TY - JOUR A1 - Guiet, Amandine A1 - Unmüssig, Tobias A1 - Göbel, Caren A1 - Vainio, Ulla A1 - Wollgarten, Markus A1 - Driess, Matthias A1 - Schlaad, Helmut A1 - Polte, Jörg A1 - Fischer, Anna T1 - Yolk@Shell Nanoarchitectures with Bimetallic Nanocores - Synthesis and Electrocatalytic Applications JF - Earth & planetary science letters KW - AgAu alloy nanoparticles KW - tin-rich ITO KW - yolk@shell materials KW - nanoreactor KW - soft-templating KW - inverse micelles KW - polystyrene-block-poly(4-vinylpyridine) Y1 - 2016 U6 - https://doi.org/10.1021/acsami.6b06595 SN - 1944-8244 VL - 8 SP - 28019 EP - 28029 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Koshkina, Olga A1 - Westmeier, Dana A1 - Lang, Thomas A1 - Bantz, Christoph A1 - Hahlbrock, Angelina A1 - Würth, Christian A1 - Resch-Genger, Ute A1 - Braun, Ulrike A1 - Thiermann, Raphael A1 - Weise, Christoph A1 - Eravci, Murat A1 - Mohr, Benjamin A1 - Schlaad, Helmut A1 - Stauber, Roland H. A1 - Docter, Dominic A1 - Bertin, Annabelle A1 - Maskos, Michael T1 - Tuning the Surface of Nanoparticles: Impact of Poly(2-ethyl-2-oxazoline) on Protein Adsorption in Serum and Cellular Uptake JF - Macromolecular bioscience N2 - Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach. With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles. KW - cellular uptake KW - nanoparticles KW - poly(2-ethyl-2oxazoline) KW - poly(ethylene glycol) KW - protein adsorption Y1 - 2016 U6 - https://doi.org/10.1002/mabi.201600074 SN - 1616-5187 SN - 1616-5195 VL - 16 SP - 1287 EP - 1300 PB - Wiley-VCH CY - Weinheim 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 - Wessig, Pablo A1 - Schulze, Tanja A1 - Pfennig, Alexandra A1 - Weidner, Steffen M. A1 - Prentzel, Sascha A1 - Schlaad, Helmut T1 - Thiol-ene polymerization of oligospiroketal rods JF - Polymer Chemistry N2 - The nucleophilic thiol-ene (thia-Michael) reaction between molecular rods bearing terminal thiols and bis-maleimides was investigated. The molecular rods have oligospiroketal (OSK) and oligospirothioketal (OSTK) backbones. Contrary to the expectations, cyclic oligomers were always obtained instead of linear rigid-rod polymers. Replacing the OS(T)K rods with a flexible chain yielded polymeric products, suggesting that the OS(T) K structure is responsible for the formation of cyclic products. The reason for the preferred formation of cyclic products is due to the presence of folded conformations, which have already been described for articulated rods. Y1 - 2017 U6 - https://doi.org/10.1039/c7py01569k SN - 1759-9954 SN - 1759-9962 VL - 8 SP - 6879 EP - 6885 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Matic, Aleksandar A1 - Schlaad, Helmut T1 - Thiol-ene photofunctionalization of 1,4-polymyrcene JF - Polymer international N2 - 1,4-Polymyrcene was synthesized by anionic polymerization of -myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, ethyl 2-mercaptopropionate and 2-methyl-2-propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4-polymyrcene decreased in the order 1 degrees thiol (ca 95%) > 2 degrees thiol (ca 80%) > 3 degrees thiol (<5%), due to the reversibility of the thiol-ene reaction. Remarkably, thiol addition to the side-chain double bonds was 8 - 10 times (1 degrees thiol) or 24 times (2 degrees thiol) faster than to the main-chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10-fold excess of thiol with respect to myrcene units, the thiol-ene addition was accompanied by chain coupling reactions, which in the extreme case of 3 degrees thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl-thioglycolate-functionalized 1,4-polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. (c) 2018 Society of Chemical Industry KW - polymyrcene KW - thiol-ene KW - photochemistry KW - regioselectivity Y1 - 2018 U6 - https://doi.org/10.1002/pi.5534 SN - 0959-8103 SN - 1097-0126 VL - 67 IS - 5 SP - 500 EP - 505 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Zou, Hua A1 - Schlaad, Helmut T1 - Thermoresponsive PNIPAM/Silica Nanoparticles by Direct Photopolymerization in Aqueous Media JF - Journal of polymer