TY - JOUR A1 - Hoang, Hoa T. A1 - Haubitz, Toni A1 - Kumke, Michael Uwe T1 - Photophysics of "Floppy" Dyadsas Potential Biomembrane Probes JF - Journal of fluorescence N2 - In the study a dyad (C6 probe), constructed of two dyes with highly different hydrophobicities, was investigated by steady-state and time-resolved spectroscopic techniques in chloroform, methanol, and in phospholipid vesicles, respectively. The dyad was built on two dyes: the lipophilic benzo[a]pyrene (BaP) and the hydrophilic sulforhodamine B (SRB). The dyes were linked via a short, but flexible alkyl chain (six C-atoms). Based on their spectroscopic properties, BaP and SRB showed a very efficient non-radiative resonance energy transfer in solution. Incorporation into a lipid bilayer limited the relative flexibility (degree of freedom) between donor and acceptor and was used for the investigation of fundamental photophysical aspects (especially of FRET) as well as to elucidate the potential of the dyad to probe the interface of vesicles (or cells). The location of the two dyes in vesicles and their respective accessibility for interactions with dye-specific antibodies was investigated. Based on the alteration of the anisotropy, on the rotational correlation time as well as on the diffusion coefficient the incorporation of the C6 probe into the vesicles was evaluated. Especially the limitation in the relative movements of the two dyes was considered and used to differentiate between potential parameters, that influence the energy transfer in the dyad. Transient absorption spectroscopy (TAS) and pulsed-interleave single molecule fluorescence experiments were performed to better understand the intramolecular interactions in the dyad. Finally, in a showcase for a biosensing application of the dyads, the binding of an SRB-specific antibody was investigated when the dyad was incorporated in vesicles. KW - Forster resonance energy transfer(FRET) KW - Antibody binding KW - Vesicles KW - Anisotropy KW - Fluorescence correlation KW - Single molecule fluorescence KW - Transient absorption KW - Pulsed interleaved excitation Y1 - 2018 U6 - https://doi.org/10.1007/s10895-018-2286-4 SN - 1053-0509 SN - 1573-4994 VL - 28 IS - 5 SP - 1225 EP - 1237 PB - Springer CY - New York 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 - Pereira, Rui F. P. A1 - Zehbe, Kerstin A1 - Günter, Christina A1 - dos Santos, Tiago A1 - Nunes, Silvia C. A1 - Almeida Paz, Filipe A. A1 - Silva, Maria M. A1 - Granja, Pedro L. A1 - Taubert, Andreas A1 - de Zea Bermudez, Verónica T1 - Ionic liquid-assisted synthesis of mesoporous silk fibroin/silica hybrids for biomedical applications JF - ACS Omega N2 - New mesoporous silk fibroin (SF)/silica hybrids were processed via a one-pot soft and energy-efficient sol-gel chemistry and self-assembly from a silica precursor, an acidic or basic catalyst, and the ionic liquid 1-butyl-3-methylimidazolium chloride, acting as both solvent and mesoporosity-inducer. The as-prepared materials were obtained as slightly transparent-opaque, amorphous monoliths, easily transformed into powders, and stable up to ca. 300 degrees C. Structural data suggest the formation of a hexagonal mesostructure with low range order and apparent surface areas, pore volumes, and pore radii of 205-263 m(2) g(-1), 0.16-0.19 cm(3) g(-1), and 1.2-1.6 nm, respectively. In all samples, the dominating conformation of the SF chains is the beta-sheet. Cytotoxicity/bioactivity resazurin assays and fluorescence microscopy demonstrate the high viability of MC3T3 pre-osteoblasts to indirect (>= 99 +/- 9%) and direct (78 +/- 2 to 99 +/- 13%) contact with the SF/silica materials. Considering their properties and further improvements, these systems are promising candidates to be explored in bone tissue engineering. They also offer excellent prospects as electrolytes for solid-state electrochemical devices, in particular for fuel cells. Y1 - 2018 U6 - https://doi.org/10.1021/acsomega.8b02051 SN - 2470-1343 VL - 3 IS - 9 SP - 10811 EP - 10822 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Haubitz, Toni A1 - Tsushima, Satoru A1 - Steudtner, Robin A1 - Drobot, Björn A1 - Geipel, Gerhard A1 - Stumpf, Thorsten A1 - Kumke, Michael Uwe T1 - Ultrafast Transient Absorption Spectroscopy of UO(2)(2+)and [UO2Cl](+) JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - For the only water coordinated "free" uranyl (VI) aquo ion in perchlorate solution we identified and assigned several different excited states and showed that the (3)Delta state is the luminescent