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 - Günther, Erika A1 - Klauß, André A1 - Toro-Nahuelpan, Mauricio A1 - Schüler, Dirk A1 - Hille, Carsten A1 - Faivre, Damien T1 - The in vivo mechanics of the magnetotactic backbone as revealed by correlative FLIM-FRET and STED microscopy JF - Scientific reports N2 - Protein interaction and protein imaging strongly benefit from the advancements in time-resolved and superresolution fluorescence microscopic techniques. However, the techniques were typically applied separately and ex vivo because of technical challenges and the absence of suitable fluorescent protein pairs. Here, we show correlative in vivo fluorescence lifetime imaging microscopy Forster resonance energy transfer (FLIM-FRET) and stimulated emission depletion (STED) microscopy to unravel protein mechanics and structure in living cells. We use magnetotactic bacteria as a model system where two proteins, MamJ and MamK, are used to assemble magnetic particles called magnetosomes. The filament polymerizes out of MamK and the magnetosomes are connected via the linker MamJ. Our system reveals that bacterial filamentous structures are more fragile than the connection of biomineralized particles to this filament. More importantly, we anticipate the technique to find wide applicability for the study and quantification of biological processes in living cells and at high resolution. Y1 - 2019 U6 - https://doi.org/10.1038/s41598-019-55804-5 SN - 2045-2322 VL - 9 PB - Nature Publ. Group CY - London 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 - 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 - 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 - 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 - 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 - 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 - Qin, Qing A1 - Zhao, Yun A1 - Schmallegger, Max A1 - Heil, Tobias A1 - Schmidt, Johannes A1 - Walczak, Ralf A1 - Gescheidt-Demner, Georg A1 - Jiao, Haijun A1 - Oschatz, Martin T1 - Enhanced Electrocatalytic N-2 Reduction via Partial Anion Substitution in Titanium Oxide-Carbon Composites JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - The electrochemical conversion of N-2 at ambient conditions using renewably generated electricity is an attractive approach for sustainable ammonia (NH3) production. Considering the chemical inertness of N-2, rational design of efficient and stable catalysts is required. Therefore, in this work, it is demonstrated that a C-doped TiO2/C (C-TixOy/C) material derived from the metal-organic framework (MOF) MIL-125(Ti) can achieve a high Faradaic efficiency (FE) of 17.8 %, which even surpasses most of the established noble metal-based catalysts. On the basis of the experimental results and theoretical calculations, the remarkable properties of the catalysts can be attributed to the doping of carbon atoms into oxygen vacancies (OVs) and the formation of Ti-C bonds in C-TixOy. This binding motive is found to be energetically more favorable for N-2 activation compared to the non-substituted OVs in TiO2. This work elucidates that electrochemical N-2 reduction reaction (NRR) performance can be largely improved by creating catalytically active centers through rational substitution of anions into metal oxides. KW - ammonia synthesis KW - anion substitution KW - MOF-derived catalysts KW - N-2 fixation KW - non-noble metal catalysts Y1 - 2019 U6 - https://doi.org/10.1002/anie.201906056 SN - 1433-7851 SN - 1521-3773 VL - 58 IS - 37 SP - 13101 EP - 13106 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Aloni, Sapir Shekef A1 - Perovic, Milena A1 - Weitman, Michal A1 - Cohen, Reut A1 - Oschatz, Martin A1 - Mastai, Yitzhak T1 - Amino acid-based ionic liquids as precursors for the synthesis of chiral nanoporous carbons JF - Nanoscale Advances N2 - The synthesis of chiral nanoporous carbons based on chiral ionic liquids (CILs) of amino acids as precursors is described. Such unique precursors for the carbonization of CILs yield chiral carbonaceous materials with high surface area (approximate to 620 m(2) g(-1)). The enantioselectivities of the porous carbons are examined by advanced techniques such as selective adsorption of enantiomers using cyclic voltammetry, isothermal titration calorimetry, and mass spectrometry. These techniques demonstrate the chiral nature and high enantioselectivity of the chiral carbon materials. Overall, we believe that the novel approach presented here can contribute significantly to the development of new chiral carbon materials that will find important applications in chiral chemistry, such as in chiral catalysis and separation and in chiral sensors. From a scientific point of view, the approach and results reported here can significantly