TY - JOUR A1 - Biermann, Ursula A1 - Meier, Michael A. R. A1 - Butte, Werner A1 - Metzger, Jürgen O. T1 - Cross-metathesis of unsaturated triglycerides with methyl acrylate synthesis of a dimeric metathesis product JF - European journal of lipid science and technology N2 - Highly functionalized dimeric triglycerides, such as compound 2, are obtained as minor products besides branched macromolecules from the acyclic triene metathesis (ATMET) polymerization of unsaturated triglycerides such as glyceryl triundec-10-enoate 1 and methyl acrylate (MA) in the presence of the second generation Hoveyda-Grubbs catalyst. The formed amount of interesting products of lower molecular weight during the ATMET reaction depends on the ratio of MA and triglyceride, reaction time, and temperature. We isolated the dimeric metathesis product 2 and synthesized the respective partially hydrogenated dimer 3 regioselectivly in a seven step reaction sequence starting from 10-undecenoic acid 7 and glycerol. Product 3 was unambiguously characterized by (13)C and (1)H NMR and MS as well as the further intermediate products of the seven step reaction including 10,11 bromo-undecanoic acid 8, the respective brominated 1,3-diglyceride 9, the brominated 1,3-triglyceride 6, and the self-metathesis products 4 and 5 which were isolated and purified. KW - Highly functionalized dimeric triglycerides KW - Olefin self- and cross-metathesis KW - Renewable resources Y1 - 2011 U6 - https://doi.org/10.1002/ejlt.201000109 SN - 1438-7697 VL - 113 IS - 1 SP - 39 EP - 45 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kreye, Oliver A1 - Toth, Tommy A1 - Meier, Michael A. R. T1 - Poly-alpha,beta-unsaturated aldehydes derived from castor oil via ADMET polymerization JF - European journal of lipid science and technology N2 - 10-Undecenal, derived by pyrolysis and reduction from castor oil, was almost quantitatively transformed into the corresponding aldol condensation product under basic conditions. This alpha,omega-diene monomer was polymerized using acyclic diene metathesis (ADMET) polymerization. In a catalyst screening, four of nine different ruthenium-based metathesis catalysts showed good reactivity under neat conditions at 80 degrees C in the presence of 1,4-benzoquinone and polymers with molecular weights up to 11 kDa were formed. Furthermore, the (1)H NMR spectra showed that the metathesis catalysts tolerate the alpha,beta-unsaturated aldehyde function and due to the addition of benzoquinone, the degree of double bond isomerization was low. Further experiments investigating reduced catalyst amounts (down to 0.2 mol%) and the temperature dependence of these ADMET polymerizations gave also satisfying results for the formation of poly-alpha,beta-unsaturated aldehydes. Moreover, ADMET polymerizations with different amounts of methyl 10-undecenoate as chain-stopper were performed and the integrals of the corresponding (1)H NMR spectra allowed the determination of an absolute degree of polymerization. Finally, a reduction of a poly-alpha,beta-unsaturated aldehyde with sodium borohydride was accomplished. The resulting poly-(allyl alcohol) could be a useful compound in the generation of polymer networks like polyesters, polyurethanes, and polycarbonates and thus be of high interest in materials research. KW - ADMET KW - Aldol condensation KW - Castor oil KW - Poly(allyl alcohol)s KW - Poly-alpha,beta-unsaturated aldehydes Y1 - 2011 U6 - https://doi.org/10.1002/ejlt.201000108 SN - 1438-7697 VL - 113 IS - 1 SP - 31 EP - 38 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Delahaye, Emilie A1 - Xie, Zailai A1 - Schäfer, Andreas A1 - Douce, Laurent A1 - Rogez, Guillaume A1 - Rabu, Pierre A1 - Günter, Christina A1 - Gutmann, Jochen S. A1 - Taubert, Andreas T1 - Intercalation synthesis of functional hybrid materials based on layered simple hydroxide hosts and ionic liquid guests - a pathway towards multifunctional ionogels without a silica matrix? JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - Functional hybrid materials on the basis of inorganic hosts and ionic liquids (ILs) as guests hold promise for a virtually unlimited number of applications. In particular, the interaction and the combination of properties of a defined inorganic matrix and a specific IL could lead to synergistic effects in property selection and tuning. Such hybrid materials, generally termed ionogels, are thus an emerging topic in hybrid materials research. The current article addresses some of the recent developments and focuses on the question why silica is currently the dominating matrix used for (inorganic) ionogel fabrication. In comparison to silica, matrix materials such as layered simple hydroxides, layered double hydroxides, clay-type substances, magnetic or catalytically active solids, and many other compounds could be much more interesting because they themselves may carry useful functionalities, which could also be exploited for multifunctional hybrid materials synthesis. The current article combines experimental results with some arguments as to how new, advanced functional hybrid materials can be generated and which obstacles will need to be overcome to successfully achieve the synthesis of a desired target material. Y1 - 2011 U6 - https://doi.org/10.1039/c1dt10841g SN - 1477-9226 VL - 40 IS - 39 SP - 9977 EP - 9988 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Marquardt, Dorothea A1 - Xie, Zailai A1 - Taubert, Andreas A1 - Thomann, Ralf A1 - Janiak, Christoph T1 - Microwave synthesis and inherent stabilization of metal nanoparticles in 1-methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - The synthesis of Co-NPs and Mn-NPs by microwave-induced decomposition of the metal carbonyls Co-2(CO)(8) and Mn-2(CO)(10), respectively, yields smaller and better separated particles in the functionalized IL 1-methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate [EmimCO(2)H][BF4] (1.6 +/- 0.3 nm and 4.3 +/- 1.0 nm, respectively) than in the non-functionalized IL 1-n-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4]. The particles are stable in the absence of capping ligands (surfactants) for more than six months although some variation in particle size could be observed by TEM. Y1 - 2011 U6 - https://doi.org/10.1039/c1dt10795j SN - 1477-9226 VL - 40 IS - 33 SP - 8290 EP - 8293 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Troll, K. A1 - Kulkarni, Amit A1 - Wang, W. A1 - Darko, C. A1 - Koumba, A. M. Bivigou A1 - Laschewsky, André A1 - Müller-Buschbaum, Peter A1 - Papadakis, Christine M. T1 - The collapse transition of poly(styrene-b-(N-isopropyl acrylamide)) diblock copolymers in aqueous solution and in thin films T2 - Colloid and polymer science : official journal of the Kolloid-Gesellschaft Y1 - 2011 U6 - https://doi.org/10.1007/s00396-010-2344-1 SN - 0303-402X VL - 289 IS - 2 SP - 227 EP - 227 PB - Springer CY - New York ER - TY - JOUR A1 - Mutlu, Hatice A1 - de Espinosa, Lucas Montero A1 - Meier, Michael A. R. T1 - Acyclic diene metathesis a versatile tool for the construction of defined polymer architectures JF - Chemical Society reviews N2 - Two decades have passed since the metathesis polymerisation of alpha,omega-dienes was successfully demonstrated by the group of Wagener and the term acyclic diene metathesis (ADMET) polymerisation was coined. Since then, the advances of metathesis chemistry have allowed to expand the scope of this versatile polymerisation reaction that nowadays finds applications in different fields, such as polymer, material, or medicinal chemistry. This critical review provides an insight into the historical aspects of ADMET and a detailed overview of the work done to date applying this versatile polymerisation reaction (221 references). Y1 - 2011 U6 - https://doi.org/10.1039/b924852h SN - 0306-0012 VL - 40 IS - 3 SP - 1404 EP - 1445 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Pimpalpalle, Tukaram M. A1 - Vidadala, Srinivasa Rao A1 - Hotha, Srinivas A1 - Linker, Torsten T1 - Lewis acid-catalyzed stereoselective lactonization and subsequent glycosidation of 2-C-malonyl carbohydrates JF - Chemical communications N2 - Gold(III) bromide is a suitable catalyst for the stereoselective cyclization of 2-C-malonyl carbohydrates to the anomeric center under retention of one ester group. Reopening of the lactones with alcohols in the presence of TMSOTf affords allyl, propargyl and benzyl glycosides with high alpha-selectivity. Y1 - 2011 U6 - https://doi.org/10.1039/c1cc13425f SN - 1359-7345 VL - 47 IS - 37 SP - 10434 EP - 10436 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Schmidt, Bernd A1 - Krehl, Stefan T1 - A single precatalyst tandem RCM-allylic oxidation sequence JF - Chemical communications N2 - Ring closing metathesis of allyloxy styrenes and a subsequent Ru-catalyzed allylic oxidation can be combined to a tandem sequence that makes coumarins accessible using less active but more conveniently available first generation catalysts. Y1 - 2011 U6 - https://doi.org/10.1039/c1cc11347j SN - 1359-7345 VL - 47 IS - 20 SP - 5879 EP - 5881 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Wischerhoff, Erik A1 - Badi, Nezha A1 - Laschewsky, André A1 - Lutz, Jean-Francois ED - Börner, Hans Gerhard ED - Lutz, JF T1 - Smart polymer surfaces concepts and