triplet state from transient absorption spectroscopy. With additional data from other spectroscopic methods (TRLFS, UV/vis) we generated a detailed Jablonski diagram and determined rate constants for several state transitions, like the inner conversion rate constant from the (3)Phi state to the (3)Delta state transition to be 0.35 ps(-1). In contrast to luminescence measurements, it was possible to observe the highly quenched uranyl(VI) ion in highly concentrated chloride solution by TAS and we were able to propose a dynamic quenching mechanism, where chloride complexation is followed by the charge transfer from the excited state uranyl(VI) to chloride. This proposed quenching route is supported by TD-DFT calculations. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpca.8b05567 SN - 1089-5639 VL - 122 IS - 35 SP - 6970 EP - 6977 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Senf, Deborah A1 - Ruprecht, Colin A1 - Kishani, Saina A1 - Matic, Aleksandar A1 - Toriz, Guillermo A1 - Gatenholm, Paul A1 - Wagberg, Lars A1 - Pfrengle, Fabian T1 - Tailormade polysaccharides with defined branching patterns BT - Enzymatic polymerization of arabinoxylan oligosaccharides JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - The heterogeneous nature of non-cellulosic polysaccharides, such as arabinoxylan, makes it difficult to correlate molecular structure with macroscopic properties. To study the impact of specific structural features of the polysaccharides on crystallinity or affinity to other cell wall components, collections of polysaccharides with defined repeating units are required. Herein, a chemoenzymatic approach to artificial arabinoxylan polysaccharides with systematically altered branching patterns is described. The polysaccharides were obtained by glycosynthase-catalyzed polymerization of glycosyl fluorides derived from arabinoxylan oligosaccharides. X-ray diffraction and adsorption experiments on cellulosic surfaces revealed that the physicochemical properties of the synthetic polysaccharides strongly depend on the specific nature of their substitution patterns. The artificial polysaccharides allow structure-property relationship studies that are not accessible by other means. KW - carbohydrates KW - enzymes KW - glycosynthases KW - structure elucidation KW - synthetic methods Y1 - 2018 U6 - https://doi.org/10.1002/anie.201806871 SN - 1433-7851 SN - 1521-3773 VL - 57 IS - 37 SP - 11987 EP - 11992 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Uchida, Ryusuke A1 - Binet, Silvia A1 - Arora, Neha A1 - Jacopin, Gwenole A1 - Alotaibi, Mohammad Hayal A1 - Taubert, Andreas A1 - Zakeeruddin, Shaik Mohammed A1 - Dar, M. Ibrahim A1 - Graetzel, Michael T1 - Insights about the Absence of Rb Cation from the 3D Perovskite Lattice BT - Effect on the Structural, Morphological, and Photophysical Properties and Photovoltaic Performance JF - Small N2 - Efficiencies >20% are obtained from the perovskite solar cells (PSCs) employing Cs+ and Rb+ based perovskite compositions; therefore, it is important to understand the effect of these inorganic cations specifically Rb+ on the properties of perovskite structures. Here the influence of Cs+ and Rb+ is elucidated on the structural, morphological, and photophysical properties of perovskite structures and the photovoltaic performances of resulting PSCs. Structural, photoluminescence (PL), and external quantum efficiency studies establish the incorporation of Cs+ (x < 10%) but amply rule out the possibility of Rb-incorporation into the MAPbI(3) (MA = CH3NH3+) lattice. Moreover, morphological studies and time-resolved PL show that both Cs+ and Rb+ detrimentally affect the surface coverage of MAPbI(3) layers and charge-carrier dynamics, respectively, by influencing nucleation density and by inducing nonradiative recombination. In addition, differential scanning calorimetry shows that the transition from orthorhombic to tetragonal phase occurring around 160 K requires more thermal energy for the Cs-containing MAPbI(3) systems compared to the pristine MAPbI(3). Investigation including mixed halide (I/Br) and mixed cation A-cation based compositions further confirms the absence of Rb+ from the 3D-perovskite lattice. The fundamental insights gained through this work will be of great significance to further understand highly promising perovskite compositions. KW - cation miscibility KW - cesium cation KW - perovskite solar cells KW - rubidium cation KW - X-ray diffraction Y1 - 2018 U6 - https://doi.org/10.1002/smll.201802033 SN - 1613-6810 SN - 