TY - JOUR A1 - Gress, Anja A1 - Heilig, Anne A1 - Smarsly, Bernd M. A1 - Heydenreich, Matthias A1 - Schlaad, Helmut T1 - Hydrogen-bonded polymer nanotubes in water N2 - Intermolecular hydrogen bonding, not hydrophobic interaction, is the driving force for the spontaneous self- assembly of glycosylated polyoxazoline chains into nanotubes in dilute aqueous solution. The structural information is encoded in the relatively simple molecular structure of chains consisting of a tertiary polyamide backbone (hydrogen- accepting) and glucose side chains (hydrogen-donating). The formation of the nanotubes should occur through bending and closing of a 2D hydrogen-bonded layer of interdigitated polymer chains. Y1 - 2009 UR - http://pubs.acs.org/loi/mamobx U6 - https://doi.org/10.1021/Ma900227t SN - 0024-9297 ER - TY - JOUR A1 - Schlaad, Helmut A1 - You, Liangchen A1 - Sigel, Reinhard A1 - Smarsly, Bernd A1 - Heydenreich, Matthias A1 - Mantion, Alexandre A1 - Masic, Admir T1 - Glycopolymer vesicles with an asymmetric membrane N2 - Direct dissolution of glycosylated polybutadiene-poly(ethylene oxide) block copolymers can lead to the spontaneous formation of vesicles or membranes, which on the outside are coated with glucose and on the inside with poly(ethylene oxide). Y1 - 2009 UR - http://www.rsc.org/ej/CC/2009/b820887e.pdf U6 - https://doi.org/10.1039/B820887e SN - 1359-7345 ER - TY - JOUR A1 - Tritschler, Ulrich A1 - Zlotnikov, Igor A1 - Keckeis, Philipp A1 - Schlaad, Helmut A1 - Cölfen, Helmut T1 - Optical properties of self-organized gold nanorod-polymer hybrid films JF - Langmuir N2 - High fractions of gold nanorods were locally aligned by means of a polymeric liquid crystalline phase. The gold nanorods constituting >80 wt % of the thin organic-inorganic composite films form a network with side-by-side and end-to-end combinations. Organization into these network structures was induced by shearing gold nanorod-LC polymer dispersions via spin-coating. The LC polymer is a polyoxazoline functionalized with pendent cholesteryl and carboxyl side groups enabling the polymer to bind to the CTAB stabilizer layer of the gold nanorods via electrostatic interactions, thus forming the glue between organic and inorganic components, and to form a chiral nematic lyotropic phase. The self-assembled locally oriented gold nanorod structuring enables control over collective optical properties due to plasmon resonance coupling, reminiscent of enhanced optical properties of natural biomaterials. Y1 - 2014 U6 - https://doi.org/10.1021/la503507u SN - 0743-7463 VL - 30 IS - 46 SP - 13781 EP - 13790 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Fuehrer, Felix N. A1 - Schlaad, Helmut T1 - ADMET polymerization of amino-acid-based diene JF - Macromolecular chemistry and physics N2 - 1,4-Di(homo)allyl-2,5-diketopiperazines are synthesized and polymerized via ADMET using the Hoveyda-Grubbs 2nd generation catalyst. The but-3-enylated diketopiperazine can be converted into unsaturated tertiary polyamide with molar mass of <3000 g mol(-1), whereas the allylated diketopiperazine cannot. Double-bond isomerization occurs regardless of whether or not benzoquinone is present. A polyesteramide with a higher molar mass of ca. 4800 g mol(-1) is obtained by the alternating copolymerization (ALTMET) of 1,4-di(but-3-enyl)-2,5-di ketopiperazine and ethylene glycol diacrylate. A post-polymerization modification of the poly(ester)amides via radical thiol-ene chemistry, however, fails. KW - acyclic diene metathesis (ADMET) polymerization KW - amino acids KW - diketopiperazine KW - metathesis KW - step-growth polymerization Y1 - 2014 U6 - https://doi.org/10.1002/macp.201400166 SN - 1022-1352 SN - 1521-3935 VL - 215 IS - 22 SP - 2268 EP - 2273 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Brosnan, Sarah M. A1 - Schlaad, Helmut T1 - Modification of polypeptide materials by Thiol-X chemistry JF - Polymer : the international journal for the science and technology of polymers