henning A1 - Manke, Ingo T1 - Correlating Morphological Evolution of Li Electrodes with Degrading Electrochemical Performance of Li/LiCoO2 and Li/S Battery Systems BT - Investigated by Synchrotron X-ray Phase Contrast Tomography JF - ACS energy letters / American Chemical Society N2 - Efficient Li utilization is generally considered to be a prerequisite for developing next-generation energy storage systems (ESSs). However, uncontrolled growth of Li microstructures (LmSs) during electrochemical cycling has prevented its practical commercialization. Herein, we attempt to understand the correlation of morphological evolution of Li electrodes with degrading electrochemical performances of Li/LiCoO2 and Li/S systems by synchrotron X-ray phase contrast tomography technique. It was found that the continuous transformation of the initial dense Li bulk to a porous lithium interface (PL1) structure intimately correlates with the gradually degrading overall cell performance of these two systems. Additionally, the formation mechanism of the PLI and its correlation with previously reported inwardly growing LmS and the lithium-reacted region have been intensively discussed. The information that we gain herein is complementary to previous investigations and may provide general insights into understanding of degradation mechanisms of Li metal anodes and also provide highly needed guidelines for effective design of reliable next-generation Li metal-based ESSs. Y1 - 2018 U6 - https://doi.org/10.1021/acsenergylett.7b01254 SN - 2380-8195 VL - 3 IS - 2 SP - 356 EP - 365 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Dai, Xiaolin A1 - Mate, Diana M. A1 - Glebe, Ulrich A1 - Garakani, Tayebeh Mirzaei A1 - Körner, Andrea A1 - Schwaneberg, Ulrich A1 - Böker, Alexander T1 - Sortase-mediated ligation of purely artificial building blocks JF - Polymers N2 - Sortase A (SrtA) from Staphylococcus aureus has been often used for ligating a protein with other natural or synthetic compounds in recent years. Here we show that SrtA-mediated ligation (SML) is universally applicable for the linkage of two purely artificial building blocks. Silica nanoparticles (NPs), poly(ethylene glycol) and poly(N-isopropyl acrylamide) are chosen as synthetic building blocks. As a proof of concept, NP-polymer, NP-NP, and polymer-polymer structures are formed by SrtA catalysis. Therefore, the building blocks are equipped with the recognition sequence needed for SrtA reaction-the conserved peptide LPETG-and a pentaglycine motif. The successful formation of the reaction products is shown by means of transmission electron microscopy (TEM), matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-ToF MS), and dynamic light scattering (DLS). The sortase catalyzed linkage of artificial building blocks sets the stage for the development of a new approach to link synthetic structures in cases where their synthesis by established chemical methods is complicated. KW - sortase-mediated ligation KW - enzymes KW - block copolymers KW - nanoparticles Y1 - 2018 U6 - https://doi.org/10.3390/polym10020151 SN - 2073-4360 VL - 10 IS - 2 PB - MDPI CY - Basel ER - TY - JOUR A1 - Roder, Phillip A1 - Hille, Carsten T1 - Local tissue manipulation via a force- and pressure-controlled AFM micropipette for analysis of cellular processes JF - Scientific reports N2 - Local manipulation of complex tissues at the single-cell level is challenging and requires excellent sealing between the specimen and the micromanipulation device. Here, biological applications for a recently developed loading technique for a force-and pressure-controlled fluidic force microscope micropipette are described. This technique allows for the exact positioning and precise spatiotemporal control of liquid delivery. The feasibility of a local loading technique for tissue applications was investigated using two fluorescent dyes, with which local loading behaviour could be optically visualised. Thus, homogeneous intracellular distribution of CellTracker Red and accumulation of SYTO 9 Green within nuclei was realised in single cells of a tissue preparation. Subsequently, physiological micromanipulation experiments were performed. Salivary gland tissue was pre-incubated with the Ca2+-sensitive dye OGB-1. An intracellular Ca2+ rise was then initiated at the single-cell level by applying dopamine via micropipette. When pre-incubating tissue with the nitric oxide (NO)-sensitive dye DAF-FM, NO release and intercellular NO diffusion was observed after local application of the NO donor SNP. Finally, local micromanipulation of a well-defined area along irregularly shaped cell surfaces of complex biosystems was shown for the first time for the fluidic force microscope micropipette. Thus, this technique is a promising tool for the investigation of the spatiotemporal effects of locally applied substances in complex tissues. Y1 - 2018 U6 - https://doi.org/10.1038/s41598-018-24255-9 SN - 2045-2322 VL - 8 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Kirpichenko, Svetlana A1 - Shainyan, Bagrat A. A1 - Kleinpeter, Erich A1 - Shlykov, Sergey A. A1 - Tran Dinh Phien, A1 - Albanov, Alexander T1 - Synthesis of 3-fluoro-3-methyl-3-silatetrahydropyran and its conformational preferences in gas and solution by GED, NMR and theoretical calculations JF - Tetrahedron N2 - The 3,3-disubstitued 3-silaheterocyclohexane with an electronegative substituent at silicon, 3-fluoro-3-methyl-3-silatetrahydropyran 1, was synthesized, and its molecular structure and conformational properties studied by gas-phase electron diffraction (GED) and low temperature C-13 and F-19 NMR spectroscopy. Quantum-chemical calculations were carried out both for the isolated species and Hcomplexes in gas and in polar medium. The predominance of the 1-FeqMeax conformer (1-F-eq:1-F-ax ratio of 65:35, Delta G degrees = 0.37 kcal/mol) determined from GED is close to the theoretically estimated conformational equilibrium, especially at the DFT level. In solution, low temperature NMR spectroscopy showed no decoalescence of the signals in C-13 (down to 95 K) and F-19 NMR spectra (down to 123 K). However, the calculated F-19 chemical shift of -173.6 ppm for the 1-FeqMeax conformer practically coincides with the experimentally observed value (-173 to -175 ppm) as distinct from that for the 1-FaxMeeq conformer (-188.8 ppm), suggesting compound 1 to be anancomeric in solution, in compliance with its theoretical and experimental preference in the gas phase. KW - 3-Fluoro-3-methyl-3-silatetrahydropyran KW - Conformational analysis KW - Gas phase electron diffraction KW - Low-temperature NMR KW - DFT KW - MP2 and CCSD(T) calculations Y1 - 2018 U6 - https://doi.org/10.1016/j.tet.2018.02.055 SN - 0040-4020 VL - 74 IS - 15 SP - 1859 EP - 1867 PB - Elsevier CY - Oxford ER - TY - THES A1 - Hermanns, Jolanda T1 - Development, use and evaluation of concepts and materials for teaching organic chemistry at university Y1 - 2021 ER - TY - JOUR A1 - Nizardo, Noverra M. A1 - Schanzenbach, Dirk A1 - Schönemann, Eric A1 - Laschewsky, Andre T1 - Exploring poly(ethylene glycol)-polyzwitterion diblock copolymers as biocompatible smart macrosurfactants featuring UCST-phase behavior in normal saline solution JF - Polymers N2 - Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST) in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol) (PEG) macroinitiator via atom transfer radical polymerization (ATRP) of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and H-1 NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30-50 degrees C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo-and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in "schizophrenic" thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature) transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model "cargos" failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions. KW - block copolymer KW - amphiphile KW - macrosurfactant KW - thermoresponsive self-assembly KW - polyzwitterion KW - upper critical solution temperature (UCST) KW - salting-in Y1 - 2018 U6 - https://doi.org/10.3390/polym10030325 SN - 2073-4360 VL - 10 IS - 3 PB - MDPI CY - Basel ER - TY - GEN A1 - Dahmani, Ismail A1 - Ludwig, Kai A1 - Chiantia, Salvatore T1 - Influenza A matrix protein M1 induces lipid membrane deformation via protein multimerization T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - The matrix protein M1 of the Influenza A virus (IAV) is supposed to mediate viral assembly and budding at the plasma membrane (PM) of infected cells. In order for a new viral particle to form, the PM lipid bilayer has to bend into a vesicle toward the extracellular side. Studies in cellular models have proposed that different viral proteins might be responsible for inducing membrane curvature in this context (including M1), but a clear consensus has not been reached. In the present study, we use a combination of fluorescence microscopy, cryogenic transmission electron microscopy (cryo-TEM), cryo-electron tomography (cryo-ET) and scanning fluorescence correlation spectroscopy (sFCS) to investigate M1-induced membrane deformation in biophysical models of the PM. Our results indicate that M1 is indeed able to cause membrane curvature in lipid bilayers containing negatively charged lipids, in the absence of other viral components. Furthermore, we prove that protein binding is not sufficient to induce membrane restructuring. Rather, it appears that stable M1–M1 interactions and