1613-6829 VL - 14 IS - 36 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Vacogne, Charlotte Dominique A1 - Wei, Chunxiang A1 - Tauer, Klaus A1 - Schlaad, Helmut T1 - Self-assembly of alpha-helical polypeptides into microscopic and enantiomorphic spirals JF - Journal of the american chemical society N2 - Helical structures are ubiquitous in biological materials and often serve a structural purpose. Bioinspired helical materials can be challenging to synthesize and rarely reach the degree of hierarchy of their natural counterparts. Here we report the first example of particles synthesized by direct emulsification of polypeptides found to display spiral morphologies in the dry state. The polypeptides were alpha-helical homo- and copolypeptides of gamma-benzyl glutamate and allylglycine. The chirality of the spirals was controlled by the chirality of the alpha-helices. Notably, right-handed alpha-helical polypeptides (rich in 1, residues) produced clockwise spirals, whereas left-handed alpha-helical polypeptides (rich in D residues) produced the enantiomorphs, i.e., counterclockwise spirals. The disruption of the alpha-helical conformation by the introduction of chiral defects led to less regular spirals and in some cases their suppression. A hypothesis for the transmission of helicity and chirality from a molecular to a higher hierarchical level, involving fibril bundling of coiled alpha-helices, is proposed. Y1 - 2018 U6 - https://doi.org/10.1021/jacs.8b06503 SN - 0002-7863 VL - 140 IS - 36 SP - 11387 EP - 11394 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Tan, Li A1 - Liu, Bing A1 - Siemensmeyer, Konrad A1 - Glebe, Ulrich A1 - Böker, Alexander T1 - Synthesis of thermo-responsive nanocomposites of superparamagnetic cobalt nanoparticlesipoly(N-isopropylacrylamide) JF - Journal of colloid and interface science N2 - Novel nanocomposites of superparamagnetic cobalt nanoparticles (Co NPs) and poly(N-isopropylacrylamide) (PNIPAM) were fabricated through surface-initiated atom-transfer radical polymerization (SI-ATRP). We firstly synthesized a functional ATRP initiator, containing an amine (as anchoring group) and a 2-bromopropionate group (SI-ATRP initiator). Oleic acid- and trioctylphosphine oxide-coated Co NPs were then modified with the initiator via ligand exchange. The process is facile and rapid for efficient surface functionalization and afterwards the Co NPs can be dispersed into polar solvent DMF without aggregation. Transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and dynamic light scattering measurements confirmed the success of ligand exchange. The following polymerization of NIPAM was conducted on the surface of Co NPs. Temperature-dependent dynamic light scattering study showed the responsive behavior of PNIPAM-coated Co NPs. The combination of superparamagnetic and thermo-responsive properties in these hybrid nanoparticles is promising for future applications e.g. in biomedicine. (C) 2018 Elsevier Inc. All rights reserved. KW - Nanoparticles KW - Superparamagnetic KW - Surface-initiated atom-transfer radical KW - polymerization KW - Responsivity Y1 - 2018 U6 - https://doi.org/10.1016/j.jcis.2018.04.074 SN - 0021-9797 SN - 1095-7103 VL - 526 SP - 124 EP - 134 PB - Elsevier CY - San Diego 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 - 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 - Franz, Alexandra A1 - Többens, Daniel M. A1 - Steckhan, Julia A1 - Schorr, Susan T1 - Determination of the miscibility gap in the solid solutions series of methylammonium lead iodide/chloride JF - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials N2 - Perovskites are widely known for their enormous possibility of elemental substitution, which leads to a large variety of physical properties. Hybrid perovskites such as CH3NH3PbI3 (MAPbI(3)) and CH3NH3PbCl3 (MAPbCl(3)) are perovskites with an A([XII])B([VI)X(-)([II)(])structure, where A is an organic molecule, B is a lead(II) cation and X is a halide anion of iodine or chlorine. Whereas MAPbCl(3) crystallizes in the cubic space group Pm (3) over barm, MAPbI(3) is in the tetragonal space group I4/mcm. The substitution of I by Cl leads to an increased tolerance against humidity but is challenging or even impossible due to their large difference in ionic radii. Here, the influence of an increasing Cl content in the reaction solution on the miscibility of the solid solution members is examined systematically. Powders were synthesized by two different routes depending on the I:Cl ratio. High-resolution synchrotron