N2 - Thiol-X chemistry has proven to be a valuable toolbox for modification of peptides, proteins, monomers, and polymers. Recently, this has become especially true for the modification of polypeptides (monomers or polymers), which has resulted in a plethora of novel polymers and materials. With this in mind, this highlight focuses on the recent literature concerning the modification of polypeptides by the use of thiol-X chemistry, in particular to synthetic polypeptides either at the monomer or polymer stage modified by thiol-ene, -Michael addition, and -yne chemistries. (C) 2014 Published by Elsevier Ltd. KW - Polypeptide KW - Thiol-X KW - Click chemistry Y1 - 2014 U6 - https://doi.org/10.1016/j.polymer.2014.08.067 SN - 0032-3861 SN - 1873-2291 VL - 55 IS - 22 SP - 5511 EP - 5516 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Debsharma, Tapas A1 - Behrendt, Felix Nicolas A1 - Laschewsky, Andre A1 - Schlaad, Helmut T1 - Ring-opening metathesis polymerization of biomass-derived levoglucosenol JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker N2 - The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100kgmol(-1) and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 degrees C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment. KW - degradable polymers KW - metathesis KW - ring-opening polymerization KW - sustainable chemistry KW - thermoplastics Y1 - 2019 U6 - https://doi.org/10.1002/anie.201814501 SN - 1433-7851 SN - 1521-3773 VL - 58 IS - 20 SP - 6718 EP - 6721 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kaya, Kerem A1 - Debsharma, Tapas A1 - Schlaad, Helmut A1 - Yagci, Yusuf T1 - Cellulose-based polyacetals by direct and sensitized photocationic ring-opening polymerization of levoglucosenyl methyl ether JF - Polymer Chemistry N2 - This study aims to explore the photoinitiated cationic ring-opening polymerization of levoglucosenyl methyl ether (LGME), a chemical obtained from the most abundant biomass - cellulose. Direct and sensitized photopolymerizations of LGME using photoinitiators acting at the near UV or visible range in conjunction with diphenyliodonium hexafluoroantimonate (DPI) yielded unsaturated polyacetals with varying molar masses and distributions. Y1 - 2020 U6 - https://doi.org/10.1039/d0py01307b SN - 1759-9954 SN - 1759-9962 VL - 11 IS - 43 SP - 6884 EP - 6889 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Shkilnyy, Andriy A1 - Brandt, Jessica A1 - Mantion, Alexandre A1 - Paris, Oskar A1 - Schlaad, Helmut A1 - Taubert, Andreas T1 - Calcium phosphate with a channel-like morphology by polymer templating N2 - Calcium phosphate mineralization from aqueous solution in the presence of organic growth modifiers has been intensely studied in the recent past. This is mostly due to potential applications of the resulting composites in the biomaterials field. Polymers in particular are efficient growth modifiers. As a result, there has been a large amount of work on polymeric growth modifiers. Interestingly, however, relatively little work has been done on polycationic additives. The current paper shows that poly(ethylene oxide)b-poly(L-lysine) block copolymers lead to an interesting morphology of calcium phosphate precipitated at room temperature and subjected to a mild heat treatment at 85 degrees C. Electron microscopy, synchrotron X-ray diffraction, and porosity analysis show that a (somewhat) porous material with channel-like features forms. Closer inspection using transmission electron microscopy shows that the channels are probably not real channels. Much rather the morphology is the result of the aggregation of ca. 100-nm-sized rodlike primary particles, which changes upon drying to exhibit the observed channel-like features. Comparison experiments conducted in the absence of polymer and with poly(ethylene oxide)-b-poly(L-glutamate) show that these features only form in the presence of the polycationic poly(L-lysine) block, suggesting a distinct interaction of the polycation