multimer formation are required in order to alter the bilayer three-dimensional structure, through the formation of a protein scaffold. Finally, our results suggest that, in a physiological context,M1-induced membrane deformation might be modulated by the initial bilayer curvature and the lateral organization of membrane components (i.e. the presence of lipid domains). T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 768 KW - confocal microscopy KW - influenza KW - lipid membranes KW - membranes KW - protein-protein interactions KW - viral matrix proteins Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-438689 SN - 1866-8372 IS - 768 ER - TY - JOUR A1 - Sand, Patrick A1 - Schmidt, Bernd T1 - Pd-catalyzed oxidative sulfoalkenylation of acetanilides and traceless removal of the catalyst directing group JF - ChemistrySelect N2 - The palladium-catalyzed oxidative Heck-reaction, also referred to as Fujiwara-Moritani-reaction, has been investigated for the synthesis of styrenylsulfonyl compounds. Acetanilides and vinylsulfonyl compounds undergo dehydrogenative coupling reactions in moderate to quantitative yields, using benzoquinone as the oxidant of choice. Potassium peroxodisulfate, which had previously been identified as a superior oxidant for the coupling with acrylates, did not provide any coupling products with these olefins. Traceless removal of the catalyst directing group through a deacetylation-diazotation-coupling (DDC) sequence was demonstrated for 2-arylethene sulfones. KW - arenes KW - C− H activation KW - Heck reactions KW - Palladium KW - sulfones Y1 - 2021 U6 - https://doi.org/10.1002/slct.202101009 SN - 2365-6549 VL - 6 IS - 14 SP - 3563 EP - 3567 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Schmidt, Marco F. A1 - Korb, Oliver A1 - Abell, Chris T1 - Antagonists of the miRNA-Argonaute 2 Protein Complex BT - Anti-miR-AGOs JF - Drug Target miRNA: Methods and Protocols N2 - microRNAs (miRNAs) have been identified as high-value drug targets. A widely applied strategy in miRNA inhibition is the use of antisense agents. However, it has been shown that oligonucleotides are poorly cell permeable because of their complex chemical structure and due to their negatively charged backbone. Consequently, the general application of oligonucleotides in therapy is limited. Since miRNAs’ functions are executed exclusively by the Argonaute 2 protein, we therefore describe a protocol for the design of a novel miRNA inhibitor class: antagonists of the miRNA-Argonaute 2 protein complex, so-called anti-miR-AGOs, that not only block the crucial binding site of the target miRNA but also bind to the protein’s active site. Due to their lower molecular weight and, thus, more drug-like chemical structure, the novel inhibitor class may show better pharmacokinetic properties than reported oligonucleotide inhibitors, enabling them for potential therapeutic use. KW - Drug design KW - microRNA KW - miRNA-Argonaute 2 protein complex KW - miRNA inhibitors KW - miRNA seed region Y1 - 2016 SN - 978-1-4939-6563-2 SN - 978-1-4939-6561-8 SN - 978-1-4939-8236-3 U6 - https://doi.org/10.1007/978-1-4939-6563-2_17 SN - 1064-3745 SN - 1940-6029 VL - 1517 SP - 239 EP - 249 PB - Springer CY - New York ER - TY - JOUR A1 - Haubitz, Toni A1 - Fudickar, Werner A1 - Linker, Torsten A1 - Kumke, Michael Uwe T1 - pH-sensitive fluorescence switching of pyridylanthracenes BT - the effect of the isomeric pattern JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - 9,10-substituted anthracenes are known for their useful optical properties like fluorescence, which makes them frequently used probes in sensing applications. In this article, we investigate the fundamental photophysical properties of three pyridyl-substituted variants. The nitrogen atoms in the pyridinium six-membered rings are located in the ortho-, meta-, and para-positions in relation to the anthracene core. Absorption, fluorescence, and transient absorption measurements were carried out and were complemented by theoretical calculations. We monitored the photophysics of the anthracene derivatives in chloroform and water investigating the protonated as well as their nonprotonated forms. We found that the optical properties of the nonprotonated forms are strongly determined by the anthracene chromophore, with only small differences to other 9,10-substituted anthracenes, for example diphenyl anthracene. In contrast, protonation leads to a strong decrease in fluorescence intensity and lifetime. Transient absorption measurements and theoretical calculations revealed the formation of a charge-transfer state in the protonated chromophores, where electron density is shifted from the anthracene moiety toward the protonated pyridyl substituents. While the para- and ortho-derivatives' charge transfer is still moderately fluorescent, the meta-derivative is affected much stronger and shows nearly no fluorescence. This nitrogen-atom-position-dependent sensitivity to hydronium activity makes a combination of these fluorophores very attractive for pH-sensing applications covering a broadened pH range. KW - Absorption KW - Aromatic compounds KW - Fluorescence KW - Hydrocarbons KW - Reaction mechanisms Y1 - 2020 U6 - https://doi.org/10.1021/acs.jpca.0c09911 SN - 1089-5639 SN - 1520-5215 VL - 124 IS - 52 SP - 11017 EP - 11024 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wessig, Pablo A1 - Freyse, Daniel A1 - Schuster, David A1 - Kelling, Alexandra T1 - Fluorescent dyes with large stokes shifts based on Benzo[1,2-d:4,5-d']bis([1,3]dithiole) (“S4-DBD Dyes”) JF - Europan journal of organic chemistry N2 - We report on a further development of [1,3]-dioxolo[4.5-f]benzodioxole (DBD) fluorescent dyes by replacement of the four oxygen atoms of the heterocyclic core by sulfur atoms. This variation causes striking changes of the photophysical properties. Whereas absorption and emission significantly shifted to longer wavelength, the fluorescence lifetimes and quantum yields are diminished compared to DBD dyes. The latter effect is presumably caused by an enhanced intersystem crossing to the triplet state due to the sulfur atoms. The very large Stokes shifts of the S-4-DBD dyes ranging from 3000 cm(-1) to 7400 cm(-1) (67 nm to 191 nm) should be especially emphasized. By analogy with DBD dyes a broad variation of absorption and emission wavelength is possible by introducing different electron withdrawing substituents. Moreover, some derivatives for coupling with biomolecules were developed. KW - fluorescent dyes KW - sulfur KW - heterocycles KW - stokes shift KW - photophysics Y1 - 2020 U6 - https://doi.org/10.1002/ejoc.202000093 SN - 1434-193X SN - 1099-0690 VL - 2020 IS - 11 SP - 1732 EP - 1744 PB - Wiley CY - Weinheim ER - TY - JOUR A1 - Lood, Kajsa A1 - Schmidt, Bernd T1 - Stereoselective synthesis of conjugated polyenes based on tethered olefin metathesis and carbonyl olefination BT - application to the total synthesis of (+)-bretonin B JF - The journal of organic chemistry N2 - The combination of a highly stereoselective tethered olefin metathesis reaction and a Julia-Kocienski olefination is presented as a strategy for the synthesis of conjugated polyenes with at least one Z-configured C=C bond. The strategy is exemplified by the synthesis of the marine natural product (+)-bretonin B. KW - absolute-configuration KW - natural-products KW - formal synthesis KW - oxidation KW - derivatives KW - aldehydes KW - catalysts KW - alcohols KW - sponge KW - ethers Y1 - 2020 U6 - https://doi.org/10.1021/acs.joc.0c00446 SN - 0022-3263 SN - 1520-6904 VL - 85 IS - 7 SP - 5122 EP - 5130 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Spricigo, Roberto A1 - Dronov, Roman A1 - Lisdat, Fred A1 - Leimkühler, Silke A1 - Scheller, Frieder W. A1 - Wollenberger, Ursula T1 - Electrocatalytic sulfite biosensor with human sulfite oxidase co-immobilized with cytochrome c in a polyelectrolyte-containing multilayer T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - An efficient electrocatalytic biosensor for sulfite detection was developed by co-immobilizing sulfite oxidase and cytochrome c with polyaniline sulfonic acid in a layer-by-layer assembly. QCM, UV-Vis spectroscopy and cyclic voltammetry revealed increasing loading of electrochemically active protein with the formation of multilayers. The sensor operates reagentless at low working potential. A catalytic oxidation current was detected in the presence of sulfite at the modified gold electrode, polarized at +0.1 V ( vs. Ag/AgCl 1 M KCl). The stability of the biosensor performance was characterized and optimized. A 17-bilayer electrode has a linear range between 1 and 60 mu M sulfite with a sensitivity of 2.19 mA M-1 sulfite and a response time of 2 min. The electrode retained a stable response for 3 days with a serial reproducibility of 3.8% and lost 20% of sensitivity after 5 days of operation. It is possible to store the sensor in a dry state for more than 2 months. The multilayer electrode was used for determination of sulfite in unspiked and spiked samples of red and white wine. The recovery and the specificity of the signals were evaluated for each sample. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 945 KW - bioelectrocatalysis KW - sulfite KW - sulfite oxidase KW - cytochrome c KW - multilayer Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-431176 SN - 1866-8372 IS - 945 SP - 225 EP - 233 ER - TY - GEN A1 - Krippendorff, Ben-Fillippo A1 - Oyarzún, Diego A. A1 - Huisinga, Wilhelm T1 - Predicting the F(ab)-mediated effect of monoclonal antibodies in vivo by combining cell-level kinetic and pharmacokinetic modelling T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Cell-level kinetic models for therapeutically relevant processes increasingly benefit the early stages of drug development. Later stages of the drug development processes, however, rely on pharmacokinetic compartment models while cell-level dynamics are typically neglected. We here present a systematic approach to integrate cell-level kinetic models and pharmacokinetic compartment models. Incorporating target dynamics into pharmacokinetic models is especially useful for the development of therapeutic antibodies because their effect and pharmacokinetics are inherently interdependent. The approach is illustrated by analysing the F(ab)-mediated inhibitory effect of therapeutic antibodies targeting the epidermal growth factor receptor. We build a multi-level model for anti-EGFR antibodies by combining a systems biology model with in vitro determined parameters and a pharmacokinetic model based on in vivo pharmacokinetic data. Using this model, we investigated in silico the impact of biochemical properties of anti-EGFR antibodies on their F(ab)-mediated inhibitory effect. The multi-level model suggests that the F(ab)-mediated inhibitory effect saturates with increasing drug-receptor affinity, thereby limiting the impact of increasing antibody affinity on improving the effect. This indicates that observed differences in the therapeutic effects of high affinity antibodies in the market and in clinical development may result mainly from Fc-mediated indirect mechanisms such as antibody-dependent cell cytotoxicity. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 958 KW - cell-level kinetics KW - pharmacokinetic models KW - therapeutic proteins KW - EGFR Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-431051 SN - 1866-8372 IS - 958 SP - 125 EP - 139 ER - TY - GEN A1 - Krueger, Tobias A1 - Kelling, Alexandra A1 - Linker, Torsten A1 - Schilde, Uwe T1 - Crystal structures of three cyclohexane‑based γ‑spirolactams BT - determination of configurations and conformations T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - The title compounds, 2-azaspiro[4.5]deca-1-one, C₉H₁₅NO, (1a), cis-8-methyl-2-azaspiro[4.5]deca-1-one, C₁₀H₁₇NO, (1b), and trans-8-methyl-2-azaspiro[4.5]deca-1-one, C₁₀H₁₇NO, (1c), were synthesized from benzoic acids 2 in only 3 steps in high yields. Crystallization from n-hexane afforded single crystals, suitable for X-ray diffraction. Thus, the configurations, conformations, and interesting crystal packing effects have been determined unequivocally. The bicyclic skeleton consists of a lactam ring, attached by a spiro junction to a cyclohexane ring. The lactam ring adopts an envelope conformation and the cyclohexane ring has a chair conformation. The main difference between compound 1b and compound 1c is the position of the carbonyl group on the 2-pyrrolidine ring with respect to the methyl group on the 8-position of the cyclohexane ring, which is cis (1b) or trans (1c). A remarkable feature of all three compounds is the existence of a mirror plane within the molecule. Given that all compounds crystallize in centrosymmetric space groups, the packing always contains interesting enantiomer-like pairs. Finally, the structures are stabilized by intermolecular N–H···O hydrogen bonds. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 738 KW - 2-Azaspiro[4.5]deca-1-ones KW - Cis- and trans-form KW - Configuration KW - Conformation KW - Lactams Y1 - 1019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-434911 IS - 738 ER - TY - JOUR A1 - Tiedemann, Kim A1 - Iobbi-Nivol, Chantal A1 - Leimkühler, Silke T1 - The Role of the Nucleotides in the Insertion of the bis-Molybdopterin Guanine Dinucleotide Cofactor into apo-Molybdoenzymes JF - Molecules N2 - The role of the GMP nucleotides of the bis-molybdopterin guanine dinucleotide (bis-MGD) cofactor of the DMSO reductase family has long been a subject of discussion. The recent characterization of the bis-molybdopterin (bis-Mo-MPT) cofactor present in the E. coli YdhV protein, which differs from bis-MGD solely by the absence of the nucleotides, now enables studying the role of the nucleotides of bis-MGD and bis-MPT cofactors in Moco insertion and the activity of molybdoenzymes in direct comparison. Using the well-known E. coli TMAO reductase TorA as a model enzyme for cofactor insertion, we were able to show that the GMP nucleotides of bis-MGD are crucial for the insertion of the bis-MGD cofactor into apo-TorA. KW - bis-MGD KW - chaperone KW - molybdenum cofactor KW - TMAO reductase Y1 - 2022 U6 - https://doi.org/10.3390/molecules27092993 SN - 1420-3049 VL - 27 SP - 1 EP - 15 PB - MDPI CY - Basel, Schweiz ET - 9 ER - TY - JOUR A1 - Mai-Linde, Yasemin A1 - Linker, Torsten T1 - Radical clock probes to determine carbohydrate radical stabilities JF - Organic letters N2 - Carbohydrate radical stabilities in the 1- and 2-position have been determined by a radical clock approach, starting from cyclopropanated sugars with xanthates as precursors. Various hexoses and pentoses afforded 1-deoxy sugars as main products, indicating that anomeric radicals are more stable than radicals in the 2-position. An additional influence of the configurations on radical stabilities has been observed. Our results should be interesting for the understanding of 1,2-radical rearrangements in carbohydrate chemistry and offer an easy access to deoxy-vinyl sugars. KW - stereoselective-synthesis KW - convenient synthesis KW - chemistry KW - cyclopropanation KW - mechanism KW - glycals KW - beta-(acyloxy)alkylrear KW - rangement KW - sugars Y1 - 2020 U6 - https://doi.org/10.1021/acs.orglett.0c00111 SN - 1523-7060 SN - 1523-7052 VL - 22 IS - 4 SP - 1525 EP - 1529 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schultze, Christiane A1 - Foß, Stefan A1 - Schmidt, Bernd T1 - 8-Prenylflavanones through microwave promoted tandem claisen rearrangement/6-endo-trig cyclization and cross metathesis JF - European journal of organic chemistry N2 - Prenylated flavanones were obtained from ortho-allyloxy chalcones through a one-pot sequence of Claisen rearrangement and 6-endo-trig cyclization, followed by olefin cross metathesis of the intermediate allyl flavanones with 2-methyl-2-butene. The synthetic utility of this route is illustrated for the synthesis of several naturally occurring prenyl flavanones. KW - tandem reactions KW - arenes KW - oxygen heterocycles KW - microwave chemistry KW - rearrangement Y1 - 2020 U6 - https://doi.org/10.1002/ejoc.202001378 SN - 1434-193X SN - 1099-0690 VL - 2020 IS - 47 SP - 7373 EP - 7384 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Gabriel, Christina T1 - Entwicklung neuer Stärkederivate für die Anwendung als wasserbasierte Filmbildner in Farben und Lacken T1 - Development of new starch derivatives for application as water-based film formers in paints and varnishes N2 - In den letzten Jahrzehnten fand auch in der Beschichtungsindustrie ein Umdenken hin zu umweltfreundlicheren Farben und Lacken statt. Allerdings basieren auch neue Lösungen meist nicht auf Biopolymeren und in einem noch geringeren Anteil auf wasserbasierten Beschichtungssystemen aus nachwachsenden Rohstoffen. Dies stellt den Anknüpfungspunkt dieser Arbeit dar, in der untersucht wurde, ob das Biopolymer Stärke das Potenzial zum wasserbasierten Filmbildner für Farben und Lacke besitzt. Dabei müssen angelehnt an etablierte synthetische Marktprodukte die folgenden Kriterien erfüllt werden: Die wässrige Dispersion muss mindestens einen 30%igen Feststoffgehalt haben, bei Raumtemperatur verarbeitet werden können und Viskositäten zwischen 10^2-10^3 mPa·s aufweisen. Die finale Beschichtung muss einen geschlossenen Film bilden und sehr gute Haftfestigkeiten zu einer spezifischen Oberfläche, in dieser Arbeit Glas, besitzen. Als Grundlage für die Modifizierung der Stärke wurde eine Kombination von molekularem Abbau und chemischer Funktionalisierung ausgewählt. Da nicht bekannt war, welchen Einfluss die Stärkeart, die gewählte Abbaureaktion als auch verschiedene Substituenten auf die Dispersionsherstellung und deren Eigenschaften sowie die Beschichtungseigenschaften ausüben könnten, wurden die strukturellen Parameter getrennt voneinander untersucht. Das erste Themengebiet beinhaltete den oxidativen Abbau von Kartoffel- und Palerbsenstärke mittels des Hypochlorit-Abbaus (OCl-) und des ManOx-Abbaus (H2O2, KMnO4). Mit beiden Abbaureaktionen konnten vergleichbare gewichtsmittlere Molmassen (Mw) von 2·10^5-10^6 g/mol (GPC-MALS) hergestellt werden. Allerdings führten die gewählten Reaktionsbedingungen beim ManOx-Abbau zur Bildung von Gelpartikeln. Diese lagen im µm-Bereich (DLS und Kryo-REM-Messungen) und hatten zur Folge, dass die ManOx-Proben deutlich erhöhte Viskositäten (c: 7,5 %; 9-260 mPa·s) im Vergleich zu den OCl--Proben (4-10 mPa·s) bei scherverdünnendem Verhalten besaßen und die Eigenschaften von viskoelastischen Gelen (G‘ > G‘‘) zeigten. Des Weiteren wiesen sie reduzierte Heißwasserlöslichkeiten (95 °C, vorrangig: 70-99 %) auf. Der OCl--Abbau führte zu hydrophileren (Carboxylgruppengehalt bis zu 6,1 %; ManOx: bis zu 3,1 %), nach 95 °C-Behandlung vollständig wasserlöslichen abgebauten Stärken, die ein Newtonsches Fließverhalten mit Eigenschaften einer viskoelastischen Flüssigkeit (G‘‘ > G‘) hatten. Die OCl--Proben