X-ray data are used to establish values for the limits of the miscibility gap which are 3.1 (1.1) mol% MAPbCl(3) in MAPI(3) and 1.0 (1) mol% MAPbI(3) in MAPCl. The establishment of relations between average pseudo-cubic lattice parameters for both phases allows a determination of the degree of substitution from the observed lattice parameters. KW - powder diffraction KW - hybrid perovskites KW - miscibility gap KW - MAPbX3 Y1 - 2018 U6 - https://doi.org/10.1107/S2052520618010764 SN - 2052-5206 VL - 74 SP - 445 EP - 449 PB - International Union of Crystallography CY - Chester ER - TY - JOUR A1 - Frede, Katja A1 - Schreiner, Monika A1 - Zrenner, R. A1 - Graefe, Jan A1 - Baldermann, Susanne T1 - Carotenoid biosynthesis of pak choi (Brassica rapa ssp chinensis) sprouts grown under different light-emitting diodes during the diurnal course JF - Photochemical & photobiological sciences N2 - Light-emitting diodes (LEDs) are considered the future of greenhouse lighting. This study investigates the carotenoid concentrations of pak choi sprouts after growth under blue, red and white LEDs at six different time points. Furthermore, the diurnal changes of RNA transcripts of key genes of the carotenoid biosynthesis pathway as well as of the carotenoid cleavage dioxygenase 4 (CCD4) gene and of the transcription factor genes elongated hypocotyl 5 (HY5) and circadian clock associated 1 (CCA1) were investigated. The carotenoid concentrations were steady throughout the day, but showed a small maximum in the afternoon. An average total carotenoid concentration of 536 +/- 29 ng mg(-1) DM produced under white LEDs was measured, which is comparable to previously described field-grown levels. The carotenoid concentrations were slightly lower under blue or red LEDs. Moreover, the diurnal RNA transcript rhythms of most of the carotenoid biosynthesis genes showed an increase during the light period, which can be correlated to the carotenoid maxima in the afternoon. Blue LEDs caused the highest transcriptional induction of biosynthetic genes as well as of CCD4, thereby indicating an increased flux through the pathway. In addition, the highest levels of HY5 transcripts and CCA1 transcripts were determined under blue LEDs. Y1 - 2018 U6 - https://doi.org/10.1039/c8pp00136g SN - 1474-905X SN - 1474-9092 VL - 17 IS - 10 SP - 1289 EP - 1300 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Erler, Alexander A1 - Riebe, Daniel A1 - Beitz, Toralf A1 - Löhmannsröben, Hans-Gerd A1 - Grothusheitkamp, Daniela A1 - Kunz, T. A1 - Methner, Frank-Jürgen T1 - Detection of volatile organic compounds in the headspace above mold fungi by GC-soft X-radiation-based APCI-MS JF - Journal of mass spectrometr N2 - Mold fungi on malting barley grains cause major economic loss in malting and brewery facilities. Possible proxies for their detection are volatile and semivolatile metabolites. Among those substances, characteristic marker compounds have to be identified for a confident detection of mold fungi in varying surroundings. The analytical determination is usually performed through passive sampling with solid phase microextraction, gas chromatographic separation, and detection by electron ionization mass spectrometry (EI-MS), which often does not allow a confident determination due to the absence of molecular ions. An alternative is GC-APCI-MS, generally, allowing the determination of protonated molecular ions. Commercial atmospheric pressure chemical ionization (APCI) sources are based on corona discharges, which are often unspecific due to the occurrence of several side reactions and produce complex product ion spectra. To overcome this issue, an APCI source based on soft X-radiation is used here. This source facilitates a more specific ionization by proton transfer reactions only. In the first part, the APCI source is characterized with representative volatile fungus metabolites. Depending on the proton affinity of the metabolites, the limits of detection are up to 2 orders of magnitude below those of EI-MS. In the second part, the volatile metabolites of the mold fungus species Aspergillus, Alternaria, Fusarium, and Penicillium are investigated. In total, 86 compounds were found with GC-EI/APCI-MS. The metabolites identified belong to the substance classes of alcohols, aldehydes, ketones, carboxylic acids, esters, substituted aromatic compounds, terpenes, and sesquiterpenes. In addition to substances unspecific for the individual fungus species, characteristic patterns of metabolites, allowing their confident discrimination, were