with either the crystal or the phosphate ions prior to mineralization. Y1 - 2009 UR - http://pubs.acs.org/journal/cmatex U6 - https://doi.org/10.1021/Cm803244z SN - 0897-4756 ER - TY - JOUR A1 - Casse, Olivier A1 - Shkilnyy, Andriy A1 - Linders, Jürgen A1 - Mayer, Christian A1 - Häussinger, Daniel A1 - Völkel, Antje A1 - Thünemann, Andreas F. A1 - Dimova, Rumiana A1 - Cölfen, Helmut A1 - Meier, Wolfgang P. A1 - Schlaad, Helmut A1 - Taubert, Andreas T1 - Solution behavior of double-hydrophilic block copolymers in dilute aqueous solution JF - Macromolecules : a publication of the American Chemical Society N2 - The self-assembly of double-hydrophilic poly(ethylene oxide)-poly(2-methyl-2-oxazoline) diblock copolymers in water has been studied. Isothermal titration calorimetry, small-angle X-ray scattering, and analytical ultracentrifugation suggest that only single polymer chains are present in solution. In contrast, light scattering and transmission electron microscopy detect aggregates with radii of ca. 100 nm. Pulsed field gradient NMR spectroscopy confirms the presence of aggregates, although only 2% of the polymer chains undergo aggregation. Water uptake experiments indicate differences in the hydrophilicity of the two blocks, which is believed to be the origin of the unexpected aggregation behavior (in accordance with an earlier study by Ke et al. [Macromolecules 2009, 42, 5339-5344]). The data therefore suggest that even in double-hydrophilic block copolymers, differences in hydrophilicity are sufficient to drive polymer aggregation, a phenomenon that has largely been overlooked or ignored so far. Y1 - 2012 U6 - https://doi.org/10.1021/ma300621g SN - 0024-9297 VL - 45 IS - 11 SP - 4772 EP - 4777 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Yuan, Jiayin A1 - ten Brummelhuis, Niels A1 - Junginger, Mathias A1 - Xie, Zailai A1 - Lu, Yan A1 - Taubert, Andreas A1 - Schlaad, Helmut T1 - Diversified applications of chemically modified 1,2-Polybutadiene JF - Macromolecular rapid communications N2 - Commercially available 1,2-PB was transformed into a well-defined reactive intermediate by quantitative bromination. The brominated polymer was used as a polyfunctional macroinitiator for the cationic ring-opening polymerization of 2-ethyl-2-oxazoline to yield a water-soluble brush polymer. Nucleophilic substitution of bromide by 1-methyl imidazole resulted in the formation of polyelectrolyte copolymers consisting of mixed units of imidazolium, bromo, and double bond. These copolymers, which were soluble in water without forming aggregates, were used as stabilizers in the heterophase polymerization of styrene and were also studied for their ionic conducting properties. KW - emulsion polymerization KW - polybutadiene KW - polyelectrolytes KW - polymer modification KW - ring-opening polymerization Y1 - 2011 U6 - https://doi.org/10.1002/marc.201100254 SN - 1022-1336 VL - 32 IS - 15 SP - 1157 EP - 1162 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Goebel, Ronald A1 - Hesemann, Peter A1 - Friedrich, Alwin A1 - Rothe, Regina A1 - Schlaad, Helmut A1 - Taubert, Andreas T1 - Modular thiol-ene chemistry approach towards mesoporous silica monoliths with organically modified pore walls JF - Chemistry - a European journal N2 - The surface modification of mesoporous silica monoliths through thiol-ene chemistry is reported. First, mesoporous silica monoliths with vinyl, allyl, and thiol groups were synthesized through a sol-gel hydrolysis-poly-condensation reaction from tetramethyl orthosilicate (TMOS) and vinyltriethoxysilane, allyltriethoxysilane, and (3-mercaptopropyl) trimethoxysilane, respectively. By variation of the molar ratio of the comonomers TMOS and functional silane, mesoporous silica objects containing different amounts of vinyl, allyl, and thiol groups were obtained. These intermediates can subsequently be derivatized through radical photoaddition reactions either with a thiol or an olefin, depending on the initial pore