applications in biosciences JF - Advances in polymer science = Fortschritte der Hochpolymeren-Forschung JF - Advances in Polymer Science N2 - Stimuli-responsive macromolecules (i.e., pH-, thermo-, photo-, chemo-, and bioresponsive polymers) have gained exponential importance in materials science, nanotechnology, and biotechnology during the last two decades. This chapter describes the usefulness of this class of polymer for preparing smart surfaces (e.g., modified planar surfaces, particles surfaces, and surfaces of three-dimensional scaffolds). Some efficient pathways for connecting these macromolecules to inorganic, polymer, or biological substrates are described. In addition, some emerging bioapplications of smart polymer surfaces (e.g., antifouling surfaces, cell engineering, protein chromatography, tissue engineering, biochips, and bioassays) are critically discussed. KW - Antifouling surfaces KW - Bioactive surfaces KW - Biocompatible polymers KW - Bioseparation KW - Cell engineering KW - Polymer-modified surfaces KW - Stimuli-responsive polymers Y1 - 2011 SN - 978-3-642-20154-7 U6 - https://doi.org/10.1007/12_2010_88 SN - 0065-3195 VL - 240 IS - 1 SP - 1 EP - 33 PB - Springer CY - Berlin ER - TY - JOUR A1 - Cywinski, Piotr J. A1 - Moro, Artur J. A1 - Ritschel, Thomas A1 - Hildebrandt, Niko A1 - Löhmannsröben, Hans-Gerd T1 - Sensitive and selective fluorescence detection of guanosine nucleotides by nanoparticles conjugated with a naphthyridine receptor JF - Analytical & bioanalytical chemistry N2 - Novel fluorescent nanosensors, based on a naphthyridine receptor, have been developed for the detection of guanosine nucleotides, and both their sensitivity and selectivity to various nucleotides were evaluated. The nanosensors were constructed from polystyrene nanoparticles functionalized by (N-(7-((3-aminophenyl) ethynyl)-1,8-naphthyridin- 2-yl) acetamide) via carbodiimide ester activation. We show that this naphthyridine nanosensor binds guanosine nucleotides preferentially over adenine, cytosine, and thymidine nucleotides. Upon interaction with nucleotides, the fluorescence of the nanosensor is gradually quenched yielding Stern-Volmer constants in the range of 2.1 to 35.9mM(-1). For all the studied quenchers, limits of detection (LOD) and tolerance levels for the nanosensors were also determined. The lowest (3 sigma) LOD was found for guanosine 3',5'-cyclic monophosphate (cGMP) and it was as low as 150 ng/ml. In addition, we demonstrated that the spatial arrangement of bound analytes on the nanosensors' surfaces is what is responsible for their selectivity to different guanosine nucleotides. We found a correlation between the changes of the fluorescence signal and the number of phosphate groups of a nucleotide. Results of molecular modeling and zeta-potential measurements confirm that the arrangement of analytes on the surface provides for the selectivity of the nanosensors. These fluorescent nanosensors have the potential to be applied in multi-analyte, array-based detection platforms, as well as in multiplexed microfluidic systems. KW - Naphthyridine receptor KW - cGMP KW - Base pairing KW - Nucleotide nanosensor KW - Fluorescence spectroscopy Y1 - 2011 U6 - https://doi.org/10.1007/s00216-010-4420-2 SN - 1618-2642 VL - 399 IS - 3 SP - 1215 EP - 1222 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Kupstat, Annette A1 - Kumke, Michael Uwe A1 - Hildebrandt, Niko T1 - Toward sensitive, quantitative point-of-care testing (POCT) of protein markers miniaturization of a homogeneous time-resolved fluoroimmunoassay for prostate-specific antigen detection JF - The analyst : the analytical journal of the Royal Society of Chemistry N2 - Point-of-care testing (POCT) systems which allow for a sensitive, quantitative detection of protein markers are extremely useful for the early detection and therapy progress monitoring of cancer. However, currently commercially available POCT devices are mainly limited to the qualitative detection of protein markers. In this study we demonstrate the successive miniaturization of a sensitive and fast assay for the quantitative detection of prostate-specific antigen (PSA) using a well established and clinically approved homogeneous time-resolved fluoroimmunoassay technology (TRACE (R)) on a commercial plate-reader system (KRYPTOR (R)). Regarding the initial requirements for the development of POCT devices we applied a 30-fold assay volume reduction (150 mu L to 5 mu L) to achieve a reasonable lab-on-a-chip volume and a 24-fold and 120-fold excitation pulse energy reduction to achieve reasonable pulse energies for low-cost miniature excitation sources. Due to highly efficient optimization of key POCT parameters our miniaturized PSA assay achieved a 30% increased sensitivity and a 2-fold improved limit of detection compared to the standard plate-reader method. Our results demonstrate the successful implementation of key parameters for a significant miniaturization and for cost reduction in the clinically approved KRYPTOR (R) platform for protein detection. The technological alterations required are easy-to-implement and can be immediately adapted for more than 30 diagnostic protein markers already available for the KRYPTOR (R) platform. These features strongly recommend our assay format to be utilized in innovative, sensitive, quantitative POCT of protein markers. Y1 - 2011 U6 - https://doi.org/10.1039/c0an00684j SN - 0003-2654 VL - 136 IS - 5 SP - 1029 EP - 1035 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Skrabania, Katja A1 - Miasnikova, Anna A1 - Bivigou Koumba, Achille Mayelle A1 - Zehm, Daniel A1 - Laschewsky, André T1 - Examining the UV-vis absorption of RAFT chain transfer agents and their use for polymer analysis JF - Polymer Chemistry N2 - The absorption characteristics of a large set of thiocarbonyl based chain transfer agents (CTAs) were studied by UV-vis spectroscopy in order to identify appropriate conditions for exploiting their absorbance bands in end-group analysis of polymers prepared by reversible addition-fragmentation chain transfer (RAFT) polymerisation. Substitution pattern and solvent polarity were found to affect notably the wavelengths and intensities of the pi-pi*- and n-pi*-transition of the thiocarbonyl bond of dithioester and trithiocarbonate RAFT agents. Therefore, it is advisable to refer in end group analysis to the spectral parameters of low molar mass analogues of the active polymer chain ends, rather than to rely on the specific RAFT agent engaged in the polymerisation. When using appropriate conditions, the quantification of the thiocarbonyl end-groups via the pi-pi* band of the thiocarbonyl moiety around 300-310 nm allows a facile, sensitive and surprisingly precise estimation of the number average molar mass of the polymers produced, without the need of particular end group labels. Moreover, when additional methods for absolute molar mass determination can be applied, the quantification of the thiocarbonyl end-groups by UV-spectroscopy provides a good estimate of the degree of active end group for a given polymer sample. Y1 - 2011 U6 - https://doi.org/10.1039/c1py00173f SN - 1759-9954 VL - 2 IS - 9 SP - 2074 EP - 2083 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Ahnert, Karsten A1 - Abel, Markus A1 - Kollosche, Matthias A1 - Jorgensen, Per Jorgen A1 - Kofod, Guggi T1 - Soft capacitors for wave energy harvesting JF - Journal of materials chemistry N2 - Wave energy harvesting could be a substantial renewable energy source without impact on the global climate and ecology, yet practical attempts have struggled with the problems of wear and catastrophic failure. An innovative technology for ocean wave energy harvesting was recently proposed, based on the use of soft capacitors. This study presents a realistic theoretical and numerical model for the quantitative characterization of this harvesting method. Parameter regions with optimal behavior are found, and novel material descriptors are determined, which dramatically simplify analysis. The characteristics of currently available materials are evaluated, and found to merit a very conservative estimate of 10 years for raw material cost recovery. Y1 - 2011 U6 - https://doi.org/10.1039/c1jm12454d SN - 0959-9428 SN - 1364-5501 VL - 21 IS - 38 SP - 14492 EP - 14497 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Koeth, Anja A1 - Appelhans, Dietmar A1 - Robertson, Daniela A1 - Tiersch, Brigitte A1 - Koetz, Joachim T1 - Use of weakly cationic dendritic glycopolymer for morphological transformation of phospholipid vesicles into tube-like networks JF - Soft matter N2 - Using cationic polyelectrolytes with different molecular architectures, only hyperbranched poly(ethyleneimine) with maltose shell is suited to tailor the morphological transformation of anionic vesicles into tube-like networks. The interaction features of those materials partly mimic biological features of tubular proteins in nature. Y1 - 2011 U6 - https://doi.org/10.1039/c1sm06439h SN - 1744-683X VL - 7 IS - 22 SP - 10581 EP - 10584 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Farra, Ramzi A1 - Thiel, Kerstin A1 - Winter, Alette A1 - Klamroth, Tillmann A1 - Poeppl, Andreas A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Taubert, Andreas A1 - Strauch, Peter