found for each of the 4 fungus species. Sixty-seven of the 86 metabolites are detected by X-ray-based APCI-MS alone. The discrimination of the fungus species based on these metabolites alone was possible. Therefore, APCI-MS in combination with collision induced dissociation alone could be used as a supervision method for the detection of mold fungi. KW - APCI KW - gas chromatography KW - mass spectrometry KW - mold fungi KW - soft X-radiation KW - volatile organic compounds Y1 - 2018 U6 - https://doi.org/10.1002/jms.4210 SN - 1076-5174 SN - 1096-9888 VL - 53 IS - 10 SP - 911 EP - 920 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Plötz, Per-Arno A1 - Megow, Jörg A1 - Niehaus, Thomas A1 - Kühn, Oliver T1 - All-DFTB Approach to the Parametrization of the System-Bath Hamiltonian Describing Exciton-Vibrational Dynamics of Molecular Assemblies JF - Journal of chemical theory and computation N2 - Spectral density functions are central to the simulation of complex many body systems. Their determination requires making approximations not only to the dynamics but also to the underlying electronic structure theory. Here, blending different methods bears the danger of an inconsistent description. To solve this issue we propose an all-DFTB approach to determine spectral densities for the description of Frenkel excitons in molecular assemblies. The protocol is illustrated for a model of a PTCDI crystal, which involves the calculation of monomeric excitation energies and Coulomb couplings between monomer transitions, as well as their spectral distributions due to thermal fluctuations of the nuclei. Using dynamically defined normal modes, a mapping onto the standard harmonic oscillator spectral densities is achieved. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jctc.8b00493 SN - 1549-9618 SN - 1549-9626 VL - 14 IS - 10 SP - 5001 EP - 5010 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Tan, Li A1 - Liu, Bing A1 - Siemensmeyer, Konrad A1 - Glebe, Ulrich A1 - Böker, Alexander T1 - Synthesis of Polystyrene-Coated Superparamagnetic and Ferromagnetic Cobalt Nanoparticles JF - Polymers N2 - Polystyrene-coated cobalt nanoparticles (NPs) were synthesized through a dual-stage thermolysis of cobalt carbonyl (Co-2(CO)(8)). The amine end-functionalized polystyrene surfactants with varying molecular weight were prepared via atom-transfer radical polymerization technique. By changing the concentration of these polymeric surfactants, Co NPs with different size, size distribution, and magnetic properties were obtained. Transmission electron microscopy characterization showed that the size of Co NPs stabilized with lower molecular weight polystyrene surfactants (M-n = 2300 g/mol) varied from 12-22 nm, while the size of Co NPs coated with polystyrene of middle (M-n = 4500 g/mol) and higher molecular weight (M-n = 10,500 g/mol) showed little change around 20 nm. Magnetic measurements revealed that the small cobalt particles were superparamagnetic, while larger particles were ferromagnetic and self-assembled into 1-D chain structures. Thermogravimetric analysis revealed that the grafting density of polystyrene with lower molecular weight is high. To the best of our knowledge, this is the first study to obtain both superparamagnetic and ferromagnetic Co NPs by changing the molecular weight and concentration of polystyrene through the dual-stage decomposition method. KW - cobalt nanoparticles KW - polystyrene KW - superparamagnetic KW - ferromagnetic KW - molecular weight Y1 - 2018 U6 - https://doi.org/10.3390/polym10101053 SN - 2073-4360 VL - 10 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 - Qi, Wenjing A1 - Zhang, Yufei A1 - Kochovski, Zdravko A1 - Wang, Jue A1 - Lu, Yan A1 - Chen, Guosong A1 - Jiang, Ming T1 - Self-assembly of Human Galectin-1 via dual supramolecular interactions and its inhibition of T-cell agglutination and apoptosis JF - Nano Research N2 - Recently, we proposed a new strategy to construct artificial plant protein assemblies, which were induced by adding a small molecule, based on dual supramolecular interactions. In this paper, we further explored this method by employing Human Galectin-1 (Gal-1) as a building block to form self-assembled microribbons. Two non-covalent interactions, including lactose-lectin binding and dimerization of Rhodamine B (RhB), induced by the small molecule ligand addition, were involved in the crosslinking of the animal protein, resulting in the formation of assemblies. By using transmission electron microscopy (TEM), cryo-electron