deepen our understanding of chirality at the nanoscale and of the structure and nature of chiral nonporous materials and surfaces. Y1 - 2019 U6 - https://doi.org/10.1039/c9na00520j SN - 2516-0230 VL - 1 IS - 12 SP - 4981 EP - 4988 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Zhang, Su-Yun A1 - Guo, Wen-Bin A1 - Tang, Ying-Ying A1 - Xu, Jin-Qiu A1 - He, Zhang-Zhen T1 - Observation of Spin Relaxation in a Vanadate Chloride with Quasi-One-Dimensional Linear Chain JF - Crystal growth & design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials N2 - A new cobalt(II) vanadate chloride, Pb2Co(OH)(V2O7)Cl, has been synthesized under mild hydrothermal conditions. It contains quasi-one-dimensional (1D) linear chains built by edge-sharing of (CoO6)-O-II octahedra. The cobalt(II) oxide chains are further interconnected by (V2O7)(4-) dimers into a three-dimensional (3D) anionic framework with Pb2+ and Cl- ions residing in Co4V8 12-member ring tunnels. The intrachain Co center dot center dot center dot Co distance is 3.041 angstrom, while the interchain distances are 8.742 and 9.256 angstrom. Magnetic measurements suggest the ferromagnetic intrachain and the antiferromagnetic interchain interactions with a specific value of J(intra)/J(inter) = 1.7 x 10(3). Zero-field heat capacity demonstrates the magnetic long-range ordering at 5.5 K. Alternating current (AC) magnetic susceptibility under zero external direct current (DC) fields displays two slow magnetic relaxations at low temperatures, giving characteristic relaxations (tau(0)) of 1.2(3) x 10(-12) and 1.9(4) x 10(-10) s with effective energy barriers (Delta(r)) of 76.1(2) and 48.4(5) K. The energy barrier between the spin up and spin-down states can be ascribed to the ferromagnetic spin chain and the Ising-like magnetic anisotropy in Pb2Co(OH)(V2O7)Cl. Y1 - 2019 U6 - https://doi.org/10.1021/acs.cgd.8b01839 SN - 1528-7483 SN - 1528-7505 VL - 19 IS - 4 SP - 2228 EP - 2234 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Mameri, Fatima A1 - Koutchoukali, Ouahiba A1 - Koutchoukali, Mohamed Salah A1 - Hartwig, Anne A1 - Nemdili, Leila A1 - Ulrich, Joachim T1 - Optimum operating conditions for manufacturing ibuprofen tablets coated with polyethylene glycol by melt crystallization process JF - Journal of Thermal Analysis and Calorimetry N2 - The aim of this work is to apply the melt crystallization technology to manufacture ibuprofen tablets coated with polyethylene glycol in a single step. This technology, based on a pastillation process, allows in situ separation between two components (active ingredient and coating material). The design and application of this technique depend on the thermo-physical properties of the substances used, as well as on the existence of a eutectic point in the phase diagram. To evaluate the prerequisite conditions, first, DSC curves, allowing the construction of the phase diagram of the binary system, were investigated and the eutectic point was determined (30 mass% ibuprofen, 52 degrees C). Then, the stability of the selected mixture (10:90 mass% of ibuprofen, PEG6000) was studied by thermogravimetric analysis. Finally, the coating quality was investigated under different operating conditions including viscosity, cooling plate temperature, the power of ultrasound and seeding. This parametric study showed that seeding with PEG6000 is necessary to obtain a hemispherical pastille shape, a suitable separation and a pure and thick coating layer. In addition to the optimization of operating conditions of the in situ coating process, it was possible to determine the optimum viscosity and the cooling plate temperature (271.77 m Pa s, 25 degrees C) to obtain a uniform and crystalline coating. During the deposition of molten drops on the cooled surface, the progression of crystal growth was monitored online by optical microscopy. According to the good separation achieved and to the purity and thickness of the microscopic cross-sectional material, the in situ coating process is conceivable for the production of PEG6000-coated ibuprofen tablets. KW - Ibuprofen KW - PEG6000 KW - Eutectic mixture KW - In situ coating KW - Melt crystallization KW - Pastillation Y1 - 2019 U6 - https://doi.org/10.1007/s10973-018-7667-z SN - 1388-6150 SN - 1588-2926 VL - 136 IS - 2 SP - 833 EP - 842 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Kosmella, Sabine A1 - Klemke, Bastian A1 - Häusler, Ines A1 - Koetz, Joachim T1 - From gel-like Pickering emulsions to highly ordered superparamagnetic magnetite aggregates with embedded gold nanoparticles JF - Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects N2 - Pickering emulsions with two types of nanoparticles, i.e., superparamagnetic magnetite nanoparticles dispersed in n-hexane and gold nanoparticles dispersed in