konnten im Vergleich zu den ManOx-Produkten (10-20 %) zu konzentrierteren Dispersionen (20-40 %) verarbeitet werden, die gleichzeitig die Einschränkung von anwendungsrelevanten Mw auf < 7·10^5 g/mol zuließen (Konzentration sollte > 30 % sein). Außerdem führten nur die OCl--Proben der Kartoffelstärke zu transparenten (alle anderen waren opak) geschlossenen Beschichtungsfilmen. Somit hebt sich die Kombination von OCl--Abbau und Kartoffelstärke mit Hinblick auf die Endanwendung ab. Das zweite Themengebiet umfasste Untersuchungen zum Einfluss von Ester- und Hydroxyalkylether-Substituenten auf Basis einer industriell abgebauten Kartoffelstärke (Mw: 1,2·10^5 g/mol) vor allem auf die Dispersionsherstellung, die rheologischen Eigenschaften der Dispersionen und die Beschichtungseigenschaften in Kombination mit Glassubstraten. Dazu wurden Ester und Ether mit DS/MS-Werten von 0,07-0,91 synthetisiert. Die Derivate konnten zu wasserbasierten Dispersionen mit Konzentrationen von 30-45 % verarbeitet werden, wobei bei hydrophoberen Modifikaten ein Co-Lösemittel, Diethylenglycolmonobutylether (DEGBE), eingesetzt werden musste. Die Feststoffgehalte sanken dabei für beide Derivatklassen vor allem mit zunehmender Alkylkettenlänge. Die anwendungsrelevanten Viskositäten (323-1240 mPa·s) stiegen auf Grund von Wechselwirkungen tendenziell mit DS/MS und Alkylkettenlänge an. Hinsichtlich der Beschichtungseigenschaften erwiesen sich die Ester vergleichend zu den Ethern als die bevorzugte Substituentenklasse, da nur die Ester geschlossene, defektfreie und mehrheitlich transparente Beschichtungsfilme bildeten, die exzellente bis sehr gute Haftfestigkeiten (ISO Klasse: 0 und 1) auf Glas besaßen. Die Ether bildeten mehrheitlich brüchige Filme. Basierend auf der Kombination der Ergebnisse aus Lösemittelaustausch, den rheologischen Untersuchungen und zusätzlichen Oberflächenspannungsmessungen (30-61 mN/m) konnte geschlossen werden, dass wahrscheinlich fehlende oder schlechte Haftfestigkeiten vorrangig akkumuliertem Wasser in den Beschichtungsfilmen (visuell: trüb oder weiß) geschuldet sind, während die Brüchigkeit vermutlich auf Wechselwirkungen (H-Brücken Wechselwirkungen, hydrophobe Wechselwirkungen) zwischen den Polymeren zurückgeführt werden kann. Insgesamt scheint die Kombination aus Kartoffelstärke basierend auf dem OCl--Abbau mit Mw < 7·10^5 g/mol und einem Estersubstituenten eine gute Wahl für wasserbasierte Dispersionen mit hohen Feststoffkonzentrationen (> 30 %), guter Filmbildung und exzellenten Haftungen auf Glas zu sein. N2 - In the last few decades, the coating industry, like many other industries, has changed its thinking towards more environmentally friendly paints and varnishes. However, even new solutions are usually not based on biopolymers and, to an even lesser extent, on water-based coating systems made from renewable raw materials. This is the starting point of this work, which aimed to investigate whether the biopolymer starch has the potential to be a water-based film former for paints and varnishes. Based on established synthetic market products, the following criteria must be fulfilled: The aqueous dispersion must have a solid content of at least 30%, be processable at room temperature and have viscosities of 10^2-10^3 mPa·s. The final coating must form a continuous film and have very good adhesion to a specific substrate, in this thesis glass. A combination of molecular degradation and chemical functionalisation was selected as the basis for the modification of the starch. Since it was not known what influence the type of starch, the chosen degradation reaction as well as different substituents could have on the dispersion production and its properties as well as on the coating properties, the structural parameters were investigated separately. The first part dealt with the oxidative degradation of potato and smooth pea starch by hypochlorite degradation (OCl-) and ManOx degradation (H2O2, KMnO4). With both degradation reactions comparable weight average molar masses (Mw) of 2·10^5-10^6 g/mol (SEC-MALS) could be synthesized. However, the selected reaction conditions led to the formation of gel particles during ManOx degradation. These were in the µm-range (DLS and cryo-REM measurements) and resulted in ManOx samples having significantly higher viscosities (c: 7.5%; 9-260 mPa·s) compared to OCl- samples (4-10 mPa·s) with shear-thinning behaviour and showing the properties of viscoelastic gels (G' > G''). Furthermore, they exhibited reduced hot water solubilities (95 °C, primarily: 70-99%). OCl- degradation led to more hydrophilic (carboxyl group content up to 6.1%; ManOx: up to 3.1%), after 95 °C treatment completely water-soluble degraded starches, which had Newtonian flow behaviour with properties of a viscoelastic liquid (G'' > G'). Compared to the ManOx products (10-20%), the OCl- samples could be processed to more concentrated dispersions (20-40%), which at the same time allowed the restriction of application-relevant Mw to < 7·10^5 g/mol (concentration should be > 30%). In addition, only the OCl- samples of the potato starch led to transparent (all others were opaque) continuous coating films. Thus, the combination of OCl- degradation and potato starch stands out with regard to the final application. The second part included investigations on the influence of ester and hydroxyalkyl ether substituents on the basis of an industrially degraded potato starch (Mw: 1.2·10^5 g/mol), particularly on dispersion preparation, rheological properties of the dispersions and the coating properties in combination with glass substrates. For this purpose, esters and ethers with DS/MS values of 0.07-0.91 were synthesized. The derivatives could be prepared to water-based dispersions with concentrations of 30-45%, whereby a co-solvent, diethylene glycol monobutyl ether (DEGBE), had to be used for more hydrophobic derivatives. The solid content of both derivative classes decreased most of all with increasing alkyl chain length. The application-relevant viscosities (323-1240 mPa·s) tended to increase due to interactions with DS/MS and alkyl chain length. With regard to the coating properties, esters proved to be the preferred substituent class compared to ethers, since only the esters formed continuous, defect free and mostly transparent coating films which had excellent to very good adhesion (ISO class: 0 and 1) on glass. The majority of ethers formed brittle films. Based on the combination of the results from solvent exchange, rheological investigations and additional surface tension measurements (30-61 mN/m), it could be concluded that probably missing or poor adhesion was primarily due to accumulated water in the coating films (visually: turbid or white), while the brittleness can probably be attributed to interactions (H-bridge interactions, hydrophobic interactions) between the polymers. Overall, the combination of potato starch based on OCl- degradation with Mw < 7·10^5 g/mol and an ester substituent seems to be a good choice for water-based dispersions with high solid concentrations (> 30%), good film formation and excellent adhesion to glass. KW - Stärke KW - starch KW - Filmbildner KW - film former KW - Beschichtung KW - coating Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-432942 ER - TY - JOUR A1 - Raju, Rajarshi Roy A1 - Koetz, Joachim T1 - Inner rotation of Pickering Janus emulsions JF - Nanomaterials : open access journal N2 - Janus droplets were prepared by vortex mixing of three non-mixable liquids, i.e., olive oil, silicone oil and water, in the presence of gold nanoparticles (AuNPs) in the aqueous phase and magnetite nanoparticles (MNPs) in the olive oil. The resulting Pickering emulsions were stabilized by a red-colored AuNP layer at the olive oil/water interface and MNPs at the oil/oil interface. The core–shell droplets can be stimulated by an external magnetic field. Surprisingly, an inner rotation of the silicon droplet is observed when MNPs are fixed at the inner silicon droplet interface. This is the first example of a controlled movement of the inner parts of complex double emulsions by magnetic manipulation via interfacially confined magnetic nanoparticles. KW - Janus droplets KW - Pickering emulsions KW - magnetic manipulation KW - gold nanoparticles KW - magnetite nanoparticles Y1 - 2021 U6 - https://doi.org/10.3390/nano11123312 SN - 2079-4991 VL - 11 IS - 12 PB - MDPI CY - Basel ER - TY - JOUR A1 - Garrido, Claudia A1 - Leimkühler, Silke T1 - The inactivation of human aldehyde oxidase 1 by hydrogen peroxide and superoxide JF - Drug metabolism and disposition / American Society for Pharmacology and Experimental Therapeutics N2 - Mammalian aldehyde oxidases (AOX) are molybdo-flavoenzymes of pharmacological and pathophysiologic relevance that are involved in phase I drug metabolism and, as a product of their enzymatic activity, are also involved in the generation of reactive oxygen species. So far, the physiologic role of aldehyde oxidase 1 in the human body remains unknown. The human enzyme hAOX1 is characterized by a broad substrate specificity, oxidizing aromatic/aliphatic aldehydes into their corresponding carboxylic acids, and hydroxylating various heteroaromatic rings. The enzyme uses oxygen as terminal electron acceptor to produce hydrogen peroxide and superoxide during turnover. Since hAOX1 and, in particular, some natural variants produce not only H2O2 but also high amounts of superoxide, we investigated the effect of both ROS molecules on the enzymatic activity of hAOX1 in more detail. We compared hAOX1 to the high-O-2(.