microscopy (cryo-EM), and three-dimensional (3D) tomographic analysis, we arrived at a possible mechanistic model for the microribbon formation. Furthermore, the morphology of protein assemblies could be fine-timed by varying the incubation time, the protein/ligand ratio, and the chemical structures of ligands. Interestingly, the formation of protein microribbons successfully inhibited Gal-1 induced T-cell agglutination and apoptosis. This is because the multivalent and dynamic interactions in protein assemblies compete with the binding between Gal-1 and the glycans on cell surfaces, which suppresses the function of Gal-1 in promotion of tumor progression and metastasis. KW - protein self-assembly KW - supramolecular interactions KW - galectin KW - cell agglutination Y1 - 2018 U6 - https://doi.org/10.1007/s12274-018-2169-7 SN - 1998-0124 SN - 1998-0000 VL - 11 IS - 10 SP - 5566 EP - 5572 PB - Tsinghua Univ Press CY - Beijing 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 - Goldhahn, Christian A1 - Schubert, Jonas A1 - Schlaad, Helmut A1 - Ferri, James K. A1 - Fery, Andreas A1 - Chanana, Munish T1 - Synthesis of Metal@Protein@Polymer Nanoparticles with Distinct Interfacial and Phase Transfer Behavior JF - Chemistry of materials : a publication of the American Chemical Society N2 - In this study, we present a novel and facile method for the synthesis of multiresponsive plasmonic nanoparticles with an interesting interfacial behavior. We used thiol-initiated photopolymerization technique to graft poly(N-isopropylacrylamide) onto the surface of protein-coated gold nanoparticles. The combination of the protein bovine serum albumin with the thermoresponsive polymer leads to smart hybrid nanoparticles, which show a stimuli-responsive behavior of their aggregation and a precisely controllable phase transfer behavior. Three interconnected stimuli, namely, temperature, ionic strength, and pH, were identified as property tuning switches. The aggregation was completely reversible and was quantified by determining Smoluchowski’s instability ratios with time-resolved dynamic light scattering. The tunable hydrophobicity via the three stimuli was used to study interfacial activity and phase transfer behavior of the nanoparticles at an octanol/water interface. Depending on the type of coating (i.e., protein or protein/polymer) as well as the three external stimuli, the nanoparticles either remained in the aqueous phase (aggregated or nonaggregated), accumulated at the oil/water interface, wet the glass wall between the glass vial and the octanol phase, or even crossed the oil/water interface. Such smart and interfacially active nanoparticles with external triggers that are capable of crossing oil/water interfaces under physiological conditions open up new avenues for a variety of applications ranging from the development of drug-delivery nanosystems across biological barriers to the preparation of new catalytic materials. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b02314 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 19 SP - 6717 EP - 6727 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Ehlert, Christopher A1 - Gühr, Markus A1 - Saalfrank, Peter T1 - An efficient first principles method for molecular pump-probe NEXAFS spectra BT - application to thymine and azobenzene JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - Pump-probe near edge X-ray absorption fine structure (PP-NEXAFS) spectra of molecules offer insight into valence-excited states, even if optically dark. In PP-NEXAFS spectroscopy, the molecule is "pumped" by UV or visible light enforcing a valence excitation, followed by an X-ray "probe" exciting core electrons into (now) partially empty valence orbitals. Calculations of PP-NEXAFS have so far been done by costly, correlated wavefunction methods which are not easily applicable to medium-sized or large molecules. Here we propose an efficient, first principles method based on density functional theory in combination with the transition potential and Delta SCF methodology (TP-DFT/Delta SCF) to compute molecular ground state and PP-NEXAFS spectra. We apply the method to n ->pi* pump/O-K-edge NEXAFS probe spectroscopy of thymine (for which both experimental and other theoretical data exist) and to n -> pi* or pi -> pi* pump/N-K-edge NEXAFS probe spectroscopies of trans-and cis-azobenzene. Published by AIP Publishing. Y1 - 2018 U6 - https://doi.org/10.1063/1.5050488 SN - 0021-9606 SN - 1089-7690 VL - 149 IS - 14 PB - American Institute of Physics CY - Melville ER -