science : A, Polymer chemistry N2 - This article presents a simple and facile method to fabricate thermoresponsive polymer-grafted silica particles by direct surface-initiated photopolymerization of N-isopropylacrylamide (NIPAM). This method is based on silica particles bearing thiol functionalities, which are transformed into thiyl radicals by irradiation with UV light to initiate the polymerization of NIPAM in aqueous media at room temperature. The photopolymerization of NIPAM could be applied to smaller thiol-functionalized particles (approximate to 48 nm) as well as to larger particles (approximate to 692 nm). Hollow poly(NIPAM) capsules could be formed after etching away the silica cores from the composite particles. It is possible to produce tailor-made composite particles or capsules for particular applications by extending this approach to other vinyl monomers. (c) 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015, 53, 1260-1267 KW - nanocomposites KW - nanoparticles KW - photopolymerization KW - silica nanoparticles KW - surface-initiated photopolymerization KW - thermoresponsive KW - thiol Y1 - 2015 U6 - https://doi.org/10.1002/pola.27593 SN - 0887-624X SN - 1099-0518 VL - 53 IS - 10 SP - 1260 EP - 1267 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Bogomolova, Anna A1 - Secker, Christian A1 - Koetz, Joachim A1 - Schlaad, Helmut T1 - Thermo-induced multistep assembly of double-hydrophilic block copolypeptoids in water JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - The aqueous solution behavior of thermoresponsive-hydrophilic block copolypeptoids, i.e., poly(N-(n-propyl)glycine) (x) -block-poly(N-methylglycine) (y) (x = 70; y = 23, 42, 76), in the temperature range of 20-45 A degrees C is studied. Turbidimetric analyses of the 0.1 wt% aqueous solutions reveal two cloud points at T (cp)similar to 30 and 45 A degrees C and a clearing point in between at T (cl)similar to 42 A degrees C. Temperature-dependent dynamic light scattering (DLS) suggest that right above the first collapse temperature, single polymer molecules assemble into large structures which upon further heating, i.e., at the clearing point temperature, disassemble into micelle-like structures. Upon further heating, the aggregates start to grow again in size, as recognized by the second cloud point, through a crystallization process. KW - Polypeptoids KW - Block copolymers KW - Thermoresponsive KW - Self-assembly Y1 - 2017 U6 - https://doi.org/10.1007/s00396-017-4044-6 SN - 0303-402X SN - 1435-1536 VL - 295 SP - 1305 EP - 1312 PB - Springer CY - New York ER - TY - JOUR A1 - Secker, Christian A1 - Voelkel, Antje A1 - Tiersch, Brigitte A1 - Koetz, Joachim A1 - Schlaad, Helmut T1 - Thermo-Induced Aggregation and Crystallization of Block Copolypeptoids in Water JF - Macromolecules : a publication of the American Chemical Society N2 - Block copolypeptoids comprising a thermosensitive, crystallizable poly(N-(n-propyl)glycine) block and a watersoluble poly(N-methylglycine) block, P70My (y = 23, 42, 76, 153, and 290), were synthesized bY ring-opening polymerization of the corresponding N-alkylglycine N-carboxyanhydrides (NCAs) and examined according to their thermo-induced aggregation and crystallization in water by turbidimetty, micro-differential scanning calorimetry (micro-DSC); cryogenic scanning electron microscopy (cryo-SEM), analytical ultracentrifugation (AUC), and static light scattering (SLS). At a temperature above the cloud point temperature, the initially formed micellar aggregates started to crystallize and grow into larger complex assemblies of about 100-500 nm, exhibiting flower-like (P70M23), ellipsoidal (P70M42 and P70M72) or irregular shapes (P70M153 and.P70M290). Y1 - 2016 U6 - https://doi.org/10.1021/acs.macromol.5b02481 SN - 0024-9297 SN - 1520-5835 VL - 49 SP - 979 EP - 985 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Secker, Christian A1 - Brosnan, Sarah M. A1 - Limberg, Felix Rolf Paul A1 - Braun, Ulrike A1 - Trunk, Matthias A1 - Strauch, Peter A1 - Schlaad, Helmut T1 - Thermally Induced Crosslinking of Poly(N-Propargyl