-)-producing natural variant L438V for their time-dependent inactivation with H2O2/O-2(.-) during substrate turnover. We show that the inactivation of the hAOX1 wild-type enzyme is mainly based on the production of hydrogen peroxide, whereas for the variant L438V, both hydrogen peroxide and superoxide contribute to the time-dependent inactivation of the enzyme during turnover. Further, the level of inactivation was revealed to be substrate-dependent: using substrates with higher turnover numbers resulted in a faster inactivation of the enzymes. Analysis of the inactivation site of the enzyme identified a loss of the terminal sulfido ligand at the molybdenum active site by the produced ROS during turnover. Y1 - 2021 U6 - https://doi.org/10.1124/dmd.121.000549 SN - 1521-009X SN - 0090-9556 VL - 49 IS - 9 SP - 729 EP - 735 PB - American Society for Pharmacology and Experimental Therapeutics CY - Bethesda ER - TY - JOUR A1 - Hermanns, Jolanda A1 - Keller, David T1 - School-related content knowledge in organic chemistry BT - How does the Bachelor and Master studies? JF - Journal of chemical education / Division of Chemical Education, Inc., American Chemical Society N2 - In this paper the development, use, and evaluation of tasks based on the construct of school-related content knowledge are described. The tasks were used in seminars on organic chemistry for bachelor and master preservice chemistry teachers at a German university. For the evaluation a questionnaire with open and closed items was used. The tasks were rated by the preservice chemistry teachers as relevant for their future profession as a chemistry teacher if the content of the tasks is part of the school curriculum. If the content does not belong to the school curriculum, they rated the nature of the tasks still as relevant; they seem to recognize the importance of conceptual knowledge for their future profession. However, the master's preservice teachers argued with this conceptual knowledge more often than the bachelor's preservice teachers. Although the study is cross-sectional, a certain shift from the focus on the content to conceptual knowledge from bachelor's to master's preservice teachers can be observed. KW - Organic Chemistry KW - Second-Year Undergraduate KW - Analogies/Transfer Y1 - 2021 U6 - https://doi.org/10.1021/acs.jchemed.0c01415 SN - 0021-9584 SN - 1938-1328 VL - 98 IS - 3 SP - 763 EP - 773 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schwarze, Thomas A1 - Riemer, Janine T1 - Highly K+ selective probes with fluorescence emission wavelengths higher than 500 nm in water JF - ChemistrySelect N2 - Herein, we report on the synthesis of highly K+/Na+ selective fluorescent probes in a feasible number of synthetic steps. These K+ selective fluorescent probes, so called fluoroionophores, 1 and 2 consists of different highly K+/Na+ selective building blocks the alkoxy-substituted N-phenylaza-18-crown-6 lariat ethers (ionophores) and "green" (cf. coumarin unit in 1) or "red" (cf. nile red unit in 2) fluorescent moieties (fluorophores). The fluorescent probes 1 and 2 show K+ induced fluorescence enhancement factors of 4.1 for 1 and 1.9 for 2 and dissociation constants for the corresponding K+ complexes of 43 mM (1+K+) and 18 mM (2+K+) in buffered aqueous solution. The fluorescence signal of 1 and 2 is changed by less than 5 % by pH values in the range of 6.8 to 8.8. Thus, 1 and 2 are capable fluorescent tools to determine extracellular K+ levels by fluorescence enhancements at wavelengths higher than 500 nm. KW - potassium KW - sodium KW - fluorescence KW - selectivity KW - probes Y1 - 2020 U6 - https://doi.org/10.1002/slct.202003785 SN - 2365-6549 VL - 5 IS - 42 SP - 13174 EP - 13178 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Intramolecular carbene stabilization via 3c,2e bonding on basis of the magnetic criterion JF - Tetrahedron : the international journal for the rapid publication of full original research papers and critical reviews in organic chemistry N2 - The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent cyclobutylcarbene 8, 1,2-diboretane-3-ylidene 9, and some carbene analogues of boron 14-18 as most intriguing examples of carbenes, which can be stabilized as homoaromatic systems with 3c,2e bonding, have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually, ring current effect/anisotropy effects as measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the degree of present 3c,2e-homoaromaticity. Results are confirmed by geometry (bond angles and bond lengths) and spectroscopic data, the delta(B-11)/ppm data and the C-13 chemical shifts of the carbene electron-deficient centre. KW - Cyclobutylcarbene KW - 1,2-diboretane-3-ylidene KW - 3c,2e-bonding KW - Through-space NMR shieldings (TSNMRS) KW - NICS Y1 - 2021 U6 - https://doi.org/10.1016/j.tet.2021.132357 SN - 0040-4020 SN - 1464-5416 VL - 95 PB - Elsevier Science CY - Amsterdam ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Quantification of sigma-acceptor and pi-donor stabilization in O, S and Hal analogues of N-heterocyclic carbenes (NHCs) on the magnetic criterion JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers. Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpca.1c05257 SN - 1089-5639 SN - 1520-5215 VL - 125 IS - 33 SP - 7235 EP - 7245 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Hermanns, Jolanda A1 - Keller, David T1 - How do preservice chemistry teachers rate tasks following the construct of school-related content knowledge in a concept-orientated course on organic chemistry? JF - Journal of chemical education / Division of Chemical Education, Inc., American Chemical Society N2 - In this paper, we describe a study on tasks following the construct of school-related content knowledge. We know from previous studies that such tasks were rated by the preservice chemistry teachers as important for their future profession. Those studies were conducted in a traditional course on organic chemistry which was organized around chemical families. Therefore, we used and evaluated the tasks again in a new course on organic chemistry which is organized around basic concepts in organic chemistry. The results of this evaluation show that the students rate the tasks equally well but use other arguments for their rating. They do not focus only on the content of the tasks and whether this content belongs to the school curriculum or not. The students of the conceptual course rated the content more often (95%) as important for their future profession compared with the students in the traditional course (57%). Both groups of students rated the importance of the nature of the task the same way. KW - Organic chemistry KW - Second-Year undergraduate KW - Alcohols KW - Curriculum KW - Molecular structure KW - Organic structure KW - Students Y1 - 2021 U6 - https://doi.org/10.1021/acs.jchemed.1c00593 SN - 0021-9584 SN - 1938-1328 VL - 98 IS - 11 SP - 3442 EP - 3449 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lood, Kajsa A1 - Tikk, Triin A1 - Krüger, Mandy A1 - Schmidt, Bernd T1 - Methylene capping facilitates cross-metathesis reactions of enals BT - a short synthesis of 7-methoxywutaifuranal from the xylochemical isoeugenol JF - The journal of organic chemistry N2 - Four combinations of type-I olefins isoeugenol and 4-hydroxy-3-methoxystyrene with type-II olefins acrolein and crotonaldehyde were investigated in cross-metathesis (CM) reactions. While both type-I olefins are suitable CM partners for this transformation, we observed synthetically useful conversions only with type-II olefin crotonaldehyde. For economic reasons, isoeugenol, a cheap xylochemical available from renewable lignocellulose or from clove oil, is the preferred type-I CM partner. Nearly quantitative conversions to coniferyl aldehyde by the CM reaction of isoeugenol and crotonaldehyde can be obtained at ambient temperature without a solvent or at high substrate concentrations of 2 mol.L-1 with the second-generation Hoveyda-Grubbs catalyst. Under these conditions, the ratio of reactants can be reduced to 1:1.5 and catalyst loadings as low as 0.25 mol % are possible. The high reactivity of the isoeugenol/crotonaldehyde combination in olefin metathesis reactions was demonstrated by a short synthesis of the natural product 7-methoxywutaifuranal, which was obtained from isoeugenol in a 44% yield over five steps. We suggest that the superior performance of crotonaldehyde in the CM reactions investigated can be rationalized by "methylene capping", i.e., the steric stabilization of the propagating Ru-alkylidene species. KW - Aldehydes KW - Catalysts KW - Hydrocarbons KW - Metathesis KW - Mixtures Y1 - 2022 U6 - https://doi.org/10.1021/acs.joc.1c02851 SN - 0022-3263 SN - 1520-6904 VL - 87 IS - 5 SP - 3079 EP - 3088 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Hermanns, Jolanda A1 - Schmidt, Bernd A1 - Glowinski, Ingrid A1 - Keller, David T1 - Online teaching in the course "organic chemistry" for nonmajor chemistry students BT - from necessity to opportunity JF - Journal of chemical education N2 - In this communication the development of an online course on the topic organic chemistry for nonmajor chemistry students is described and discussed. For this online course, the existing classroom course was further developed. New elements such as podcasts, task navigators, and a forum for discussing