wall functionality, to yield silica monoliths with different pore-wall chemistries. Nitrogen sorption, small-angle X-ray scattering, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis, and redox titration demonstrate that the synthetic pathway influences the morphology and pore characteristics of the resulting monoliths and also plays a significant role in the efficiency of functionalization. Moreover, the different reactivity of the vinyl and allyl groups on the pore wall affects the addition reaction, and hence, the degree of the pore-wall functionalization. This report demonstrates that thiol-ene photoaddition reactions are a versatile platform for the generation of a large variety of organically modified silica monoliths with different pore surfaces. KW - mesoporous materials KW - photochemistry KW - sol-gel processes KW - surface chemistry Y1 - 2014 U6 - https://doi.org/10.1002/chem.201403982 SN - 0947-6539 SN - 1521-3765 VL - 20 IS - 52 SP - 17579 EP - 17589 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Löbbicke, Ruben A1 - Chanana, Munish A1 - Schlaad, Helmut A1 - Pilz-Allen, Christine A1 - Günter, Christina A1 - Möhwald, Helmuth A1 - Taubert, Andreas T1 - Polymer Brush Controlled Bioinspired Calcium Phosphate Mineralization and Bone Cell Growth JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - Polymer brushes on thiol-modified gold surfaces were synthesized by using terminal thiol groups for the surface initiated free radical polymerization of methacrylic acid and dimethylaminotheyl methacrylate, respectively. Atomic force microscopy shows that the resulting poly(methacrylic acid (PMAA) and poly(dimethylaminothyl methacrylate) (PDM- AEMA) brushes are homogeneous. Contact angle measurements show that the brushes are pH responsive and can reversibly be protonated and deprotonated. Mineralization of the brushes with calcium phosphate at different pH yields homogeneously mineralized surfaces, and preosteoblastic cells proliferate-on be number of living cells on the mineralized hybrid surface is ca. 3 times (P corresponding nonmineralized brushes. Y1 - 2011 U6 - https://doi.org/10.1021/bm200991b SN - 1525-7797 VL - 12 IS - 10 SP - 3753 EP - 3760 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Chandran, Sivasurender A1 - Dold, Stefanie A1 - Buvignier, Amaury A1 - Krannig, Kai-Steffen A1 - Schlaad, Helmut A1 - Reiter, Günter A1 - Reiter, Renate T1 - Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States JF - Langmuir N2 - Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films. Y1 - 2015 U6 - https://doi.org/10.1021/acs.langmuir.5b01212 SN - 0743-7463 VL - 31 IS - 23 SP - 6426 EP - 6435 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Knecht, Volker A1 - Reiter, Guenter A1 - Schlaad, Helmut A1 - Reiter, Renate T1 - Structure Formation in Langmuir Peptide Films As Revealed from Coarse-Grained Molecular Dynamics Simulations JF - Langmuir N2 - Molecular dynamics simulations in conjunction with the Martini coarse-grained model have been used to investigate the (nonequilibrium) behavior of helical 22-residue poly(gamma-benzyl-L-glutamate) (PBLG) peptides at the water/vapor interface. Preformed PBLG mono- or bilayers homogeneously covering the water surface laterally collapse in tens of nanoseconds, exposing significant proportions of empty water surface. This behavior was also observed in recent AFM experiments at similar areas per monomer, where a complete coverage had been assumed in earlier work. In the simulations, depending on the area per monomer, either elongated clusters or fibrils form, whose heights (together with the portion of empty water surface) increase over time. Peptides tend to align with respect to the fiber axis or with the major principal axis of the cluster, respectively. The aspect ratio of the cluster observed is 1.7 and, hence, comparable to though somewhat smaller than the aspect ratio of the peptides in alpha-helical conformation, which is 2.2. The heights of the fibrils is 