Glycine) JF - Macromolecular chemistry and physics N2 - As polypeptoids become increasingly popular, they present a more soluble and processable alternative to natural and synthetic polypeptides; the breadth of their potential functionality slowly comes into focus. This report analyzes the ability of an alkyne-functionalized polypeptoid, poly(N-propargyl glycine), to crosslink upon heating. The crosslinking process is analyzed by thermal analysis (differential scanning calorimetry and thermogravimetric analysis), Fourier-transform infrared, electron paramagnetic resonance, and solid-state NMR spectroscopy. While a precise mechanism cannot be confidently assigned, it is clear that the reaction proceeds by a radical mechanism that exclusively involves the alkyne functionality, which, upon crosslinking, yields alkene and aromatic products. KW - Fourier-transform infrared KW - metal-free crosslinking KW - polypeptoid KW - propargyl KW - solid-state NMR Y1 - 2015 U6 - https://doi.org/10.1002/macp.201500223 SN - 1022-1352 SN - 1521-3935 VL - 216 IS - 21 SP - 2080 EP - 2085 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Raju, Rajarshi Roy A1 - Liebig, Ferenc A1 - Hess, Andreas A1 - Schlaad, Helmut A1 - Koetz, Joachim T1 - Temperature-triggered reversible breakdown of polymer-stabilized olive BT - silicone oil Janus emulsions JF - RSC Advances N2 - A one-step moderate energy vibrational emulsification method was successfully employed to produce thermo-responsive olive/silicone-based Janus emulsions stabilized by poly(N,N-diethylacrylamide) carrying 0.7 mol% oleoyl side chains. Completely engulfed emulsion droplets remained stable at room temperature and could be destabilized on demand upon heating to the transition temperature of the polymeric stabilizer. Time-dependent light micrographs demonstrate the temperature-induced breakdown of the Janus droplets, which opens new aspects of application, for instance in biocatalysis. KW - microgels KW - step Y1 - 2019 U6 - https://doi.org/10.1039/c9ra03463c SN - 2046-2069 VL - 9 IS - 35 SP - 19271 EP - 19277 PB - RSC Publishing CY - London ER - TY - JOUR A1 - Koshkina, Olga A1 - Lang, Thomas A1 - Thiermann, Raphael A1 - Docter, Dominic A1 - Stauber, Roland H. A1 - Secker, Christian A1 - Schlaad, Helmut A1 - Weidner, Steffen A1 - Mohr, Benjamin A1 - Maskos, Michael A1 - Bertin, Annabelle T1 - Temperature-Triggered Protein Adsorption on Polymer-Coated Nanoparticles in Serum JF - Langmuir N2 - The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region. Y1 - 2015 U6 - https://doi.org/10.1021/acs.langmuir.5b00537 SN - 0743-7463 VL - 31 IS - 32 SP - 8873 EP - 8881 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Doriti, Afroditi A1 - Brosnan, Sarah M. A1 - Weidner, Steffen M. A1 - Schlaad, Helmut T1 - Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base JF - Polymer Chemistry N2 - Polysarcosine (M-n = 3650-20 000 g mol(-1), D similar to 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator. Y1 - 2016 U6 - https://doi.org/10.1039/c6py00221h SN - 1759-9954 SN - 1759-9962 VL - 7 SP - 3067 EP - 3070 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Doriti, Afroditi A1 - Brosnan, Sarah M. A1 - Weidner, Steffen M. A1 - Schlaad, Helmut T1 - Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base JF - Polymer Chemistry N2 - Polysarcosine (Mn = 3650–20 000 g mol−1, Đ ∼ 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator. KW - ring-opening polymerization KW - activated urethane derivatives KW - phosgene-free synthesis KW - carboxyanhydrides KW - polypeptides KW - acids KW - copolymers Y1 - 2016 U6 - https://doi.org/10.1039/C6PY00221H SN - 1759-9954 SN - 1759-9962 VL - 7 SP - 3067 EP - 3070 PB - RSC Publ. CY - Cambridge ER - TY - JOUR A1 - Goldhahn, Christian A1 - Schubert, Jonas A1 - Schlaad, Helmut A1 - Ferri, James K. A1 - Fery, Andreas A1 - Chanana, Munish T1 - Synthesis of Metal@Protein@Polymer Nanoparticles with Distinct Interfacial and Phase Transfer Behavior JF - Chemistry of materials : a publication of the American Chemical Society N2 - In this study, we present a novel and