water, were formed by rigorous mixing in presence of surface active polymeric surfactants. Monodisperse magnetite nanoparticles with a mean particle size of 4 nm were obtained by a microwave-assisted synthesis in n-hexane in presence of oleic acid, and gold nanoparticles were produced in aqueous solution in presence of the hyperbranched poly(ethyleneimine) (PEI) or sodium citrate as reducing and stabilizing agent. After mixing the prepared nanoparticle dispersions in presence of the Pluronics an intermediate gel-like phase is formed. The Pickering emulsion droplets in the intermediate phase are stabilized by both types of nanoparticles, as to be seen by cryo-SEM micrographs. After separating, solvent evaporation and redispersion in water highly ordered Pluronic-stabilized superparamagnetic magnetite nanoparticle aggregates with embedded gold nanoparticles can be obtained. KW - Pickering emulsions KW - Pluronics KW - Magnetite and gold nanoparticles KW - Ring tensiometry KW - Cryo-SEM KW - HRTEM KW - Magnetization measurements Y1 - 2019 U6 - https://doi.org/10.1016/j.colsurfa.2019.03.017 SN - 0927-7757 SN - 1873-4359 VL - 570 SP - 331 EP - 338 PB - Elsevier Science CY - Amsterdam ER - TY - JOUR A1 - Otte, Fabian A1 - Schmidt, Bernd T1 - Matsuda-Heck Arylation of Glycals for the Stereoselective Synthesis of Aryl C-Glycosides JF - The journal of organic chemistry N2 - The methoxymethyl-protected glycal L-amicetal, synthesized de novo from L-ethyl lactate through tandem ring-closing metathesis-isomerization sequence, undergoes a highly trans-diastereoselective Heck-type coupling reaction with various arene diazonium salts to furnish 2,3-unsaturated aryl C-glycosides in moderate to excellent yields. The products can be further functionalized, e.g., by hydrogenation, epoxidation, or dihydroxylation to furnish 2,3,6-tridesoxy, 2,3-anhydro-6-desoxy, or 6-desoxy aryl C-glycosides, respectively. The method was applied to the synthesis of an a-configured 6-desoxy-gliflozin derivative. Y1 - 2019 U6 - https://doi.org/10.1021/acs.joc.9b02410 SN - 0022-3263 SN - 1520-6904 VL - 84 IS - 22 SP - 14816 EP - 14829 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Yang, Guang A1 - Zheng, Wei A1 - Tao, Guoqing A1 - Wu, Libin A1 - Zhou, Qi-Feng A1 - Kochovski, Zdravko A1 - Ji, Tan A1 - Chen, Huaijun A1 - Li, Xiaopeng A1 - Lu, Yan A1 - Ding, Hong-ming A1 - Yang, Hai-Bo A1 - Chen, Guosong A1 - Jiang, Ming T1 - Diversiform and Transformable Glyco-Nanostructures Constructed from Amphiphilic Supramolecular Metallocarbohydrates through Hierarchical Self-Assembly: The Balance between Metallacycles and Saccharides JF - ACS nano N2 - During the past decade, self-assembly of saccharide-containing amphiphilic molecules toward bioinspired functional glycomaterials has attracted continuous attention due to their various applications in fundamental and practical areas. However, it still remains a great challenge to prepare hierarchical glycoassemblies with controllable and diversiform structures because of the complexity of saccharide structures and carbohydrate-carbohydrate interactions. Herein, through hierarchical self-assembly of modulated amphiphilic supramolecular metallocarbohydrates, we successfully prepared various well-defined glyco-nanostructures in aqueous solution, including vesicles, solid spheres, and opened vesicles depending on the molecular structures of metallocarbohydrates. More attractively, these glyco-nanostructures can further transform into other morphological structures in aqueous solutions such as worm-like micelles, tubules, and even tupanvirus-like vesicles (TVVs). It is worth mentioning that distinctive anisotropic structures including the opened vesicles (OVs) and TVVs were rarely reported in glycobased nano-objects. This intriguing diversity was mainly controlled by the subtle structural trade-off of the two major components of the amphiphiles, i.e., the saccharides and metallacycles. To further understand this precise structural control, molecular simulations provided deep physical insights on the morphology evolution and balancing of the contributions from saccharides and metallacycles. Moreover, the multivalency of glyco-nanostructures with different shapes and sizes was demonstrated by agglutination with a diversity of sugarbinding protein receptors such as the plant lectins Concanavalin A (ConA). This modular synthesis strategy provides access to systematic tuning of molecular structure and self-assembled architecture, which undoubtedly will broaden our horizons on the controllable fabrication of biomimetic glycomaterials such as biological membranes and supramolecular lectin inhibitors. KW - glycomaterials KW - diversiform structures KW - hierarchical self-assembly KW - metallocarbohydrates KW - anisotropic structures