T1 - Tetrahalidocuprates(II)-structure and EPR spectroscopy Part 1: Tetrabromidocuprates(II) JF - New journal of chemistry N2 - Tetrahalidocuprates(II) show a high degree of structural flexibility. We present the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of four new tetrabromidocuprate(II) compounds and compare the results with previously reported data. The cations in the new compounds are the sterically demanding benzyltriphenylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, and hexadecyltrimethylammonium ions; they were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. X-Ray crystallography shows that in all four complexes the [CuBr4](2-) units have a distorted tetrahedral coordination geometry which is in agreement with DFT calculations. The EPR hyperfine structure was not resolved. This is due to the exchange broadening resulting from still incomplete separation of the paramagnetic Cu(II) centres. Nevertheless, the principal values of the electron Zeemann tensor (g(parallel to) and g(perpendicular to)) of the complexes could be determined. A correlation of structural (X-ray) parameters with the spin density at the copper centres (DFT) is well reflected in the EPR spectra of the bromidocuprates. This enables the correlation of X-ray and EPR parameters to predict the structure of tetrabromidocuprates in physical states other than the crystalline state. As a result, we provide a method to structurally characterize [CuBr4](2-) in, for example, ionic liquids or in solution, which has important implications for e.g. catalysis or materials science. Y1 - 2011 U6 - https://doi.org/10.1039/c1nj20271e SN - 1144-0546 VL - 35 IS - 12 SP - 2793 EP - 2803 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Haase, Martin F. A1 - Grigoriev, Dmitry A1 - Moehwald, Helmuth A1 - Tiersch, Brigitte A1 - Shchukin, Dmitry G. T1 - Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions JF - Langmuir N2 - The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte. Y1 - 2011 U6 - https://doi.org/10.1021/la1027724 SN - 0743-7463 VL - 27 IS - 1 SP - 74 EP - 82 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Möller, Eleonore A1 - Beuermann, Sabine T1 - Homogeneous phase copolymerizations of vinylidene fluoride and hexafluoropropene in supercritical carbon dioxide JF - Macromolecular reaction engineering N2 - Copolymerizations of vinylidene fluoride (VDF) and hexafluoropropene (HFP) were carried out in homogeneous phase with supercritical carbon dioxide up to complete VDF conversion using conventional peroxide initiators. The HFP monomer feed ratios, f(HFP), were varied between 0.65 and 0.20. Depending on f(HFP) amorphous or semi-crystalline copolymers were obtained. f(HFP) also determines the minimum pressure required to allow for homogeneous phase reactions. For example, HFP-rich copolymerizations in 70 wt.-% CO(2) at 100 degrees C require a pressure of around 500 bar. Further, bulk copolymerizations in homogenous phase were feasible for f(HFP) 0.65 at 900 bar up to complete VDF conversion. Copolymerizations in the presence of perfluorinated hexyl iodide carried out at 75 degrees C gave access to low dispersity polymers. Due to homogeneous phase conditions the use of any surfactants or fluorinated cosolvent is avoided. KW - copolymerization KW - hexafluoropropene KW - phase behavior KW - supercritical CO(2) KW - vinylidene fluoride Y1 - 2011 U6 - https://doi.org/10.1002/mren.201000031 SN - 1862-832X VL - 5 IS - 1 SP - 8 EP - 21 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Awad, Duha Jawad A1 - Schilde, Uwe A1 - Strauch, Peter T1 - 4,4 '-Bis(tert-butyl)-2,2 '-bipyridinedichlorometal(II) - Synthesis, structure and EPR spectroscopy JF - Inorganica chimica acta : the international inorganic chemistry journal N2 - Due to the better solubility of the 4,4'-substituted bipyridine ligand a series of 4,4'0-bis(tert-butyl)-2,2'-bipyridinedichlorometal(II) complexes, [M(tbbpy)Cl(2)], with M = Cu, Ni, Zn, Pd, Pt was synthesised and characterised. The blue copper complex 4,4'-bis(tert-butyl)-2,2'-bipyridinedichlorocopper(II) was isolated in two different polymorphic forms, as prisms 1 with a solvent inclusion and solvent-free as needles 2. Both structures were determined by X-ray structure analysis. They crystallise in the monoclinic space group P2(1)/c with four molecules in the unit cell, but with different unit cells and packing motifs. Whereas in the prisms 1, with the unit cell parameters a = 12.1613(12), b = 10.6363(7), c = 16.3074(15) angstrom, eta = 94.446(8)degrees, the packing is dominated by intra-and intermolecular hydrogen bonds, in the needles 2, with a = 7.738(1), b = 18. 333(2), c = 13.291(3) angstrom, beta = 97.512(15)degrees, only intramolecular hydrogen bonds appear and the complex molecules are arranged in columns which are stabilised by p-p-stacking interactions. In both complexes the copper has a tetrahedrally distorted coordination sphere. These copper complexes were also studied by EPR spectroscopy in solution, as frozen glass and diamagnetically diluted powder with the analogue [Pd(tbbpy)Cl(2)] as host lattice. KW - 4,4 '-Bis(tert-butyl)-2,2 '-bipyridine KW - X-ray structure KW - EPR KW - Copper(II) KW - Transition metals Y1 - 2011 U6 - https://doi.org/10.1016/j.ica.2010.08.035 SN - 0020-1693 VL - 365 IS - 1 SP - 127 EP - 132 PB - Elsevier CY - Lausanne ER - TY - JOUR A1 - Schreiber, Ulrike A1 - Hosemann, Benjamin A1 - Beuermann, Sabine T1 - 1H,1H,2H,2H-Perfluorodecyl-Acrylate-Containing block copolymers from ARGET ATRP JF - Macromolecular chemistry and physics N2 - Block copolymers of 1H,1H,2H,2H-perfluorodecyl acrylate (AC8) were obtained from ARGET ATRP. To obtain block copolymers of low dispersity the PAC8 block was synthesized in anisole with a CuBr(2)/PMDETA catalyst in the presence of tin(II) 2-ethylhexanoate as a reducing agent. The PAC8 block was subsequently used as macroinitiator for copolymerization with butyl and tert-butyl acrylate carried out in scCO(2). To achieve catalyst solubility in CO(2) two fluorinated ligands were employed. The formation of block copolymers was confirmed by size exclusion chromatography and DSC. KW - atom transfer radical polymerization (ATRP) KW - block copolymers KW - fluoropolymers KW - supercritical carbon dioxide Y1 - 2011 U6 - https://doi.org/10.1002/macp.201000307 SN - 1022-1352 VL - 212 IS - 2 SP - 168 EP - 179 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Prevost, Sylvain A1 - Wattebled, Laurent A1 - Laschewsky, André A1 - Gradzielski, Michael T1 - Formation of monodisperse charged vesicles in mixtures of cationic gemini surfactants and anionic SDS JF - Langmuir N2 - The aggregation behavior of catanionics formed by the mixture of cationic geminis derived from dodecyltrimethylammonium chloride (DTAC) and anionic sodium dodecylsulfate (SDS) was studied by means of phase studies and comprehensive small-angle neutron scattering (SANS) experiments at 25 degrees C and 50 mM overall concentration. The results are compared to those for the previously studied SDS + DTAC system. Various gemini spacers of different natures and geometries were used, but all of them had similar lengths: an ethoxy bridge, a double bond, and an aromatic ring binding the two DTACs in three different substitutions (ortho, meta, and para). SANS and SAXS data analysis indicates that the spacer has no large effect on the spheroidal micelles of pure surfactants formed at low concentration in water; however, specific effects appear with the addition of electrolytes. Microstructures formed in the catanionic mixtures are rather strongly dependent on the nature of the spacer. The most important finding is that for the hydrophilic, flexible ethoxy bridge, monodisperse vesicles with a fixed anionic/cationic charge ratio (depending only on the surfactant in excess) are formed. Furthermore, the composition of these vesicles shows that strongly charged aggregates are formed. This study therefore provides new opportunities for developing tailor-made gemini surfactants that allow for the fine tuning of catanionic structures. Y1 - 2011 U6 - https://doi.org/10.1021/la103976p SN - 0743-7463 VL - 27 IS - 2 SP - 582 EP - 591 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Glatzel, Stefan A1 - Laschewsky, André A1 - Lutz, Jean-Francois T1 - Well-Defined uncharged polymers with a sharp UCST in water and in physiological milieu JF - Macromolecules : a publication of the American Chemical Society Y1 - 2011 U6 - https://doi.org/10.1021/ma102677k SN - 0024-9297 VL - 44 IS - 2 SP - 413 EP - 415 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Tremblay, Jean Christophe A1 - Klinkusch, Stefan A1 - Klamroth, Tillmann A1 - Saalfrank, Peter T1 - Dissipative many-electron dynamics of ionizing systems JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - In this paper, we perform many-electron dynamics using the time-dependent configuration-interaction method in its reduced density matrix formulation (rho-TDCI). Dissipation is treated implicitly using the Lindblad formalism. To include the effect of ionization on the state-resolved dynamics, we extend a recently introduced heuristic model for ionizing states to the rho-TDCI method, which leads to a reduced density matrix evolution that is not norm-preserving. We apply the new