facile method for the synthesis of multiresponsive plasmonic nanoparticles with an interesting interfacial behavior. We used thiol-initiated photopolymerization technique to graft poly(N-isopropylacrylamide) onto the surface of protein-coated gold nanoparticles. The combination of the protein bovine serum albumin with the thermoresponsive polymer leads to smart hybrid nanoparticles, which show a stimuli-responsive behavior of their aggregation and a precisely controllable phase transfer behavior. Three interconnected stimuli, namely, temperature, ionic strength, and pH, were identified as property tuning switches. The aggregation was completely reversible and was quantified by determining Smoluchowski’s instability ratios with time-resolved dynamic light scattering. The tunable hydrophobicity via the three stimuli was used to study interfacial activity and phase transfer behavior of the nanoparticles at an octanol/water interface. Depending on the type of coating (i.e., protein or protein/polymer) as well as the three external stimuli, the nanoparticles either remained in the aqueous phase (aggregated or nonaggregated), accumulated at the oil/water interface, wet the glass wall between the glass vial and the octanol phase, or even crossed the oil/water interface. Such smart and interfacially active nanoparticles with external triggers that are capable of crossing oil/water interfaces under physiological conditions open up new avenues for a variety of applications ranging from the development of drug-delivery nanosystems across biological barriers to the preparation of new catalytic materials. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b02314 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 19 SP - 6717 EP - 6727 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kedracki, Dawid A1 - Chekini, Mahshid A1 - Maroni, Plinio A1 - Schlaad, Helmut A1 - Nardin, Corinne T1 - Synthesis and Self-Assembly of a DNA Molecular Brush JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - We report herein on the polymer-crystallization-assisted thiol-ene photosynthesis of an amphiphilic comb/graft DNA copolymer, or molecular brush, composed of a hydrophobic poly(2-oxazoline) backbone and hydrophilic short single-stranded nucleic acid grafts. Coupling efficiencies are above 60% and thus higher as compared with the straight solid-phase-supported synthesis of amphiphilic DNA block copolymers. The DNA molecular brushes self-assemble into sub-micron-sized spherical structures in water as evidenced by light scattering as well as atomic force and electron microscopy imaging. The nucleotide sequences remain functional, as assessed by UV and fluorescence spectroscopy subsequent to isoindol synthesis at the surface of the structures. The determination of a vesicular morphology is supported by encapsulation and subsequent spectroscopy monitoring of the release of a water-soluble dye and spectroscopic quantification of the hybridization efficiency (30% in average) of the functional nucleic acid strands engaged in structure formation: about one-half of the nucleotide sequences are available for hybridization, whereas the other half are hindered within the self-assembled structure. Because speciation between complementary and non complementary sequences in the medium could be ascertained by confocal laser scanning microscopy, the stable self-assembled molecular brushes demonstrate the potential for sensing applications. Y1 - 2014 U6 - https://doi.org/10.1021/bm5008713 SN - 1525-7797 SN - 1526-4602 VL - 15 IS - 9 SP - 3375 EP - 3382 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 - Dani, Alessandro A1 - Tauber, Karoline A1 - Zhang, Weiyi A1 - Schlaad, Helmut A1 - Yuan, Jiayin T1 - Stable Covalently Photo-Crosslinked Poly(Ionic Liquid) Membrane with Gradient Pore Size JF - Macromolecular rapid communications N2 - Porous polyelectrolyte membranes stable in a highly ionic environment are obtained by covalent crosslinking of an imidazolium-based poly(ionic liquid). The crosslinking reaction involves the UV light-induced thiol-ene (click) chemistry, and