TY - JOUR A1 - Mai, Tobias A1 - Rakhmatullina, Ekaterina A1 - Bleek, Katrin A1 - Boye, Susanne A1 - Yuan, Jiayin A1 - Voelkel, Antje A1 - Graewert, Marlies A1 - Cheaib, Zeinab A1 - Eick, Sigrun A1 - Günter, Christina A1 - Lederer, Albena A1 - Lussi, Adrian A1 - Taubert, Andreas T1 - Poly(ethylene oxide)-b-poly(3-sulfopropyl methacrylate) block copolymers for calcium phosphate mineralization and biofilm inhibition JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - Poly(ethylene oxide) (PEO) has long been used as an additive in toothpaste, partly because it reduces biofilm formation on teeth. It does not, however, reduce the formation of dental calculus or support the remineralization of dental enamel or dentine. The present article describes the synthesis of new block copolymers on the basis of PEO and poly(3-sulfopropyl methacrylate) blocks using atom transfer radical polymerization. The polymers have very large molecular weights (over 10(6) g/mol) and are highly water-soluble. They delay the precipitation of calcium phosphate from aqueous solution but, upon precipitation, lead to relatively monodisperse hydroxyapatite (HAP) spheres. Moreover, the polymers inhibit the bacterial colonization of human enamel by Streptococcus gordonii, a pioneer bacterium in oral biofilm formation, in vitro. The formation of well-defined HAP spheres suggests that a polymer-induced liquid precursor phase could be involved in the precipitation process. Moreover, the inhibition of bacterial adhesion suggests that the polymers could be utilized in caries prevention. Y1 - 2014 U6 - https://doi.org/10.1021/bm500888q SN - 1525-7797 SN - 1526-4602 VL - 15 IS - 11 SP - 3901 EP - 3914 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Mai, Tobias A1 - Boye, Susanne A1 - Yuan, Jiayin A1 - Völkel, Antje A1 - Gräwert, Marlies A1 - Günter, Christina A1 - Lederer, Albena A1 - Taubert, Andreas T1 - Poly(ethylene oxide)-based block copolymers with very high molecular weights for biomimetic calcium phosphate mineralization JF - RSC Advances : an international journal to further the chemical sciences N2 - The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution. Y1 - 2015 U6 - https://doi.org/10.1039/c5ra20035k SN - 2046-2069 IS - 5 SP - 103494 EP - 103505 PB - RSC Publishing CY - London ER - TY - GEN A1 - Mai, Tobias A1 - Boye, Susanne A1 - Yuan, Jiayin A1 - Völkel, Antje A1 - Gräwert, Marlies A1 - Günter, Christina A1 - Lederer, Albena A1 - Taubert, Andreas T1 - Poly(ethylene oxide)-based block copolymers with very high molecular weights for biomimetic calcium phosphate mineralization N2 - The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 208 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-85299 ER - TY - JOUR A1 - Mai, Tobias A1 - Boye, Susanne A1 - Yuan, Jiayin A1 - Voelkel, Antje A1 - Graewert, Marlies A1 - Günter, Christina A1 - Lederer, Albena A1 - Taubert, Andreas T1 - Poly(ethylene oxide)-based block copolymers with very high molecular weights for biomimetic calcium phosphate mineralization JF - RSC Advances N2 - The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine) s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium) ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 10(6) g mol(-1). All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal M-n = 100 000 g mol(-1)). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution. Y1 - 2015 U6 - https://doi.org/10.1039/c5ra20035k SN - 2046-2069 VL - 5 IS - 125 SP - 103494 EP - 103505 PB - Royal Society of Chemistry CY - Cambridge ER - TY - THES A1 - Mai, Tobias T1 - Polymerunterstützte Calciumphosphatmineralisation T1 - Polymer supported calcium phosphate mineralization N2 - Im Verlauf dieser Arbeit sind Blockcopolymere verschiedener Ladung auf Basis von PEO mit hohen Molekulargewichten durch lebendende freie radikalische Polymerisation hergestellt worden. Die Polymere sind einfach im Grammmaßstab herstellbar. Sie zeigen sowohl einen großen Einfluss auf die Nukleation als auch auf die Auflösung von Calciumphosphat. Gleichwohl scheint das Vorhandensein von positiven Gruppen (Kationen, Ampholyten und Betainen) keinen dramatischen Einfluss auf die Nukleation zu haben. So verursachen Polymere mit positiven Ladungen die gleiche Retentionwirkung wie solche, die ausschließlich anionische Gruppen enthalten. Aus der Verwendung der kationischen, ampholytischen und betainischen Copolymere resultiert allerdings eine andersartige Morphologie der Niederschläge, als aus der Verwendung der Anionischen hervorgeht. Bei der Stabilisierung einer HAP-Oberfläche setzt sich dieser Trend fort, das heißt, rein anionische Copolymere wirken stärker stabilisierend als solche, die positive Ladungen enthalten. Durch Inkubation von menschlichem Zahnschmelz mit anionischen Copolymeren konnte gezeigt werden, dass die Biofilmbildung verglichen mit einer unbehandelten Zahnoberfläche eingeschränkt abläuft. All dies macht die Polymere zu interessanten Additiven für Zahnpflegeprodukte. Zusätzlich konnten auf Basis dieser rein anionischen Copolymere Polymerbürsten, ebenfalls über lebendende freie radikalische Polymerisation, hergestellt werden. Diese zeichnen sich durch einen großen Einfluss auf die Kristallphase aus und bilden mit dem CHAP des AB-Types das Material, welches auch in Knochen und Zähnen vorkommt. Erste Cytotoxizitätstests lassen auf das große Potential dieser Polymerbürsten für Beschichtungen in der Medizintechnik schließen. N2 - The thesis at hand describes the preparation of block-copolymers composed of uncharged polyethyleneoxides and differently charged methacrylate-based blocks. Synthesized via living free-radical polymerization the charged blocks were prepared by using of the following monomers: I) for anionic blocks 3-Sulfopropyl methacrylate potassium salt (SPM); II) for cationic blocks 2-(trimethyl ammonium) ethyl methacrylate chloride (TMAEMA) or2-(N-3-Cyanopropyl-N,N-dimethyl ammonium chloride) ethyl methacrylate (CPDMAEMA); III) for betainic blocks [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (MEDSAH) and IV) for ampholytic blocks the anionic SPM and one of the two cationic monomers TMAEMA or CPDMAEMA were used in equal parts. The polymers were accessible in a multigram scale. The resulting block-copolymers show a strong effect on both the dissolution and the nucleation of calcium phosphate. The presence of positively charged moieties in case of applying polycations, polyampholytes and polybetaines does not seem to influence the nucleation in a different manner than the negatively charged polyanions. Nontheless the application of cationic, betainic or ampholytic polymers leads to different morphology of the calcium phosphate precipitates compared to the anionic polymers. The presence of anions results in the formation of spherical well-separated particles whereas cations, ampholytes and betaines cause the composition of smaller particles. In contrast to this data obtained by energy-dispersive X-ray spectroscopy and X-ray crystallography show that calcium deficient hydroxyapatite was formed in all cases. Therefore it can be concluded that the polymers' charge influences the morphology but not the crystal phase. This observation extends to the stabilization of the hydroxyapatite's (HAP) surface. A comparison of polymers containing cations and anionic polymers reveals a stronger stabilizing effect for anions. With the calcium phosphate's dissolution per monomer unit taken into consideration only the anionic charges lead to a stabilization of the HAP-surface at low polymer concentrations while in presence of positive charges a destabilization is observed. By incubating human enamel specimen with mixtures of anionic copolymers and natural human saliva a reduced biofilm formation could be detected when compared to polymer free saliva. Thus the polymers could be potentially used for dental care products. Additionally it was possible to synthesize polymer brushes based on the anionic copolymers' architecture. Again SPM was polymerized yet fastened on a silicon surface via living free-radical polymerization in a grafting-from mechanism. The brushes stand out due to a great influence on the crystal phase of calcium phosphate. They promote the formation of AB-type carbonate substituted hydroxyapatite (CHAP) a material in human bones and teeth that is formed increasingly with age. Initial cytotoxicity tests of both mineralized and unmineralized brushes indicate a high potential of the brushes for biomedical engineering. KW - Polymerchemie KW - polymer chemistry KW - Calciumphosphat KW - calcium phosphate KW - Mineralisation KW - mineralization Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89056 ER - TY - JOUR A1 - Mai, Tobias A1 - Wolski, Karol A1 - Puciul-Malinowska, Agnieszka A1 - Kopyshev, Alexey A1 - Gräf, Ralph A1 - Bruns, Michael A1 - Zapotoczny, Szczepan A1 - Taubert, Andreas T1 - Anionic polymer brushes for biomimetic calcium phosphate mineralization BT - A surface with application potential in biomaterials JF - Polymers N2 - This article describes the synthesis of anionic polymer brushes and their mineralization with calcium phosphate. The brushes are based on poly(3-sulfopropyl methacrylate potassium salt) providing a highly charged polymer brush surface. Homogeneous brushes with reproducible thicknesses are obtained via surface-initiated atom transfer radical polymerization. Mineralization with doubly concentrated simulated body fluid yields polymer/inorganic hybrid films containing AB-Type carbonated hydroxyapatite (CHAP), a material resembling the inorganic component of bone. Moreover, growth experiments using Dictyostelium discoideum amoebae demonstrate that the mineral-free and the mineral-containing polymer brushes have a good biocompatibility suggesting their use as biocompatible surfaces in implantology or related fields. KW - polymer brushes KW - calcium phosphate KW - hydroxyapatite KW - carbonated apatite KW - bone mimic KW - biocompatibility KW - Dictyostelium discoideum Y1 - 2018 U6 - https://doi.org/10.3390/polym10101165 SN - 2073-4360 VL - 10 IS - 10 PB - MDPI CY - Basel ER - TY - JOUR A1 - Ihlenburg, Ramona A1 - Mai, Tobias A1 - Thünemann, Andreas F. A1 - Baerenwald, Ruth A1 - Saalwächter, Kay A1 - Koetz, Joachim A1 - Taubert, Andreas T1 - Sulfobetaine hydrogels with a complex multilength-scale hierarchical structure JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - Hydrogels with a hierarchical structure were prepared from a new highly water-soluble crosslinker N,N,N',N'-tetramethyl-N,N'-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and from the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The free radical polymerization of the two compounds is rapid and yields near-transparent hydrogels with sizes up to 5 cm in diameter. Rheology shows a clear correlation between the monomer-to-crosslinker ratio and the storage and loss moduli of the hydrogels. Cryo-scanning electron microscopy, low-field nuclear magnetic resonance (NMR) spectroscopy, and small-angle X-ray scattering show that the gels have a hierarchical structure with features spanning the nanometer to the sub-millimeter scale. The NMR study is challenged by the marked inhomogeneity of the gels and the complex chemical structure of the sulfobetaine monomer. NMR spectroscopy shows how these complications can be addressed via a novel fitting approach that considers the mobility gradient along the side chain of methacrylate-based monomers. KW - Defects KW - Hydrogels KW - Nuclear magnetic resonance spectroscopy KW - Scattering KW - X-ray scattering Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpcb.0c10601 SN - 1520-6106 SN - 1520-5207 VL - 125 IS - 13 SP - 3398 EP - 3408 PB - American Chemical Society CY - Washington ER -