method to the laser-driven excitation of H(2) in a strongly dissipative environment, for which the state-resolve lifetimes are tuned to a few femtoseconds, typical for dynamics of adsorbate at metallic surfaces. Further testing is made on the laser-induced intramolecular charge transfer in a quinone derivative as a model for a molecular switch. A modified scheme to treat ionizing states is proposed to reduce the computational burden associated with the density matrix propagation, and it is thoroughly tested and compared to the results obtained with the former model. The new approach scales favorably (similar to N(2)) with the number of configurations N used to represent the reduced density matrix in the rho-TDCI method, as compared to a N(3) scaling for the model in its original form. Y1 - 2011 U6 - https://doi.org/10.1063/1.3532410 SN - 0021-9606 VL - 134 IS - 4 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Piluso, Susanna A1 - Hiebl, Bernhard A1 - Gorb, Stanislav N. A1 - Kovalev, Alexander A1 - Lendlein, Andreas A1 - Neffe, Axel T. T1 - Hyaluronic acid-based hydrogels crosslinked by copper-catalyzed azide-alkyne cycloaddition with tailorable mechanical properties JF - The international journal of artificial organs N2 - Biopolymers of the extracellular matrix are attractive starting materials for providing degradable and biocompatible biomaterials. In this study, hyaluronic acid-based hydrogels with tunable mechanical properties were prepared by the use of copper-catalyzed azide-alkyne cycloaddition (known as "click chemistry"). Alkyne-functionalized hyaluronic acid was crosslinked with linkers having two terminal azide functionalities, varying crosslinker density as well as the lengths and rigidity of the linker molecules. By variation of the crosslinker density and crosslinker type, hydrogels with elastic moduli in the range of 0.5-4 kPa were prepared. The washed materials contained a maximum of 6.8 mg copper per kg dry weight and the eluate of the gel crosslinked with diazidostilbene did not show toxic effects on L929 cells. The hyaluronic acid-based hydrogels have potential as biomaterials for cell culture or soft tissue regeneration applications. KW - Biomaterial KW - Hydrogel KW - Hyaluronic acid KW - Microindentation KW - Rheology Y1 - 2011 U6 - https://doi.org/10.5301/IJAO.2011.6394 SN - 0391-3988 VL - 34 IS - 2 SP - 192 EP - 197 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Graf, Philipp A1 - Mantion, Alexandre A1 - Haase, Andrea A1 - Thuenemann, Andreas F. A1 - Masic, Admir A1 - Meier, Wolfgang P. A1 - Luch, Andreas A1 - Taubert, Andreas T1 - Silicification of peptide-coated silver nanoparticles-A biomimetic soft chemistry approach toward chiral hybrid core-shell materials JF - ACS nano N2 - Silica and silver nanoparticles are relevant materials for new applications in optics, medicine, and analytical chemistry. We have previously reported the synthesis of pH responsive, peptide-templated, chiral silver nanoparticles. The current report shows that peptide-stabilized nanoparticles can easily be coated with a silica shell by exploiting the ability of the peptide coating to hydrolyze silica precursors such as TEOS or TMOS. The resulting silica layer protects the nanoparticles from chemical etching, allows their inclusion in other materials, and renders them biocompatible. Using electron and atomic force microscopy, we show that the silica shell thickness and the particle aggregation can be controlled simply by the reaction time. Small-angle X ray scattering confirms the Ag/peptide@silica core-shell structure. UV-vis and circular dichroism spectroscopy prove the conservation of the silver nanoparticle chirality upon silicification. Biological tests show that the biocompatibility in simple bacterial systems is significantly improved once a silica layer is deposited on the silver particles. KW - peptide-templated materials KW - silver nanoparticles KW - chiral nanoparticles KW - Ag/peptide@SiO(2) nanostructures KW - core-shell structures Y1 - 2011 U6 - https://doi.org/10.1021/nn102969p SN - 1936-0851 VL - 5 IS - 2 SP - 820 EP - 833 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zaupa, Alessandro A1 - Neffe, Axel T. A1 - Pierce, Benjamin F. A1 - Lendlein, Andreas A1 - Hofmann, Dieter T1 - A molecular dynamic analysis of gelatin as an amorphous material Prediction of mechanical properties of gelatin systems JF - The international journal of artificial organs N2 - Biomaterials are used in regenerative medicine for induced autoregeneration and tissue engineering. This is often challenging, however, due to difficulties in tailoring and controlling the respective material properties. Since functionalization is expected to offer better control, in this study gelatin chains were modified with physically interacting groups based on tyrosine with the aim of causing the formation of physical crosslinks. This method permits application-specific properties like swelling and better tailoring of mechanical properties. The design of the crosslink strategy was supported by molecular dynamic (MD) simulations of amorphous bulk models for gelatin and functionalized gelatins at different water contents (0.8 and 25 wt.-%). The results permitted predictions to be formulated about the expected crosslink density and its influence on equilibrium swelling behavior and on elastic material properties. The models of pure gelatin were used to validate the strategy by comparison between simulated and experimental data such as density, backbone conformation angle distribution, and X-ray scattering spectra. A key result of the simulations was the prediction that increasing the number of aromatic functions attached to the gelatin chain leads to an increase in the number of physical netpoints observed in the simulated bulk packing models. By comparison with the Flory-Rehner model, this suggested reduced equilibrium swelling of the functionalized materials in water, a prediction that was subsequently confirmed by our experimental work. The reduction and control of the equilibrium degree of swelling in water is a key criterion for the applicability of functionalized gelatins when used, for example, as matrices for induced autoregeneration of tissues. KW - Physical Network KW - Biopolymer material KW - Molecular modeling KW - Gelatin Y1 - 2011 U6 - https://doi.org/10.5301/IJAO.2010.6083 SN - 0391-3988 VL - 34 IS - 2 SP - 139 EP - 151 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Havelius, Kajsa G. V. A1 - Reschke, Stefan A1 - Horn, Sebastian A1 - Doerlng, Alexander A1 - Niks, Dimitri A1 - Hille, Russ A1 - Schulzke, Carola A1 - Leimkühler, Silke A1 - Haumann, Michael T1 - Structure of the molybdenum site in YedY, a sulfite oxidase homologue from escherichia coli JF - Inorganic chemistry N2 - YedY from Escherichia coil is a new member of the sulfite oxidase family of molybdenum cofactor (Moco)-containing oxidoreductases. We investigated the atomic structure of the molybdenum site in YedY by X-ray absorption spectroscopy, in comparison to human sulfite oxidase (hSO) and to a Mo(IV) model complex. The K-edge energy was indicative of Mo(V) in YedY, in agreement with X- and Q-band electron paramagnetic resonance results, whereas the hSO protein contained Mo(VI). In YedY and hSO, molybdenum is coordinated by two sulfur ligands from the molybdopterin ligand of the Moco, one thiolate sulfur of a cysteine (average Mo-S bond length of similar to 2.4 angstrom), and one (axial) oxo ligand (Mo=O, similar to 1.7 angstrom). hSO contained a second oxo group at Mo as expected, but in YedY, two species in about a 1:1 ratio were found at the active site, corresponding to an equatorial Mo-OH bond (similar to 2.1 angstrom) or possibly to a shorter M-O(-) bond. Yet another oxygen (or nitrogen) at a similar to 2.6 angstrom distance to Mo in YedY was identified, which could originate from a water molecule in the substrate binding cavity or from an amino acid residue close to the molybdenum site, i.e., Glu104, that is replaced by a glycine in hSO, or Asn45. The addition of the poor substrate dimethyl sulfoxide to YedY left the molybdenum coordination unchanged at high pH. In contrast, we found indications that the better substrate trimethylamine N-oxide and the substrate analogue acetone were bound at a similar to 2.6 angstrom distance to the molybdenum, presumably replacing the equatorial oxygen ligand. These findings were used to interpret the recent crystal structure of YedY and bear implications for its catalytic mechanism. Y1 - 2011 U6 - https://doi.org/10.1021/ic101291j SN - 0020-1669 VL - 50 IS - 3 SP - 741 EP - 748 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Huber, Christian A1 - Klamroth, Tillmann T1 - Explicitly time-dependent coupled cluster singles doubles calculations of laser-driven many-electron dynamics JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - We report explicitly time-dependent coupled cluster singles doubles (TD-CCSD) calculations, which simulate the laser-driven correlated many-electron dynamics in molecular systems. Small molecules, i.e., HF, H(2)O, NH(3), and CH(4), are treated mostly with polarized valence double zeta basis sets. We determine the coupled cluster ground states by imaginary time propagation for these molecules. Excited state