Y1 - 2019 U6 - https://doi.org/10.1021/acsnano.9b07134 SN - 1936-0851 SN - 1936-086X VL - 13 IS - 11 SP - 13474 EP - 13485 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Yuan, Jinkai A1 - Neri, Wilfrid A1 - Zakri, Cecile A1 - Merzeau, Pascal A1 - Kratz, Karl A1 - Lendlein, Andreas A1 - Poulin, Philippe T1 - Shape memory nanocomposite fibers for untethered high-energy microengines JF - Science N2 - Classic rotating engines are powerful and broadly used but are of complex design and difficult to miniaturize. It has long remained challenging to make large-stroke, high-speed, high-energy microengines that are simple and robust. We show that torsionally stiffened shape memory nanocomposite fibers can be transformed upon insertion of twist to store and provide fast and high-energy rotations. The twisted shape memory nanocomposite fibers combine high torque with large angles of rotation, delivering a gravimetric work capacity that is 60 times higher than that of natural skeletal muscles. The temperature that triggers fiber rotation can be tuned. This temperature memory effect provides an additional advantage over conventional engines by allowing for the tunability of the operation temperature and a stepwise release of stored energy. Y1 - 2019 U6 - https://doi.org/10.1126/science.aaw3722 SN - 0036-8075 SN - 1095-9203 VL - 365 IS - 6449 SP - 155 EP - 158 PB - American Assoc. for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Polley, Nabarun A1 - Basak, Supratim A1 - Hass, Roland A1 - Pacholski, Claudia T1 - Fiber optic plasmonic sensors BT - Providing sensitive biosensor platforms with minimal lab equipment JF - Biosensors and bioelectronics : the principal international journal devoted to research, design development and application of biosensors and bioelectronics N2 - A simple, convenient, and inexpensive method to fabricate optical fiber based biosensors which utilize periodic hole arrays in gold films for signal transduction is reported. The process of hole array formation mainly relies on self-assembly of hydrogel microgels in combination with chemical gold film deposition and subsequent transfer of the perforated film onto an optical fiber tip. In the fabrication process solely chemical wet lab techniques are used, avoiding cost-intensive instrumentation or clean room facilities. The presented method for preparing fiber optic plasmonic sensors provides high throughput and is perfectly suited for commercialization using batch processing. The transfer of the perforated gold film onto an optical fiber tip does not affect the sensitivity of the biosensor ((420 +/- 83) nm/refractive index unit (RIU)), which is comparable to sensitivities of sensor platforms based on periodic hole arrays in gold films prepared by significantly more complex methods. Furthermore, real-time and in-line immunoassay studies with a specially designed 3D printed flow cell are presented exploiting the presented optical fiber based biosensors. KW - Surface plasmon resonance KW - Optical fiber KW - Bottom-up fabrication KW - Biosensor KW - 3D printed flow-cell Y1 - 2019 U6 - https://doi.org/10.1016/j.bios.2019.03.020 SN - 0956-5663 SN - 1873-4235 VL - 132 SP - 368 EP - 374 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Keller, Sebastian A1 - Wetterhorn, Karl M. A1 - Vecellio, Alison A1 - Seeger, Mark A1 - Rayment, Ivan A1 - Schubert, Torsten T1 - Structural and functional analysis of an l-serine O-phosphate decarboxylase involved in norcobamide biosynthesis JF - FEBS letters : the journal for rapid publication of short reports in molecular biosciences N2 - Structural diversity of natural cobamides (Cbas, B12 vitamers) is limited to the nucleotide loop. The loop is connected to the cobalt‐containing corrin ring via an (R)‐1‐aminopropan‐2‐ol O‐2‐phosphate (AP‐P) linker moiety. AP‐P is produced by the l‐threonine O‐3‐phosphate (l‐Thr‐P) decarboxylase CobD. Here, the CobD homolog SMUL_1544 of the organohalide‐respiring epsilonproteobacterium Sulfurospirillum multivorans was characterized as a decarboxylase that produces ethanolamine O‐phosphate (EA‐P) from l‐serine O‐phosphate (l‐Ser‐P). EA‐P is assumed to serve as precursor of the linker moiety of norcobamides that function as cofactors in the respiratory reductive dehalogenase. SMUL_1544 (SmCobD) is a pyridoxal‐5′‐phosphate (PLP)‐containing enzyme. The structural analysis of the SmCobD apoprotein combined with the characterization of truncated mutant proteins uncovered a role of the SmCobD N‐terminus in efficient l‐Ser‐P conversion. KW - cobamides KW - ethanolamine phosphate KW - norcobamide biosynthesis KW - serine phosphate decarboxylase Y1 - 2019 U6 - https://doi.org/10.1002/1873-3468.13543 SN - 0014-5793 SN - 1873-3468 VL - 593 IS - 21 SP - 3040 EP - 3053 PB - Wiley CY - Hoboken ER -