TY - GEN A1 - Inal, Sahika A1 - Kölsch, Jonas D. A1 - Sellrie, Frank A1 - Schenk, Jörg A. A1 - Wischerhoff, Erik A1 - Laschewsky, André A1 - Neher, Dieter T1 - A water soluble fluorescent polymer as a dual colour sensor for temperature and a specific protein N2 - We present two thermoresponsive water soluble copolymers prepared via free radical statistical copolymerization of N-isopropylacrylamide (NIPAm) and of oligo(ethylene glycol) methacrylates (OEGMAs), respectively, with a solvatochromic 7-(diethylamino)-3-carboxy-coumarin (DEAC)- functionalized monomer. In aqueous solutions, the NIPAm-based copolymer exhibits characteristic changes in its fluorescence profile in response to a change in solution temperature as well as to the presence of a specific protein, namely an anti-DEAC antibody. This polymer emits only weakly at low temperatures, but exhibits a marked fluorescence enhancement accompanied by a change in its emission colour when heated above its cloud point. Such drastic changes in the fluorescence and absorbance spectra are observed also upon injection of the anti-DEAC antibody, attributed to the specific binding of the antibody to DEAC moieties. Importantly, protein binding occurs exclusively when the polymer is in the well hydrated state below the cloud point, enabling a temperature control on the molecular recognition event. On the other hand, heating of the polymer–antibody complexes releases a fraction of the bound antibody. In the presence of the DEAC-functionalized monomer in this mixture, the released antibody competitively binds to the monomer and the antibody-free chains of the polymer undergo a more effective collapse and inter-aggregation. In contrast, the emission properties of the OEGMA-based analogous copolymer are rather insensitive to the thermally induced phase transition or to antibody binding. These opposite behaviours underline the need for a carefully tailored molecular design of responsive polymers aimed at specific applications, such as biosensing. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 249 KW - intramolecular charge-transfer KW - phase-transitions KW - responsive polymers KW - sensitivity KW - thermometer KW - dyes KW - modulation KW - assemblies KW - antibodies KW - binding Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-95336 SP - 6373 EP - 6381 ER - TY - GEN A1 - Bubeck, Christoph A1 - Laschewsky, André A1 - Lupo, Donald A1 - Neher, Dieter A1 - Ottenbreit, Petra A1 - Paulus, Wolfgang A1 - Prass, Werner A1 - Ringsdorf, Helmut A1 - Wegner, Gerhard T1 - Amphiphilic dyes for nonlinear optics: Dependence of second harmonic generation on functional group substitution T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 082 Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17201 ER - TY - GEN A1 - Hildebrand, Viet A1 - Laschewsky, André A1 - Päch, Michael A1 - Müller-Buschbaum, Peter A1 - Papadakis, Christine M. T1 - Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates) N2 - A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers’ precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 298 Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-102028 ER - TY - GEN A1 - Schönemann, Eric A1 - Laschewsky, André A1 - Rosenhahn, Axel T1 - Exploring the long-term hydrolytic behavior of zwitterionic polymethacrylates and polymethacrylamides T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-(N-2-methacryloylethyl-N,N-dimethyl) ammoniopropanesulfonate) (“sulfobetaine methacrylate”), and poly(3-(N-3-methacryamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) (“sulfobetaine methacrylamide”) as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by ¹H NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradation of the carboxyl ester or amide was observed after one year in PBS, 1 M HCl, or in sodium carbonate buffer of pH 10. This demonstrates their basic suitability for anti-fouling applications. Poly(sulfobetaine methacrylamide) proved even to be stable for one year in 1 M NaOH without any signs of degradation. The stability is ascribed to a steric shielding effect. The hemisulfate group in the polysulfabetaines, however, was found to be partially labile. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1091 KW - polyzwitterions KW - stability KW - polymer degradation KW - hydrolysis KW - polysulfobetaine KW - polysulfabetaine KW - anti-fouling materials Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-473052 SN - 1866-8372 IS - 1091 ER - TY - GEN A1 - Köberle, Peter A1 - Laschewsky, André T1 - Hybrid materials from organic polymers and inorganic salts N2 - The prepaparation of amorphous, homogeneous blends of zwitterionic polymers and transition metal salts was investigated. Homogeneous miscibility was achieved in many cases up to equimolar amounts of salt, depending on the anion and cation chosen. Various analytical techniques point to a solid state solution of the inorganic ions in the polymer matrix. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 086 Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-26884 ER - TY - GEN A1 - Elbert, R. A1 - Laschewsky, André A1 - Ringsdorf, H. T1 - Hydrophilic spacer groups in polymerizable lipids: formation of biomembrane models from bulk polymerized lipids N2 - A variety of polymerizable lipids containing a hydrophilic spacer group between the reactive group and the main amphiphilic structure have been synthesized. They were investigated in monolayers, liposomes, and multilayers. When the spacer concept was used, efficient decoupling of the motions of the polymeric chain and the amphiphilic side groups is achieved. Thus, the often found loss of the important fluid phases by polymerization is avoided. Polymeric monolayers of the spacer lipid, prepared either by polymerization in the monolayer or by spreading of prepolymerized lipid, exhibit nearly identical surface pressure-area diagrams. Most distinctly, the successful decoupling of the motions of the polymer main chain and the membrane forming amphiphilic side groups is demonstrated by the self-organization of bulk polymerized spacer lipids to polymeric liposomes. In addition, spacer lipids are able to build polymeric Langmuir-Blodgett multilayers. The decoupling of the polymer main chain and the membrane-forming amphiphilic side groups enables the deposition of already polymeric monolayers onto supports to form defined multilayers. If, alternatively, monomeric monolayers are deposited and polymerized on the support, defects in the layers due to structural changes during the polymerization are avoided by the flexible spacer group. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 095 Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17361 ER - TY - GEN A1 - Enzenberg, Anne A1 - Laschewsky, André A1 - Boeffel, Christine A1 - Wischerhoff, Erik T1 - Influence of the near molecular vicinity on the temperature regulated fluorescence response of poly(N-vinylcaprolactam) N2 - A series of new fluorescent dye bearing monomers, including glycomonomers, based on maleamide and maleic esteramide was synthesized. The dye monomers were incorporated by radical copolymerization into thermo-responsive poly(N-vinyl-caprolactam) that displays a lower critical solution temperature (LCST) in aqueous solution. The effects of the local molecular environment on the polymers' luminescence, in particular on the fluorescence intensity and the extent of solvatochromism, were investigated below as well as above the phase transition. By attaching substituents of varying size and polarity in the close vicinity of the fluorophore, and by varying the spacer groups connecting the dyes to the polymer backbone, we explored the underlying structure-property relationships, in order to establish rules for successful sensor designs, e.g., for molecular thermometers. Most importantly, spacer groups of sufficient length separating the fluorophore from the polymer backbone proved to be crucial for obtaining pronounced temperature regulated fluorescence responses. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 363 KW - thermo-responsive polymers KW - poly(N-vinylcaprolactam) KW - lower critical solution temperature KW - fluorescent dyemonomers KW - naphthalimide KW - solvatochromism KW - polymeric sensors KW - molecular thermometers Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-400634 ER - TY - GEN A1 - Laschewsky, André A1 - Paulus, Wolfgang A1 - Ringsdorf, Helmut A1 - Schuster, A. A1 - Frick, G. A1 - Mathy, A. T1 - Mixed polymeric monolayers and Langmuir-Blodgett multilayers with functional low molecular weight guest compounds N2 - Mixed monolayers and Langmuir-Blodgett multilayers of functional low molecular weight guest compounds, especially nonlinear optical (NLO) dyes, within the matrix of an amphotropic spacer polymer have been prepared. The polymer matrix enabled the transfer of guest compounds not capable of self-organizing at the air-water interface by themselves. The structure of the LB multilayers and the transfer process were studied by small angle X-ray scattering and UV-visible spectroscopy. Good NLO coefficients were found in the mixed films. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 060 Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17233 ER - TY - GEN A1 - Hildebrand, Viet A1 - Laschewsky, André A1 - Wischerhoff, Erik T1 - Modulating the solubility of zwitterionic poly((3- methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties N2 - Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition–fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 309 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-103040 SP - 731 EP - 740 ER - TY - GEN A1 - Laschewsky, André T1 - Molecular concepts, self-organisation and properties of polysoaps N2 - The article reviews water-soluble polymers characterized by surfactant side chains, and related amphiphilic polymers. Various synthetic approaches are presented, and rules for useful molecular architectures are given. Models for the self-organization of such polymers in water are presented comparing them with the micellization of low molecular weight surfactants. Highlighting key properties of aqueous polysoap solutions such as viscosity, surface tension and solubilization power, some structure-property relationships are established. Further, the formation of mesophases and of superstructures in bulk is addressed. Finally, the functionalization of polysoaps, and potential applications are discussed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 087 Y1 - 1995 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-26895 ER -