energies are obtained from the Fourier transform of the time-dependent dipole moment after an ultrashort, broadband laser excitation. The time-dependent expectation values are calculated from the complex cluster amplitudes using the corresponding configuration interaction singles doubles wave functions. Also resonant laser excitations of these excited states are simulated, in order to explore the limits for the numerical stability of our current TD-CCSD implementation, which uses time-independent molecular orbitals to form excited configurations. Y1 - 2011 U6 - https://doi.org/10.1063/1.3530807 SN - 0021-9606 VL - 134 IS - 5 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Xie, Zai-Lai A1 - Taubert, Andreas T1 - Thermomorphic behavior of the ionic liquids [C(4)mim][FeCl4] and [C(12)mim][FeCl4] JF - ChemPhysChem : a European journal of chemical physics and physical chemistry N2 - The iron-containing ionic liquids 1-butyl-3-methylimidazolium tetrachloroferrate(III) [C(4)mim][FeCl4] and 1-dodecyl-3-methylimidazolium tetrachloroferrate(III) [C(12)mim][FeCl4] exhibit a thermally induced demixing with water (thermomorphism). The phase separation temperature varies with IL weight fraction in water and can be tuned between 100 degrees C and room temperature. The reversible lower critical solution temperature (LCST) is only observed at IL weight fractions below ca. 35% in water. UV/Vis, IR, and Raman spectroscopy along with elemental analysis prove that the yellow-brown liquid phase recovered after phase separation is the starting IL [C(4)mim][FeCl4] and [C(12)mim][FeCl4], respectively. Photometry and ICP-OES show that about 40% of iron remains in the water phase upon phase separation. Although the process is thus not very efficient at the moment, the current approach is the first example of an LCST behavior of a metal-containing IL and therefore, although still inefficient, a prototype for catalyst removal or metal extraction. KW - imidazolium KW - ionic liquids KW - phase transitions KW - Raman spectroscopy KW - thermomorphism Y1 - 2011 U6 - https://doi.org/10.1002/cphc.201000808 SN - 1439-4235 VL - 12 IS - 2 SP - 364 EP - 368 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kreye, Oliver A1 - Toth, Tommy A1 - Meier, Michael A. R. T1 - Introducing multicomponent reactions to polymer science passerini reactions of renewable monomers JF - Journal of the American Chemical Society N2 - Combination of the Passerini three component-reaction (3CR) and olefin metathesis led to the formation of poly[1-(alkyl carbamoyl)alkyl alkanoates], a new class of polyesters with amide moieties in their side chain, from renewable resources. Two different approaches were studied and compared to each other. First, monomers were synthesized by the Passerini-3CR and then polymerized via acyclic diene metathesis. Alternatively, bifunctional monomers were synthesized by self-metathesis and then polymerized by Passerini-3CR. Both approaches led to the formation of high-molecular-weight polymers. Moreover, Passerini-3CRs were shown to be a versatile grafting-onto method. The results clearly demonstrate that the Passerini-3CR offers an interesting new access to monomers and polymers and thus broadens the synthetic portfolio of polymer science. Y1 - 2011 U6 - https://doi.org/10.1021/ja1113003 SN - 0002-7863 VL - 133 IS - 6 SP - 1790 EP - 1792 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schmidt, Bernd A1 - Staude, Lucia A1 - Kelling, Alexandra A1 - Schilde, Uwe T1 - A Cross-Metathesis-Conjugate addition route to enantiopure gamma-Butyrolactams and gamma-Lactones from a C-2-Symmetric Precursor JF - European journal of organic chemistry N2 - A protected derivative of (3R, 4R)-hexa-1,5-diene-3,4-diol, a conveniently accessible C-2-symmetric building block, undergoes single or double cross metathesis with methyl acryl-ate. The cross metathesis products are amenable to stereoselective conjugate addition reactions and can be converted into either gamma-butyrolactones or gamma-lactams. KW - Lactams KW - Lactones KW - Oxygen heterocycles KW - Metathesis KW - Desymmetrization Y1 - 2011 U6 - https://doi.org/10.1002/ejoc.201001528 SN - 1434-193X IS - 9 SP - 1721 EP - 1727 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Yarman, Aysu A1 - Nagel, Thomas A1 - Gajovic-Eichelmann, Nenad A1 - Fischer, Anna A1 - Wollenberger, Ursula A1 - Scheller, Frieder W. T1 - Bioelectrocatalysis by Microperoxidase-11 in a Multilayer Architecture of Chitosan Embedded Gold Nanoparticles JF - Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis N2 - We report on the redox behaviour of the microperoxidase-11 (MP-11) which has been electrostatically immobilized in a matrix of chitosan-embedded gold nanoparticles on the surface of a glassy carbon electrode. MP-11 contains a covalently bound heme c as the redox active group that exchanges electrons with the electrode via the gold nanoparticles. Electroactive surface concentration of MP-11 at high scan rate is between 350+/-50 pmol cm(-2), which reflects a multilayer process. The formal potential (E degrees') of MP-11 in the gold nanoparticles-chitosan film was estimated to be -(267.7+/-2.9) mV at pH 7.0. The heterogeneous electron transfer rate constant (k(s)) starts at 1.21 s(-1) and levels off at 6.45 s(-1) in the scan rate range from 0.1 to 2.0 V s(-1). Oxidation and reduction of MP-11 by hydrogen peroxide and superoxide, respectively have been coupled to the direct electron transfer of MP-11. KW - Microperoxidase KW - Direct electron transfer KW - Nanoparticles KW - Hydrogen peroxide KW - Superoxide KW - Bioelectrocatalysis Y1 - 2011 U6 - https://doi.org/10.1002/elan.201000535 SN - 1040-0397 VL - 23 IS - 3 SP - 611 EP - 618 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Neuvonen, Kari A1 - Neuvonen, Helmi A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - NBO analysis of polar and steric effect using the axial-equatorial equilibrium of cyclohexyl acetates as a probe JF - Computational and theoretical chemistry N2 - The proportion of the axial conformer increases in the ax reversible arrow eq equilibrium of cyclohexyl acetates (RCOOC(6)H(11), R reversible arrow Me, Et, iPr, tBu, CH(2)Cl, CHCl(2), CO(3). CH(2)Br, CHBr(2), CBr(3)) with the increasing size of the acyloxy substitution. The nature of this unexpected steric substituent effect, which is opposite to general stereochemical concepts, was studied by means of ab kiln MO method, accompanied by NBO and isodesmic calculations. NBO parameters seem to be good descriptors for quantitative prediction of the experimental Delta G degrees value of the title conformational equilibrium. The origin and propagation of the substituent effect of the polar substitutions (CH(2)Cl, CHCl(2), CCl(3), CH(2)Br, CHBr(2), CBr(3)) differ, however, from those of the pure alkyl (Me, Et, iPr, tBu) substitutions. The Delta G degrees value of the polar derivatives depends on the qC8 charges, on the occupation of the sigma(center dot)(C1-07) orbital and on the hyperconjugative pi(center dot)(c=O) -> sigma(center dot)(C10-X) and sigma(center dot)(C10-X) -> pi(center dot)(c=O) interactions. The substituent sensitivity of these NBC parameters for the two conformers differ to the effect that the ax reversible arrow eq equilibrium is shifted to the left side with increasing electron withdrawing character of the acyloxy group. The Delta G degrees values of the alkyl derivatives are interpreted in terms of the calculated dipole moments. The destabilization in the non-polar medium (the experimental Delta G degrees values used were measured in CD(2)Cl(2)) due to the enhanced dipolar character is more prominent in the case of the equatorial alkyl conformers. As the consequence, the ax reversible arrow eq equilibrium is shifted to the left despite the increasing size of the R group when going from Me to tBu substitution. KW - Substituent effects KW - Ab initio MO computations KW - Conformational equilibria KW - Cyclohexyl esters KW - NBO analysis Y1 - 2011 U6 - https://doi.org/10.1016/j.comptc.2010.12.033 SN - 2210-271X VL - 964 IS - 1-3 SP - 234 EP - 242 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Mengibar, M. A1 - Ganan, M. A1 - Miralles, B. A1 - Carrascosa, A. V. A1 - Martinez-Rodriguez, Adolfo J. A1 - Peter, Martin G. A1 - Heras, A. T1 - Antibacterial activity of products of depolymerization of chitosans with lysozyme and chitosanase against Campylobacter jejuni JF - Carbohydrate polymers : an international journal devoted to scientific and technological aspects of industrially important polysaccharides N2 - Chitosan has several biological properties useful for the food industry, but the most attractive is its potential use as a food preservative of natural origin due to its antimicrobial activity against a wide range of food-borne microorganisms. Among food-borne pathogens, Campylobacter jejuni and related species are recognised as the most common causes of bacterial food-borne diarrhoeal disease throughout the world. Recently, it has been demonstrated that campylobacters are highly sensitive to chitosan. Even though chitosan is known to have important functional activities, poor solubility makes them difficult to use in food and biomedical applications. Unlike chitosan, the low viscosity and good solubility of chitosan