the solving of tasks or problems with the content were added. This new online course was evaluated. Therefore, a questionnaire was developed. This consists of questions with regard to the longtime learning behavior of the students and to the online learning. The results of this evaluation show that a preference for online learning and a preference for classroom teaching can be measured separately in two scales. Students values on the scale representing a preference for online learning correlate positively and significantly with confidence in the choice of the study subject, enthusiasm about the subject, and the ability to organize their learning, learning environment, and time management. They correlate also with the satisfaction concerning the materials provided. Students values for one of those teaching methods also correlate with their rating with regard to their exam preparation. Values representing a preference for online teaching correlate positively with students better feeling of exam preparation. Values representing a preference for classroom teaching show negative correlations with the values representing students similar or even better preparation for the exams as a result of online teaching. It is therefore not surprising that the ratings for the two scales correlate with the wish for a combination of online teaching and classroom teaching in the future. As a solution, a new course concept for the time after the corona virus crisis that suits all students is outlined in the outlook. KW - first-year undergraduate/general KW - organic chenlistry KW - computer-based KW - learning KW - distance learning/self instruction Y1 - 2020 U6 - https://doi.org/10.1021/acs.jchemed.0c00658 SN - 0021-9584 SN - 1938-1328 VL - 97 IS - 9 SP - 3140 EP - 3146 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Fudickar, Werner A1 - Linker, Torsten T1 - Structural motives controlling the binding affinity of 9,10-bis(methylpyridinium)anthracenes towards DNA JF - Bioorganic & medicinal chemistry : a Tetrahedron publication for the rapid dissemination of full original research papers and critical reviews on biomolecular chemistry, medicinal chemistry and related disciplines N2 - In the search of new DNA groove binding agents a series of substituted 9,10-methylpyridiniumanthracenes have been synthesized and their interactions with DNA have been studied by UV/vis absorption, CD and fluorescence spectroscopy. A minor groove binding mode is confirmed by DNA melting studies, strong CD effects, the dependence of the binding affinity on ionic strength, and the differentiation between AT and GC base pairs. No binding occurs to GC sequences. Binding constants to calf thymus DNA (ct-DNA) and poly(dA:dT) in the range between 1 x 10(4) and 3 x 10(5) M-1 have been determined. The binding strength decreases with the size of substituents attached at the anthracene site. Variation of the substitution pattern of the charged groups shows that methyl groups in meta position cause slightly stronger binding than methyl groups in para position. In contrast, with these groups in ortho position, no binding interaction has been observed. The strongest binding is achieved with an expansion of the peripheral heterocycle from pyridine to quinoline. Molecular modeling reveals the pivotal role of the substitution pattern: Anthracenes with para and meta pyridines align along the minor grooves. On the other hand, the ortho derivative adopts no groove-alignment. KW - groove binding KW - anthracenes KW - ct-DNA KW - fluorescence enhancement KW - docking Y1 - 2020 U6 - https://doi.org/10.1016/j.bmc.2020.115432 SN - 0968-0896 SN - 1464-3391 VL - 28 IS - 8 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Hermanns, Jolanda T1 - The task navigator following the STRAKNAP concept BT - Development, application, and evaluation of a new scaffold to support nonmajor chemistry students while solving tasks in organic chemistry JF - Journal of chemical education / Division of Chemical Education, Inc., American Chemical Society N2 - Educational Scaffolding was first mentioned in 1976 by Wood et al. Several examples for scaffolding in chemistry are also known from the literature. As written scaffolds, stepped supporting tools to support students while solving problems in organic chemistry were developed, applied, and evaluated. Although the students rated the tool as very helpful, a think-aloud study showed that the support given by this scaffold was not sufficient. As a further development of stepped supporting tools, task navigators were therefore developed, applied, and evaluated. This new scaffold gives tips on strategy, knowledge, and application of knowledge after the STRAKNAP concept. The evaluation of this tool shows that the students rated the tool as being very helpful. A think-aloud study showed that the scaffold supports the students while they solve a problem. Because of the stepwise construction of the task navigators and the providing of the knowledge needed for the application, the students can solve parts of the task successfully even if they do not solve all parts correctly; the students can always start from scratch. When students use the tool regularly, their knowledge of organic chemistry increases compared to students who did not use the tool at all. The task navigator is not only a scaffold for the content of the task but also for the development of methodological competences on the field of strategies and applying knowledge. KW - First-Year Undergraduate/General KW - Organic Chemistry KW - Distance KW - Learning/Chemistry Education Research Y1 - 2021 U6 - https://doi.org/10.1021/acs.jchemed.0c01162 SN - 0021-9584 SN - 1938-1328 VL - 98 IS - 4 SP - 1077 EP - 1087 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Krüger, Tobias A1 - Bramborg, Andrea A1 - Kelling, Alexandra A1 - Sperlich, Eric A1 - Linker, Torsten T1 - Birch Reduction of Arenes as an Easy Entry to γ-Spirolactones JF - European journal of organic chemistry N2 - A convenient method for the synthesis of γ-spirolactones in only 2–3 steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of ethylene oxide affords hydroxy acids, which undergo direct lactonization during work-up. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and dicarboxylic acids. Subsequent hydrogenation proceeds smoothly with Pd/C as catalyst and saturated γ-spirolactones are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation with Raney nickel or Wilkinson's catalyst to obtain products with 1 double bond. Overall, more than 30 new γ-spirolactones have been synthesized in analytically pure form. KW - Arenes KW - Birch reduction KW - Hydrogenation KW - Lactones KW - Synthetic methods Y1 - 2021 U6 - https://doi.org/10.1002/ejoc.202101018 SN - 1434-193X SN - 1099-0690 VL - 2021 IS - 46 SP - 6383 EP - 6391 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Krüger, Tobias A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Linker, Torsten T1 - Simple Synthesis of gamma-Spirolactams by Birch Reduction of Benzoic Acids JF - European journal of organic chemistry N2 - A convenient synthesis of gamma-spirolactams in only two steps was developed. Birch reduction of benzoic acids and immediate alkylation with chloroacetonitrile afforded cyclohexadienes in high yields. The products could be isolated by crystallization on a large scale in analytically pure form. Subsequent hydrogenation with platinum(IV) oxide as the catalyst reduced the nitrile functionality and the double bonds in the same step with excellent stereoselectivity. The relative configurations were determined unequivocally by X-ray analyses. Direct cyclization of the intermediary formed amino acids afforded the desired gamma-spirolactams in excellent overall yields. The procedure is characterized by few steps, cheap reagents, and can be performed on a large scale, interesting for industrial processes. KW - Diastereoselectivity KW - Hydrogenation KW - Lactams KW - Reduction KW - Synthetic methods Y1 - 2016 U6 - https://doi.org/10.1002/ejoc.201601650 SN - 1434-193X SN - 1099-0690 IS - 6 SP - 1074 EP - 1077 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Polley, Nabarun A1 - Werner, Peter A1 - Balderas-Valadez, Ruth Fabiola A1 - Pacholski, Claudia T1 - Bottom, top, or in between BT - combining plasmonic nanohole arrays and hydrogel microgels for optical fiber snsor applications JF - Advanced materials interfaces N2 - Attractive label-free plasmonic optical fiber sensors can be developed by cleverly choosing the arrangement of plasmonic nanostructures and other building blocks. Here, the final response depends very much on the alignment and position (stacking) of the individual elements. In this work, three different types of fiber optic sensing geometries fabricated by simple layer-by-layer stacking are presented, consisting of stimulus-sensitive poly-N-isopropylacrylamide (polyNIPAM) microgel arrays and plasmonic nanohole arrays (NHAs), namely NHA/polyNIPAM, polyNIPAM/NHA, polyNIPAM/NHA/polyNIPAM. Their optical response to a representative stimulus, namely temperature, is investigated. NHA/polyNIPAM monitors the volume phase transition of polyNIPAM microgels through changes in the spectral position and the amplitude of the reflection minimum of plasmonic NHA. In contrast, polyNIPAM/NHA shows a more complex response to the swelling and collapse of polyNIPAM microgels in their reflectance spectra. The most pronounced changes in optical response are observed by monitoring the amplitude of the reflectance minimum of this sensor during heating/cooling cycles. Finally, the triple stack of polyNIPAM/NHA/polyNIPAM at the end of a optical fiber tip combines the advantages of the NHA/polyNIPAM, polyNIPAM/NHA double stacks for optical sensing. The unique layer-by-layer stacking of microgel and nanostructure is customizable and can be easily adopted for other applications. KW - bottom-up fabrication KW - layer-by-layer stacking KW - microgel arrays KW - optical KW - fiber sensors KW - plasmonic nanohole arrays Y1 - 2022 U6 - https://doi.org/10.1002/admi.202102312 SN - 2196-7350 VL - 9 IS - 15 PB - Wiley CY - Hoboken ER - TY - GEN A1 - Pacholski, Claudia A1 - Agarwal, Vivechana A1 - Balderas-Valadez, Ruth Fabiola T1 - Fabrication of porous silicon-based optical sensors using metal-assisted chemical etching N2 - Optical biosensors based on porous silicon were fabricated by metal assisted chemical etching. Thereby double layered porous silicon structures were obtained consisting of porous pillars with large pores on top of a porous silicon layer with smaller pores. These structures showed a similar sensing performance in comparison to electrochemically produced porous silicon interferometric sensors. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 316 KW - fourier-transform spectroscopy KW - nanostructures KW - nanowires Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-394426 SP - 21430 EP - 21434 ER - TY - JOUR A1 - Balderas-Valadez, Ruth Fabiola A1 - Antunez, E. E. A1 - Olive-Mendez, Sion Federico A1 - Pacholski, Claudia A1 - Campos-Alvarez, Jose A1 - Bokhimi, Xim A1 - Agarwal, V. T1 - Porous silicon pillar and bilayer structure as a nucleation center for the formation of aligned vanadium pentoxide nanorods JF - Ceramics International N2 - Porous silicon single layer (PSM), bilayer (PSB) and pillar (PSP) structures have been evaluated as nucleation centers for vanadium pentoxide (V2O5) crystals. Deposition of vanadium precursor over different substrates (drop casting technique), followed by annealing treatment under Ar-H-2 (5% H-2) atmosphere, induced crystallization of vanadium oxide. With respect to c-Si/SiO2 substrate, V2O5 nanorods with relatively large aspect ratio were formed over and within PSP structures. On the other hand, pores in PSM and PSB were found to be filled with relatively smaller crystals. Additionally, PSB provided a nucleation substrate capable to align the nanocrystals in a preferential orientation, while V2O5 crystals grown on PSP were found to be randomly aligned around the nanoporous pillar microstructure. Nanorods and nanocrystals were identified as V2O5 by temperature-controlled XRD measurements and evidence of their crystalline nature was observed via transmission electron microscopy. A careful analysis of electronic microscopy images allows the identification of the facets composing the ends of the crystals and its corresponding surface free energy has been evaluated employing the Wulff theorem. Such high surface area composite structures have potential applications as cathode material in Lithium-ion batteries. KW - Porous silicon KW - Vanadium pentoxide KW - Nanorods KW - Crystallization KW - Nanostructures Y1 - 2017 U6 - https://doi.org/10.1016/j.ceramint.2017.03.114 SN - 0272-8842 SN - 1873-3956 VL - 43 SP - 8023 EP - 8030 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Balderas-Valadez, Ruth Fabiola A1 - Schürmann, Robin Mathis A1 - Pacholski, Claudia T1 - One Spot-Two Sensors: Porous Silicon Interferometers in Combination With Gold Nanostructures Showing Localized Surface Plasmon Resonance JF - Frontiers in chemistry N2 - Sensors composed of a porous silicon monolayer covered with a film of nanostructured gold layer, which provide two optical signal transduction methods, are fabricated and thoroughly characterized concerning their sensing performance. For this purpose, silicon substrates were electrochemically etched in order to obtain porous silicon monolayers, which were subsequently immersed in gold salt solution facilitating the formation of a porous gold nanoparticle layer on top of the porous silicon. The deposition process was monitored by reflectance spectroscopy, and the appearance of a dip in the interference pattern of the porous silicon layer was observed. This dip can be assigned to the absorption of light by the deposited gold nanostructures leading to localized surface plasmon resonance. The bulk sensitivity of these sensors was determined by recording reflectance spectra in media having different refractive indices and compared to sensors exclusively based on porous silicon or gold nanostructures. A thorough analysis of resulting shifts of the different optical signals in the reflectance spectra on the wavelength scale indicated that the optical response of the porous silicon sensor is not influenced by the presence of a gold nanostructure on top. Moreover, the adsorption of thiol-terminated polystyrene to the sensor surface was solely detected by changes in the position of the dip in the reflectance spectrum, which is assigned to localized surface plasmon resonance in the gold nanostructures. The interference pattern resulting from the porous silicon layer is not shifted to longer wavelengths by the adsorption indicating the independence of the optical response of the two nanostructures, namely porous silicon and nanostructured gold layer, to refractive index changes and pointing to the successful realization of two sensors in one spot. KW - porous silicon KW - interferometry KW - gold nanostructures KW - surface plasmon resonance KW - optical sensor Y1 - 2019 U6 - https://doi.org/10.3389/fchem.2019.00593 SN - 2296-2646 VL - 7 PB - Frontiers Research Foundation CY - Lausanne ER - TY - JOUR A1 - Zheng, Ju-Sheng A1 - Luan, Jian'an A1 - Sofianopoulou, Eleni A1 - Imamura, Fumiaki A1 - Stewart, Isobel D. A1 - Day, Felix R. A1 - Pietzner, Maik A1 - Wheeler, Eleanor A1 - Lotta, Luca A. A1 - Gundersen, Thomas E. A1 - Amiano, Pilar A1 - Ardanaz, Eva A1 - Chirlaque, Maria-Dolores A1 - Fagherazzi, Guy A1 - Franks, Paul W. A1 - Kaaks, Rudolf A1 - Laouali, Nasser A1 - Mancini, Francesca Romana A1 - Nilsson, Peter M. A1 - Onland-Moret, N. Charlotte A1 - Olsen, Anja A1 - Overvad, Kim A1 - Panico, Salvatore A1 - Palli, Domenico A1 - Ricceri, Fulvio A1 - Rolandsson, Olov A1 - Spijkerman, Annemieke M. W. A1 - Sanchez, Maria-Jose A1 - Schulze, Matthias B. A1 - Sala, Nuria A1 - Sieri, Sabina A1 - Tjonneland, Anne A1 - Tumino, Rosario A1 - van der Schouw, Yvonne T. A1 - Weiderpass, Elisabete A1 - Riboli, Elio A1 - Danesh, John A1 - Butterworth, Adam S. A1 - Sharp, Stephen J. A1 - Langenberg, Claudia A1 - Forouhi, Nita G. A1 - Wareham, Nicholas J. T1 - Plasma vitamin C and type 2 diabetes BT - genome-wide association study and Mendelian randomization analysis in European populations JF - Diabetes care N2 - OBJECTIVE: Higher plasma vitamin C levels are associated with lower type 2 diabetes risk, but whether this association is causal is uncertain. To investigate this, we studied the association of genetically predicted plasma vitamin C with type 2 diabetes. RESEARCH DESIGN AND METHODS: We conducted genome-wide association studies of plasma vitamin C among 52,018 individuals of European ancestry to discover novel genetic variants. We performed Mendelian randomization analyses to estimate the association of genetically predicted differences in plasma vitamin C with type 2 diabetes in up to 80,983 case participants and 842,909 noncase participants. We compared this estimate with the observational association between plasma vitamin C and incident type 2 diabetes, including 8,133 case participants and 11,073 noncase participants. RESULTS: We identified 11 genomic regions associated with plasma vitamin C (P < 5 x 10(-8)), with the strongest signal at SLC23A1, and 10 novel genetic loci including SLC23A3, CHPT1, BCAS3, SNRPF, RER1, MAF, GSTA5, RGS14, AKT1, and FADS1. Plasma vitamin C was inversely associated with type 2 diabetes (hazard ratio per SD 0.88; 95% CI 0.82, 0.94), but there was no association between genetically predicted plasma vitamin C (excluding FADS1 variant due to its apparent pleiotropic effect) and type 2 diabetes (1.03; 95% CI 0.96, 1.10). CONCLUSIONS: These findings indicate discordance between biochemically measured and genetically predicted plasma vitamin C levels in the association with type 2 diabetes among European populations. The null Mendelian randomization findings provide no strong evidence to suggest the use of vitamin C supplementation for type 2 diabetes prevention. Y1 - 2020 U6 - https://doi.org/10.2337/dc20-1328 SN - 0149-5992 SN - 1935-5548 VL - 44 IS - 1 SP - 98 EP - 106 PB - American Diabetes Association CY - Alexandria ER - TY - JOUR A1 - Ziemann, Martin Andreas A1 - Madariaga, Juan Manuel T1 - Applications of Raman spectroscopy in art and archaeology JF - Journal of Raman spectroscopy N2 - The 10th edition of the International Congress on the Application of Raman Spectroscopy in Art and Archaeology (RAA2019) was held in Potsdam (Germany) from 3 to 7 September 2019, with eight keynote lectures, 35 oral presentations and 18 Poster Presentations. The number of active participants was 68 delegates from 20 countries among the 236 authors that presented at least one work. Y1 - 2020 U6 - https://doi.org/10.1002/jrs.6054 SN - 0377-0486 SN - 1097-4555 VL - 52 IS - 1 SP - 8 EP - 14 PB - Wiley CY - Hoboken ER - TY - THES A1 - Bilkay, Taybet T1 - Thiophen