the phase separation, occurring during the crosslinking step, generates a fully interconnected porous structure in the membrane. The porosity is on the order of the micrometer scale and the membrane shows a gradient of pore size across the membrane cross-section. The membrane can separate polystyrene latex particles of different size and undergoes actuation in contact with acetone due to the asymmetric porous structure. KW - membrane KW - photo-crosslinked KW - poly(ionic liquid) KW - porous structure Y1 - 2017 U6 - https://doi.org/10.1002/marc.201700167 SN - 1022-1336 SN - 1521-3927 VL - 38 PB - Wiley-VCH CY - Weinheim 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 - Vacogne, Charlotte Dominique A1 - Wei, Chunxiang A1 - Tauer, Klaus A1 - Schlaad, Helmut T1 - Self-assembly of alpha-helical polypeptides into microscopic and enantiomorphic spirals JF - Journal of the american chemical society N2 - Helical structures are ubiquitous in biological materials and often serve a structural purpose. Bioinspired helical materials can be challenging to synthesize and rarely reach the degree of hierarchy of their natural counterparts. Here we report the first example of particles synthesized by direct emulsification of polypeptides found to display spiral morphologies in the dry state. The polypeptides were alpha-helical homo- and copolypeptides of gamma-benzyl glutamate and allylglycine. The chirality of the spirals was controlled by the chirality of the alpha-helices. Notably, right-handed alpha-helical polypeptides (rich in 1, residues) produced clockwise spirals, whereas left-handed alpha-helical polypeptides (rich in D residues) produced the enantiomorphs, i.e., counterclockwise spirals. The disruption of the alpha-helical conformation by the introduction of chiral defects led to less regular spirals and in some cases their suppression. A hypothesis for the transmission of helicity and chirality from a molecular to a higher hierarchical level, involving fibril bundling of coiled alpha-helices, is proposed. Y1 - 2018 U6 - https://doi.org/10.1021/jacs.8b06503 SN - 0002-7863 VL - 140 IS - 36 SP - 11387 EP - 11394 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Debsharma, Tapas A1 - Schmidt, Bernd A1 - Laschewsky, Andre A1 - Schlaad, Helmut T1 - Ring-opening metathesis polymerization of unsaturated carbohydrate derivatives BT - levoglucosenyl alkyl ethers JF - Macromolecules : a publication of the American Chemical Society N2 - A series of biomass-derived levoglucosenyl alkyl ethers (alkyl = methyl, ethyl, n-propyl, isopropyl, and n-butyl) were synthesized and polymerized by ring-opening olefin metathesis polymerization using the Grubbs catalyst C793 at room temperature. Polymerizations were successfully performed in conventional solvents such as 1,4-dioxane and dichloromethane as well as in polar aprotic "green" solvents such as 2-methyltetrahydrofuran, dihydrolevoglucosenone (Cyrene), and ethyl acetate. The prepared polyacetals with degrees of polymerization of similar to 100 exhibit Schulz-Flory-type molar mass distributions and are thermoplastic materials with rather low glass transition temperatures in the range of 43-0 degrees C depending on the length of the alkyl substituent. Kinetic studies revealed that the polymerization proceeded rapidly to a steady state with a certain minimum monomer concentration threshold. When the steady state was reached, just about half of the [Ru] catalyst had been effective to initiate the polymerization, indicating that the initiation step was a slow process. The remaining catalyst was still active and did no longer react with monomers but with in-chain double bonds, cutting the formed polymer chains into shorter fragments. In the long term, all catalyst was consumed and propagating [Ru] chain ends were deactivated by the elimination of [Ru] from the chain ends to form inactive chains with terminal aldehyde groups. Y1 - 2021 U6 - https://doi.org/10.1021/acs.macromol.0c02821 SN - 0024-9297 SN - 1520-5835 VL - 54 IS - 6 SP - 2720 EP - 2728 PB - American Chemical Society CY - Washington ER -