oligosaccharides (COS) make them especially attractive in an important number of useful applications. In the present work, the effect of different COS on C. jejuni was investigated. Variables such as the physicochemical characteristics of chitosan and the enzyme used in COS preparation were studied. The COS had been fractioned using ultrafiltration membranes and each fraction was characterized regarding its FA and molecular weight distribution. It has been demonstrated that the biological properties of COS on Campylobacter depend on the composition of the fraction analysed. COS prepared by enzymatic hydrolysis with chitosanase were more active against Campylobacter that lysozyme-derived COS, and this behaviour seems to be related with the acetylation of the chains. On the other hand. the 10-30 kDa fraction was the most active COS fraction, independently of the enzyme used for the hydrolysis. These results have shown that COS could be useful as antimicrobial in the control of C. jejuni. KW - Campylobacter jejuni KW - Chitooligosaccharides KW - Chitosanase KW - Lysozyme KW - Depolymerization Y1 - 2011 U6 - https://doi.org/10.1016/j.carbpol.2010.04.042 SN - 0144-8617 VL - 84 IS - 2 SP - 844 EP - 848 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Vijayakrishnan, Balakumar A1 - Issaree, Arisara A1 - Corilo, Yuri E. A1 - Ferreira, Christina Ramires A1 - Eberlin, Marcos N. A1 - Peter, Martin G. T1 - MSn of the six isomers of (GlcN)(2)(GlcNAc)(2) aminoglucan tetrasaccharides (diacetylchitotetraoses) rules of fragmentation for the sodiated molecules and application to sequence analysis of hetero-chitooligosaccharides JF - Carbohydrate polymers : an international journal devoted to scientific and technological aspects of industrially important polysaccharides N2 - The six possible isomers of di-N-acetylchitotetraoses [AADD, ADDA, ADAD, DADA, DAAD, and DDAA, where D stands for 2-amino-2-deoxy-3-D-glucose (GlcN) and A for 2-acetamido-2-deoxy-beta-D-glucose (GlcNAc)] were analyzed by ESI(+)-MSn. Collision induced dissociation via MSn experiments were performed for the sodiated molecules of m/z 769 [M+Na](+) for each isomer, and fragments were generated mainly by glycosidic bond and cross-ring cleavages. Rules of fragmentation were then established. A reducing end D residue yields the (O.2)A(4) cross-ring [M-59+Na](+) fragment of m/z 710 as the most abundant, whereas isomers containing a reducing end A prefer to lose water to form the [M-18+Na](+) ion of m/z 751, as well as abundant (O.2)A(4) cross-ring [M-101+Na](+) fragments of m/z 668 and B-3 [M-221+Na](+) ions of m/z 548. MS3 of C- and Y-type ions shows analogous fragmentation behaviour that allows identification of the reducing end next-neighbour residue. Due to gas-phase anchimeric assistance, B-type cleavage between the glycosidic oxygen and the anomeric carbon atom is favoured when the glycon is an A residue. Relative ion abundances are generally in the order B >> C > Y, but may vary depending on the next neighbour towards the non-reducing end. These fragmentation rules were used for partial sequence analysis of hetero-chitooligosaccharides of the composition D(2)A(3), D(3)A(3), D(2)A(4), D(4)A(3), and D(3)A(4). KW - Chitosan KW - Fragmentation KW - Oligosaccharides KW - Sequence analysis KW - Tandem mass spectrometry Y1 - 2011 U6 - https://doi.org/10.1016/j.carbpol.2010.04.041 SN - 0144-8617 VL - 84 IS - 2 SP - 713 EP - 726 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Wirth, Jonas A1 - Monturet, Serge A1 - Klamroth, Tillmann A1 - Saalfrank, Peter T1 - Adsorption and (photo-) electrochemical splitting of water on rutile ruthenium dioxide JF - epl : a letters journal exploring the frontiers of physics N2 - In this work, the adsorption and splitting of the water molecule by light and/or an external potential is investigated in the frame of (photo-) electrochemical cells using a rutile ruthenium dioxide anode. With the help of periodic density functional calculations, the adsorbed structures of H(2)O and some radicals involved in the splitting process (O, OH, OOH) are obtained and compared with the available experimental results. On the basis of these electronic-structure calculations, we use a method to calculate the stability of the reaction intermediates and conclude on the thermodynamical possibility of the water splitting reaction at the surface. We demonstrate that a moderate overpotential of 0.64 V is required for the reaction to take place at the RuO(2)(110) surface. Y1 - 2011 U6 - https://doi.org/10.1209/0295-5075/93/68001 SN - 0295-5075 VL - 93 IS - 6 PB - EDP Sciences CY - Mulhouse ER - TY - JOUR A1 - Neumann, Mike A1 - Noeske, Robert A1 - Bach, Grete A1 - Glaubauf, Thomas A1 - Bartoszek, Michael A1 - Strauch, Peter T1 - A procedure for rapid determination of the silicon content in plant materials JF - Zeitschrift für Naturforschung : B, Chemical sciences N2 - An efficient, reliable and low-cost procedure to determine the silicon content in plant material is presented which allows to monitor the agricultural aspects like growth and yield. The presented procedure consists of a hydrochloric acid pre-treatment and a subsequent thermal oxidation. The method is compared to other processes like dissolution in hydrofluoric acid combined with ICP OES, energy-dispersive X-ray fluorescence spectroscopy (EDXRF) or aqua regia treatment. KW - Silica Determination KW - Silicon Content KW - Plant Material Y1 - 2011 SN - 0932-0776 VL - 66 IS - 3 SP - 289 EP - 294 PB - De Gruyter CY - Tübingen ER - TY - JOUR A1 - Wessig, Pablo A1 - Matthes, Annika T1 - Preparation of Strained Axially Chiral (1,5)Naphthalenophanes by Photo-dehydro-Diels-Alder Reaction JF - Journal of the American Chemical Society N2 - The preparation of 10 (1,5)naphthalenophanes (10a-j) by photo-dehydro-Diels-Alder (PDDA) reaction is described. Owing to hindered rotation around the biaryl axis, compounds 10 are axially chiral and the separation of enantiomers by chiral HPLC was demonstrated in three cases (10a,b,e). The absolute configuration of the isolated enantiomers could be unambiguously determined by comparison of calculated and measured circular dichroism (CD) spectra. Furthermore, we analyzed ring strain phenomena of (1,5)naphthalenophanes 10. Depending on the length of the linker units, one can distinguish three classes of naphthalenophanes. Compounds 10a-c are highly strained (E-STR = 7-31 kcal/mol), and the strain is caused by small bond angles in the linker unit and deformation of the naphthalene moiety. Another type of strain is observed if the linker unit becomes relatively long (10g,h) originating from transannular interactions and is comparable with the well-known strain of medium sized rings. The naphthalenophanes 10d-f with a linker length of 10-14 atoms are only marginally strained. To clearly discriminate the different sources of strain, we defined two geometrical parameters (average central dihedral angle delta(C) and naphthalene thickness D-N) and demonstrated that they are well-suited to indicate naphthalene deformation of our naphthalenophanes 10 as well as of ten model naphthalenophanes (I-X) with different linker lengths and linking positions. Y1 - 2011 U6 - https://doi.org/10.1021/ja109118m SN - 0002-7863 VL - 133 IS - 8 SP - 2642 EP - 2650 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Reznichenko, Alexander L. A1 - Emge, Thomas J. A1 - Audoersch, Stephan A1 - Klauber, Eric G. A1 - Hultzsch, Kai C. A1 - Schmidt, Bernd T1 - Group 5 metal binaphtholate complexes for catalytic asymmetric hydroaminoalkylation and hydroamination/cyclization JF - Organometallics N2 - 3,3'-Silylated binaphtholate tantalum and niobium complexes were shown to be efficient catalysts for the asymmetric hydroaminoalkylation of N-methylaniline derivatives and N-benzylmethylamine with simple alkenes in enantioselectivities of up to 80% ee. No hydroaminoalkylation was observed with aminoalkenes; rather, exclusive asymmetric hydroamination/cyclization took place in up to 81% ee. Y1 - 2011 U6 - https://doi.org/10.1021/om1011006 SN - 0276-7333 VL - 30 IS - 5 SP - 921 EP - 924 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Yin, Jian A1 - Linker, Torsten T1 - Stereoselective diversity-oriented syntheses of functionalized saccharides from bicyclic carbohydrate 1,2-lactones JF - Tetrahedron N2 - Bicyclic carbohydrate 1,2-lactones have been synthesized in only two steps and high yields by saponification and subsequent cyclization from known malonate addition products to glycals. The gluco-configured lactone serves as an important precursor for diversity-oriented syntheses. Thus, stereoselective opening of the lactone ring was realized with various nucleophiles in the presence of Sc(OTf)(3). This enabled the introduction of different substituents at the anomeric position, to afford a broad variety of 1-functionalized carbohydrates. On the other hand, stereoselective alpha-substitution of the gluco-configured lactone with different electrophiles and subsequent ring opening gives a collection of 2-functionalized saccharides. More than 30 products have been isolated in analytically pure form, and their configurations were unequivocally established by various NMR methods. Thus, carbohydrate 1,2-lactones are attractive precursors for the