und Benzodithiophen basierte organische Halbleiter für aus Lösung prozessierbare Feldeffekttransistoren T1 - Thiophene and benzodithiophene based organic semiconductors for solution processable field effect transistors N2 - Diese Arbeit befasst sich mit der Synthese und Charakterisierung von organolöslichen Thiophen und Benzodithiophen basierten Materialien und ihrer Anwendung als aktive lochleitende Halbleiterschichten in Feldeffekttransistoren. Im ersten Teil der Arbeit wird durch eine gezielte Modifikation des Thiophengrundgerüstes eine neue Comonomer-Einheit für die Synthese von Thiophen basierten Copolymeren erfolgreich dargestellt. Die hydrophoben Hexylgruppen in der 3-Position des Thiophens werden teilweise durch hydrophile 3,6-Dioxaheptylgruppen ersetzt. Über die Grignard-Metathese nach McCullough werden statistische Copolymere mit unterschiedlichen molaren Anteilen vom hydrophoben Hexyl- und hydrophilem 3,6-Dioxaheptylgruppen 1:1 (P-1), 1:2 (P-2) und 2:1 (P-3) erfolgreich hergestellt. Auch die Synthese eines definierten Blockcopolymers BP-1 durch sequentielle Addition der Comonomere wird realisiert. Optische und elektrochemische Eigenschaften der neuartigen Copolymere sind vergleichbar mit P3HT. Mit allen Copolymeren wird ein charakteristisches Transistorverhalten in einem Top-Gate/Bottom-Kontakt-Aufbau erhalten. Dabei werden mit P-1 als die aktive Halbleiterschicht im Bauteil, PMMA als Dielektrikum und Silber als Gate-Elektrode Mobilitäten von bis zu 10-2 cm2/Vs erzielt. Als Folge der optimierten Grenzfläche zwischen Dielektrikum und Halbleiter wird eine Verbesserung der Luftstabilität der Transistoren über mehrere Monate festgestellt. Im zweiten Teil der Arbeit werden Benzodithiophen basierte organische Materialien hergestellt. Für die Synthese der neuartigen Benzodithiophen-Derivate wird die Schlüsselverbindung TIPS-BDT in guter Ausbeute dargestellt. Die Difunktionalisierung von TIPS-BDT in den 2,6-Positionen über eine elektrophile Substitution liefert die gewünschten Dibrom- und Distannylmonomere. Zunächst werden über die Stille-Reaktion alternierende Copolymere mit alkylierten Fluoren- und Chinoxalin-Einheiten realisiert. Alle Copolymere zeichnen sich durch eine gute Löslichkeit in gängigen organischen Lösungsmitteln, hohe thermische Stabilität und durch gute Filmbildungseigenschaften aus. Des Weiteren sind alle Copolymere mit HOMO Lagen höher als -6.3 eV, verglichen mit den Thiophen basierten Copolymeren (P-1 bis P-3), sehr oxidationsstabil. Diese Copolymere zeigen amorphes Verhalten in den Halbleiterschichten in OFETs auf und es werden Mobilitäten bis zu 10-4 cm2/Vs erreicht. Eine Abhängigkeit der Bauteil-Leistung von dem Zinngehalt-Rest im Polymer wird nachgewiesen. Ein Zinngehalt von über 0.6 % kann enormen Einfluss auf die Mobilität ausüben, da die funktionellen SnMe3-Gruppen als Fallenzustände wirken können. Alternativ wird das alternierende TIPS-BDT/Fluoren-Copolymer P-5-Stille nach der Suzuki-Methode polymerisiert. Mit P-5-Suzuki als die aktive organische Halbleiterschicht im OFET wird die höchste Mobilität von 10-2 cm2/Vs erzielt. Diese Mobilität ist somit um zwei Größenordnungen höher als bei P-5-Stille, da die Fallenzustände in diesem Fall minimiert werden und folglich der Ladungstransport verbessert wird. Sowohl das Homopolymer P-12 als auch das Copolymer mit dem aromatischen Akzeptor Benzothiadiazol P-9 führen zu schwerlöslichen Polymeren. Aus diesem Grund werden einerseits Terpolymere aus TIPS-BDT/Fluoren/BTD-Einheiten P-10 und P-11 aufgebaut und andererseits wird versucht die TIPS-BDT-Einheit in die Seitenkette des Styrols einzubringen. Mit der Einführung von BTD in die Hauptpolymerkette werden insbesondere die Absorptions- und die elektrochemischen Eigenschaften beeinflusst. Im Vergleich zu dem TIPS-BDT/Fluoren-Copolymer reicht die Absorption bis in den sichtbaren Bereich und die LUMO Lage wird zu niederen Werten verschoben. Eine Verbesserung der Leistung in den Bauteilen wird jedoch nicht festgestellt. Die erfolgreiche erstmalige Synthese von TIPS-BDT als Seitenkettenpolymer an Styrol P-13 führt zu einem löslichen und amorphen Polymer mit vergleichbaren Mobilitäten von Styrol basierten Polymeren (µ = 10-5 cm2/Vs) im OFET. Ein weiteres Ziel dieser Arbeit ist die Synthese von niedermolekularen organolöslichen Benzodithiophen-Derivaten. Über Suzuki- und Stille-Reaktionen ist es erstmals möglich, verschiedenartige Aromaten über eine σ-Bindung an TIPS-BDT in den 2,6-Positionen zu knüpfen. Die UV/VIS-Untersuchungen zeigen, dass die Absorption durch die Verlängerung der π-Konjugationslänge zu höheren Wellenlängen verschoben wird. Darüber hinaus ist es möglich, thermisch vernetzbare Gruppen wie Allyloxy in das Molekülgerüst einzubauen. Das Einführen von F-Atomen in das Molekülgerüst resultiert in einer verstärkten Packungsordnung im Fluorbenzen funktionalisiertem TIPS-BDT (SM-4) im Festkörper mit sehr guten elektronischen Eigenschaften im OFET, wobei Mobilitäten bis zu 0.09 cm2/Vs erreicht werden. N2 - This work describes the synthesis and characterization of organo-soluble thiophene and benzodithiophene based materials and their application as hole-transporting active semiconductor layers in field effect transistors. The first part of this work introduces the targeted modification of the thiophene base unit, obtaining new comonomers for the corresponding copolymers. The hydrophobic hexyl groups in the 3-position of thiophene are partially replaced by hydrophilic 3,6-Dioxaheptyl groups. Using the Grignard metathesis developed by McCullough, statistical copolymers with different molar ratios of hydrophobic and hydrophilic side groups 1:1 (P-1), 1:2 (P-2) and 2:1 (P-3) are synthesized. Furthermore a defined blockcopolymer is synthesized by a sequential comonomer addition. Optical and electrochemical properties of the novel copolymers are comparable to the homopolymer P3HT. All copolymers show clearly transistor characteristics in a top-gate/bottom-contact configuration. Devices with P-1 as active semiconductor layer, PMMA as dielectric and silver as the gate electrode show mobilities up to 10-2 cm2/Vs. As a result of the optimized semiconductor and dielectric interface an improvement of the air stability of the transistors is observed for several months. The second part describes the synthesis of benzodithiophene based organic materials. For the synthesis of the novel benzodithiophene-derivatives the key intermediate TIPS-BDT is obtained in high yields. A difunctionalization of TIPS-BDT in 2,6-position is observed by electrophilic substitution reactions and provided the desired dibromo- and distannyl-monomers. Via Stille-reaction alternated copolymers with alkylated fluorene and quinoxaline groups are synthesized. All copolymers are soluble in common organic solvents, show high thermal stability and good film forming properties. Furthermore all copolymers have HOMO values above -6.3 eV and are more oxidation stable compared to the thiophene based copolymers (P-1 up to P-3). These copolymers show an amorphous behavior as semiconductor layer in OFETs and mobilities up to 10-4 cm2/Vs are observed. A correlation between the device performance and the tin amount in the polymer could be demonstrated. Hence the functional SnMe3 groups can act as traps, a tin amount higher than 0.6 % can negatively influence the mobility. Alternatively the alternated TIPS-BDT/Fluoren-copolymer P-5-Stille is polymerized by the Suzuki-Method. The highest mobility of 10-2 cm2/Vs is obtained with P-5-Suzuki as active semiconductor layer in OFET. In comparison to P-5-Stille this mobility is two orders of magnitude higher, because in P-5-Suzuki traps are minimized and the charge transfer is improved. The synthesis of homopolymer P-12 as well as the copolymer with aromatic benzothiadiazole P-9 resulted in insoluble polymers. For this reason terpolymers containing TIPS-BDT/Fluoren/BTD units are designed. Additionally an attempt has been made to introduce the TIPS-BDT unit in the side chain of styrene. The introduction of BTD in the conjugated main chain influences especially the absorption and electrochemical properties. Compared to TIPS-BDT/Fluoren-copolymer the absorption of the terpolymer is shifted to the visible region and the LUMO values decreased. An improvement in the device performance is not observed. A side chain polystyrene containing TIPS-BDT P-13 is synthesized successfully. The amorphous and soluble P-13 showed comparable mobilities (µ = 10-5 cm2/Vs) as known styrene based polymers. A further aim of this work is the synthesis of organo-soluble benzodithiophene based small molecules. Using Suzuki- and Stille-reactions different aromatic cores as endcappers are connected by σ-bonds at the 2,6-position of TIPS-BDT. UV/VIS-measurements show a red-shift of the absorption maxima with extension of the π-conjugated system. Furthermore it is possible to introduce thermal cross linkable allyloxy-groups. The F-atoms in the molecule lead to stronger intermolecular interactions in the solid state, which improves the electronic properties and lead to high mobilities up to 0.09 cm2/Vs for TIPS-BDT (SM-4). KW - Thiophen und Benzodithiophen Copolymere KW - konjugierte kleine Moleküle KW - organische Halbleiter KW - OFET KW - Ladungstransport KW - Thiophene and Benzodithiophene copolymers KW - conjugated small molecules KW - organic semiconductors KW - OFET KW - charge transfer Y1 - 2012 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-66164 ER -