3 nm after 20 ns and increases to 4.5 nm if the relaxation time is increased by 2 orders of magnitude, in agreement with the experiment. Aggregates with heights of about 3 or 4.5 nm are found to correspond to local bi- or trilayer structures, respectively. Y1 - 2017 U6 - https://doi.org/10.1021/acs.langmuir.7b01455 SN - 0743-7463 VL - 33 SP - 6492 EP - 6502 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Noack, Sebastian A1 - Schanzenbach, Dirk A1 - Koetz, Joachim A1 - Schlaad, Helmut T1 - Polylactide-based amphiphilic block copolymers BT - Crystallization-Induced Self-Assembly and Stereocomplexation JF - Macromolecular rapid communications N2 - The aqueous self-assembly behavior of a series of poly(ethylene glycol)-poly(l-/d-lactide) block copolymers and corresponding stereocomplexes is examined by differential scanning calorimetry, dynamic light scattering, and transmission electron microscopy. Block copolymers assemble into spherical micelles and worm-like aggregates at room temperature, whereby the fraction of the latter seemingly increases with decreasing lactide weight fraction or hydrophobicity. The formation of the worm-like aggregates arises from the crystallization of the polylactide by which the spherical micelles become colloidally unstable and fuse epitaxically with other micelles. The self-assembly behavior of the stereocomplex aggregates is found to be different from that of the block copolymers, resulting in rather irregular-shaped clusters of spherical micelles and pearl-necklace-like structures. KW - crystallization KW - polylactide KW - self-assembly KW - stereocomplexation Y1 - 2018 U6 - https://doi.org/10.1002/marc.201800639 SN - 1022-1336 SN - 1521-3927 VL - 40 IS - 1 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Matic, Aleksandar A1 - Hess, Andreas A1 - Schanzenbach, Dirk A1 - Schlaad, Helmut T1 - Epoxidized 1,4-polymyrcene JF - Polymer chemistry N2 - 1,4-Polymyrcene was synthesized by anionic polymerization and epoxidized using meta-chloroperbenzoic acid. Samples with different degrees of epoxidation (25%, 49%, 74%, and 98%) were prepared and examined according to their chemical and thermal properties. Epoxidation was found to increase the glass transition temperature (T-g = 14 degrees C for the 98% epoxidized 1,4-polymyrcene) as well as the shelf live (>10 months). The trisubstituted epoxide groups were remarkably stable against nucleophiles under basic conditions but cross-linked or hydrolyzed in the presence of an acid. Also, highly epoxidized 1,4-polymyrcene readily cross-linked upon annealing at 260 degrees C to produce an epoxy resin. KW - comb poly(beta-myrcene)-graft-poly(l-lactide) copolymers KW - thermoplastic elastomer synthesis KW - myrcen KW - polymerization KW - epoxidation Y1 - 2020 U6 - https://doi.org/10.1039/c9py01783f SN - 1759-9954 SN - 1759-9962 VL - 11 IS - 7 SP - 1364 EP - 1368 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Glatzel, Julia A1 - Noack, Sebastian A1 - Schanzenbach, Dirk A1 - Schlaad, Helmut T1 - Anionic polymerization of dienes in ‘green’ solvents JF - Polymer international N2 - Isoprene and beta-myrcene were polymerized by anionic polymerization in bulk and in the 'green' ether solvents cyclopentyl methyl ether and 2-methyltetrahydrofuran and, for comparison, in cyclohexane and tetrahydrofuran. The polydienes produced in bulk and in cyclohexane contained high amounts of 1,4 units (>90%) whereas those produced in ether solvents were rich in 1,2 and 3,4 units (36%-86%). Comparison of the microstructures and glass transition temperatures of the polydienes obtained in the various solvents suggests that conventionally used solvents can be substituted by environmentally more friendly alternatives. KW - isoprene KW - β‐myrcene KW - anionic polymerization KW - green KW - solvents KW - microstructure KW - glass transition Y1 - 2020 U6 - https://doi.org/10.1002/pi.6152 SN - 0959-8103 SN - 1097-0126 VL - 70 IS - 2 SP - 181 EP - 184 PB - Wiley CY - Hoboken ER -