stereoselective synthesis of diverse saccharides. KW - Carbohydrates KW - Lactones KW - Glycosides KW - Molecular diversity KW - Synthetic methods Y1 - 2011 U6 - https://doi.org/10.1016/j.tet.2011.01.069 SN - 0040-4020 VL - 67 IS - 13 SP - 2447 EP - 2461 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Kirpichenko, Svetlana V. A1 - Kleinpeter, Erich A1 - Ushakov, Igor A. A1 - Shainyan, Bagrat A. T1 - Conformational Analysis of 3-Methyl-3-Silathiane and 3-Fluoro-3-Methyl-3-Silathiane JF - Journal of physical organic chemistry N2 - The conformational equilibria of 3-methyl-3-silathiane 5, 3-fluoro-3-methyl-3-silathiane 6 and 1-fluoro-1-methyl-1- silacyclohexane 7 have been studied using low temperature C-13 NMR spectroscopy and theoretical calculations. The conformer ratio at 103 K was measured to be about 5(ax):5(eq) - 15:85, 6(ax):6(eq)-50:50 and 7(ax):7(eq)-25:75. The equatorial preference of the methyl group in 5 (0.35 kcal mol(-1)) is much less than in 3-methylthiane 9 (1.40 kcal mol(-1)) but somewhat greater than in 1-methyl-1-silacyclohexane 1 (0.23 kcal mol(-1)). Compounds 5-7 have low barriers to ring inversion: 5.65 (ax -> eq) and 6.0 kcal mol(-1) (eq -> ax) (5), 4.6 kcal mol(-1) (6), 5.1 kcal mol(-1) (Me-ax -> Me-eq), and 5.4 kcal mol(-1) (Me-eq -> Me-ax) (7). Steric effects cannot explain the observed conformational preferences, like equal population of the two conformers of 6, or different conformer ratio for 5 and 7. Actually, by employing the NBO analysis, in particular, considering the second order perturbation energies, vicinal stereoelectronic interactions between the Si-X and adjacent C-H, C-S, and C-C bonds proved responsible. KW - conformational analysis KW - low-temperature NMR spectroscopy KW - NBO analysis KW - quantum chemical calculations KW - 3-silathianes Y1 - 2011 U6 - https://doi.org/10.1002/poc.1758 SN - 0894-3230 VL - 24 IS - 4 SP - 320 EP - 326 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Adelsberger, Joseph A1 - Meier-Koll, Andreas A1 - Bivigou Koumba, Achille Mayelle A1 - Busch, Peter A1 - Holderer, Olaf A1 - Hellweg, Thomas A1 - Laschewsky, André A1 - Müller-Buschbaum, Peter A1 - Papadakis, Christine M. T1 - The collapse transition and the segmental dynamics in concentrated micellar solutions of P(S-b-NIPAM) diblock copolymers JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - We investigate concentrated solutions of poly(styrene-b-N-isopropyl acrylamide) (P(S-b-NIPAM)) diblock copolymers in deuterated water (D2O). Both structural changes and the changes of the segmental dynamics occurring upon heating through the lower critical solution temperature (LCST) of PNIPAM are studied using small-angle neutron scattering and neutron spin-echo spectroscopy. The collapse of the micellar shell and the cluster formation of collapsed micelles at the LCST as well as an increase of the segmental diffusion coefficient after crossing the LCST are detected. Comparing to our recent results on a triblock copolymer P(S-b-NIPAM-b-S) [25], we observe that the collapse transition of P(S-b-NIPAM) is more complex and that the PNIPAM segmental dynamics are faster than in P(S-b-NIPAM-b-S). KW - Block copolymers KW - Responsive polymers KW - Small-angle neutron scattering KW - Neutron spin-echo spectroscopy Y1 - 2011 U6 - https://doi.org/10.1007/s00396-011-2382-3 SN - 0303-402X VL - 289 IS - 5-6 SP - 711 EP - 720 PB - Springer CY - New York ER - TY - JOUR A1 - Haase, Andrea A1 - Arlinghaus, Heinrich F. A1 - Tentschert, Jutta A1 - Jungnickel, Harald A1 - Graf, Philipp A1 - Mantion, Alexandre A1 - Draude, Felix A1 - Galla, Sebastian A1 - Plendl, Johanna A1 - Goetz, Mario E. A1 - Masic, Admir A1 - Meier, Wolfgang P. A1 - Thuenemann, Andreas F. A1 - Taubert, Andreas A1 - Luch, Andreas T1 - Application of Laser Postionization Secondary Neutral Mass Spectrometry/Time-of-Flight Secondary Ion Mass Spectrometry in Nanotoxicology: Visualization of Nanosilver in Human Macrophages and Cellular Responses JF - ACS nano N2 - Silver nanoparticles (SNP) are the subject of worldwide commercialization because of their antimicrobial effects. Yet only little data on their mode of action exist. Further, only few techniques allow for visualization and quantification of unlabeled nanoparticles inside cells. To study SNP of different sizes and coatings within human macrophages, we introduce a novel laser postionization secondary neutral mass spectrometry (Laser-SNMS) approach and prove this method superior to the widely applied confocal Raman and transmission electron microscopy. With time-of-flight secondary ion mass spectrometry (TOF-SIMS) we further demonstrate characteristic fingerprints in the lipid pattern of the cellular membrane indicative of oxidative stress and membrane fluidity changes. Increases of protein carbonyl and heme oxygenase-1 levels in treated cells confirm the presence of oxidative stress biochemically. Intriguingly, affected phagocytosis reveals as highly sensitive end point of SNP-mediated adversity In macrophages. The cellular responses monitored are. hierarchically linked, but follow individual kinetics and are partially reversible. KW - nanosilver KW - Laser-SNMS KW - TOF-SIMS KW - confocal Raman microscopy KW - oxidative stress KW - protein carbonyls Y1 - 2011 U6 - https://doi.org/10.1021/nn200163w SN - 1936-0851 VL - 5 IS - 4 SP - 3059 EP - 3068 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Weigel, A. A1 - Dobryakov, A. A1 - Klaumünzer, Bastian A1 - Sajadi, M. A1 - Saalfrank, Peter A1 - Ernsting, N. P. T1 - Femtosecond stimulated raman spectroscopy of flavin after optical excitation JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - In blue-light photoreceptors using flavin (BLUF), the signaling state is formed already within several 100 ps after illumination, with only small changes of the absorption spectrum. The accompanying structural evolution can, in principle, be monitored by femtosecond stimulated Raman spectroscopy (FSRS). The method is used here to characterize the excited-state properties of riboflavin and flavin adenine dinucleotide in polar solvents. Raman modes are observed in the range 90-1800 cm(-1) for the electronic ground state S-0 and upon excitation to the S-1 state, and modes >1000 cm(-1) of both states are assigned with the help of quantum-chemical calculations. Line shapes are shown to depend sensitively on resonance conditions. They are affected by wavepacket motion in any of the participating electronic states, resulting in complex amplitude modulation of the stimulated Raman spectra. Wavepackets in S-1 can be marked, and thus isolated, by stimulated-emission pumping with the picosecond Raman pulses. Excited-state absorption spectra are obtained from a quantitative comparison of broadband transient fluorescence and absorption. In this way, the resonance conditions for FSRS are determined. Early differences of the emission spectrum depend on excess vibrational energy, and solvation is seen as dynamic Stokes shift of the emission band. The ne state is evidenced only through changes of emission oscillator strength during solvation. S-1 quenching by adenine is seen with all methods in terms of dynamics, not by spectral intermediates. Y1 - 2011 U6 - https://doi.org/10.1021/jp1117129 SN - 1520-6106 VL - 115 IS - 13 SP - 3656 EP - 3680 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Laemmermann, Anica A1 - Kühn, Heiner T1 - Synthesis and NMR spectra of the syn and anti isomers of substituted cyclobutanes-evidence for steric and spatial hyperconjugative interactions JF - Tetrahedron N2 - The syn and anti isomers of cis,cis-tricyclo[5.3.0.0(2.6)]dec-3-ene derivatives have been synthesized and their (1)H and (13)C NMR spectra unequivocally analyzed. Both their structures and their (1)H and (13)C NMR chemical shifts were calculated by DFT, the latter two calculations employing the GIAO perturbation method. Additionally, calculated NMR shielding values were partitioned into Lewis and non-Lewis contributions from the bonds and lone pairs involved in the molecules by accompanying NBO and NCS analyses. The differences between the syn and anti isomers were evaluated with respect to steric and spatial hyperconjugation interactions. KW - Conformational analysis KW - cis,cis-Tricyclo[5.3.0.0(2,6)]dec-3-enes KW - NMR KW - DFT calculation KW - NBO/NCS analysis Y1 - 2011 U6 - https://doi.org/10.1016/j.tet.2011.02.012 SN - 0040-4020 VL - 67 IS - 14 SP - 2596 EP - 2604 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Marsat, Jean-Noel A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Berlepsch, Hans V. A1 - Boettcher, Christoph A1 - Laschewsky, André T1 - Self-Assembly into multicompartment micelles and selective solubilization by Hydrophilic-Lipophilic-Fluorophilic block copolymers JF - Macromolecules : a publication of the American Chemical Society N2 - Amphiphilic linear ternary block copolymers (ABC) were synthesized in three consecutive steps by the reversible addition fragmentation chain transfer (RAFT) method. Using oligo(ethylene oxide) monomethyl ether acrylate, benzyl acrylate, and 1H,1H-perfluorobutyl acrylate monomers, the triblock copolymers consist of a hydrophilic (A), a lipophilic (B), and a fluorophilic (C) block. The block sequence of the triphilic copolymers was varied systematically to provide all possible variations: ABC, ACB, and BAC. All blocks have glass transition temperatures below 0 degrees C. Self-assembly into spherical micellar aggregates was observed in aqueous solution, where hydrophobic cores undergo local phase separation into various ultrastructures as shown by cryogenic transmission electron microscopy (cryo-TEM). Selective solubilization of substantial quantities of hydrocarbon and fluorocarbon low molar mass compounds by the lipophilic and fluorophilic block, respectively, is demonstrated. Y1 - 2011 U6 - https://doi.org/10.1021/ma200032j SN - 0024-9297 VL - 44 IS - 7 SP - 2092 EP - 2105 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Weiss, Jan A1 - Laschewsky, André T1 - Temperature-induced self-assembly of triple-responsive triblock copolymers in aqueous solutions JF - Langmuir N2 - A series of triple-thermoresponsive triblock copolymers from poly(N-n-propylacrylamide) (PNPAM, A), poly(methoxydiethylene glycol acrylate) (PMDEGA, B), and poly(N-ethylacrylamide) (PNEAM, C) was synthesized by sequential reversible addition-fragmentation chain transfer polymerizations. Polymers of differing block sequences, ABC, BAC, and ACB, with increasing phase transition temperatures in the order A < B < C were prepared. Their aggregation behavior in dilute aqueous solution was investigated using dynamic light scattering, turbidimetry, and NMR spectroscopy. The self-organization of such polymers was found to dependent strongly on the block sequence. While polymers with a terminal low-LCST (lower critical solution temperature) block undergo aggregation above the first phase transition temperature at 20-25 degrees C, triblock copolymers with the low-LCST block in the middle show aggregation only above the second phase transition. The collapse of the middle block is not sufficient to induce aggregation but produces instead stable, unimolecular micelles with a collapsed middle block, as supported by NMR and fluorescence probe data. Continued heating of all copolymers led to two additional thermal transitions at 40-55 and 70-80 degrees C, which could be correlated to the phase transitions of the B and C blocks, respectively. All polymers show a high tendency for cluster formation, once aggregation is induced. The carrier abilities of the triple responsive triblock copolymers for hydrophobic agents were probed with the solvatochromic fluorescence dye Nile Red. With passing through the first thermal transition, the block copolymers are capable of solubilizing Nile Red. In the case of block copolymers with sequences ABC or ACB, which bear the low-LCST block at one terminus, notable amounts of dye are solubilized already at this stage. In contrast, the hydrophobic probe is much less efficiently incorporated by the BAC triblock copolymer, which forms unimolecular micelles. Only after the collapse of the B block, when reaching the second phase transition at about 45 degrees C, does aggregation occur and solubilization becomes efficient. In the case of ABC and ACB polymers, the hydrophobic probe seems to partition between the originally collapsed A chains and the additional hydrophobic chains formed after the collapse of the less hydrophobic B block. Y1 - 2011 U6 - https://doi.org/10.1021/la200115p SN - 0743-7463 VL - 27 IS - 8 SP - 4465 EP - 4473 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Vukicevic, Radovan A1 - Beuermann, Sabine T1 - Fullerenes decorated with poly(vinylidene fluoride) JF - Macromolecules : a publication of the American Chemical Society N2 - Fullerenes decorated with poly(vinylidene fluoride) (PVDF) were synthesized in a three-step procedure: Iodine transfer polymerization of vinylidene fluoride with C(6)F(12)I(2) as the chain transfer agent was carried out in supercritical carbon dioxide to synthesize iodine-terminated PVDF, which was subsequently transformed to azide-terminated polymer. Finally, azide-terminated PVDF chains were attached to a fullerene core under microwave irradiation at 160 degrees C in 1.5 h. The materials were characterized by NMR, FT-IR, UV/vis, GPC, elemental analysis, and DSC. On average, 4-5 PVDF chains are attached to one C(60) moiety. FT-IR spectra and DSC measurements indicate that the polymer end groups strongly affect the crystallinity of the material. For PVDF with azide end groups and PVDF attached to fullerenes the fraction of the beta polymorph is dominant while alpha polymorphs are almost absent. Y1 - 2011 U6 - https://doi.org/10.1021/ma102754c SN - 0024-9297 VL - 44 IS - 8 SP - 2597 EP - 2603 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Idzik, Krzysztof Ryszard A1 - Cywinski, Piotr J. A1 - Cranfield, Charles G. A1 - Mohr, Gerhard J. A1 - Beckert, Rainer T1 - Molecular recognition of the antiretroviral drug abacavir towards the development of a novel carbazole-based fluorosensor JF - Journal of fluorescence N2 - Due to their optical and electro-conductive attributes, carbazole derivatives are interesting materials for a large range of biosensor applications. In this study, we present the synthesis routes and fluorescence evaluation of newly designed carbazole fluorosensors that, by modification with uracil, have a special affinity for antiretroviral drugs via either Watson-Crick or Hoogsteen base pairing. To an N-octylcarbazole-uracil compound, four different groups were attached, namely thiophene, furane, ethylenedioxythiophene, and another uracil; yielding four different derivatives. Photophysical properties of these newly obtained derivatives are described, as are their interactions with the reverse transcriptase inhibitors such as abacavir, zidovudine, lamivudine and didanosine. The influence of each analyte on biosensor fluorescence was assessed on the basis of the Stern-Volmer equation and represented by Stern-Volmer constants. Consequently we have demonstrated that these structures based on carbazole, with a uracil group, may be successfully incorporated into alternative carbazole derivatives to form biosensors for the molecular recognition of antiretroviral drugs. KW - HIV KW - HAART KW - Antiretroviral drugs KW - Carbazole KW - Base pairing KW - Fluorescence spectroscopy Y1 - 2011 U6 - https://doi.org/10.1007/s10895-010-0798-7 SN - 1053-0509 SN - 1573-4994 VL - 21 IS - 3 SP - 1195 EP - 1204 PB - Springer CY - New York ER - TY - JOUR A1 - Vidadala, Srinivasa Rao A1 - Pimpalpalle, Tukaram M. A1 - Linker, Torsten A1 - Hotha, Srinivas T1 - Gold-Catalyzed reactions of 2-C-Branched carbohydrates mild glycosidations and selective anomerizations JF - European journal of organic chemistry N2 - 2-C-branched methyl glycosides react with various alcohols under gold catalysis to transglycosylated products. The method is applicable for the convenient synthesis of disaccharides. Without nucleophile a selective anomerization occurs, giving first access to alpha-configured 2-C-nitromethyl glycosides. The results are interesting for the mechanism of gold-catalyzed glycosidations. KW - Anomerization KW - Carbohydrates KW - Glycosidation KW - Gold KW - Synthetic methods Y1 - 2011 U6 - https://doi.org/10.1002/ejoc.201100134 SN - 1434-193X IS - 13 SP - 2426 EP - 2430 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Prieto, Susana A1 - Shkilnyy, Andriy A1 - Rumplasch, Claudia A1 - Ribeiro, Artur A1 - Javier Arias, F. A1 - Carlos Rodriguez-Cabello, Jose A1 - Taubert, Andreas T1 - Biomimetic calcium phosphate mineralization with multifunctional elastin-like recombinamers JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - Biomimetic hybrid materials based on a polymeric and an inorganic component such as calcium phosphate are potentially useful for bone repair. The current study reports on a new approach toward biomimetic hybrid materials using a set of recombinamers (recombinant protein materials obtained from a synthetic gene) as crystallization additive for calcium phosphate. The recombinamers contain elements from elastin, an elastic structural protein, and statherin, a salivary protein. Via genetic engineering, the basic elastin sequence was modified with the SN(A)15 domain of statherin, whose interaction with calcium phosphate is well-established. These new materials retain the biocompatibility, "smart" nature, and desired mechanical behavior of the elastin-like recombinamer (ELR) family. Mineralization in simulated body fluid (SBF) in the presence of these recombinamers reveals surprising differences. Two of the polymers inhibit calcium phosphate deposition (although they contain the statherin segment). In contrast, the third polymer, which has a triblock structure, efficiently controls the calcium phosphate formation, yielding spherical hydroxyapatite (HAP) nanoparticles with diameters from 1 to 3 nm after 1 week in SBF at 37 degrees C. However, at lower temperatures, no precipitation is observed with any of the polymers. The data thus suggest that the molecular design of ELRs containing statherin segments and the selection of an appropriate polymer structure are key parameters to obtain functional materials for the development of intelligent systems for hard tissue engineering and subsequent in vivo applications. Y1 - 2011 U6 - https://doi.org/10.1021/bm200287c SN - 1525-7797 VL - 12 IS - 5 SP - 1480 EP - 1486 PB - American Chemical Society CY - Washington ER -