Search results for "polymerization"
showing 10 items of 1689 documents
Joining Two Natural Motifs: Catechol-Containing Poly(phosphoester)s.
2017
Numerous catechol-containing polymers, including biodegradable polymers, are currently heavily discussed for modern biomaterials. However, there is no report combining poly(phosphoester)s (PPEs) with catechols. Adhesive PPEs have been prepared via acyclic diene metathesis polymerization. A novel acetal-protected catechol phosphate monomer was homo- and copolymerized with phosphoester comonomers with molecular weights up to 42000 g/mol. Quantitative release of the catechols was achieved by careful hydrolysis of the acetal groups without backbone degradation. Degradation of the PPEs under basic conditions revealed complete and statistical degradation of the phosphotri- to phosphodiesters. In …
Universal Concept for the Implementation of a Single Cleavable Unit at Tunable Position in Functional Poly(ethylene glycol)s
2013
Poly(ethylene glycol) (PEG) with acid-sensitive moieties gained attention particularly for various biomedical applications, such as the covalent attachment of PEG (PEGylation) to protein therapeutics, the synthesis of stealth liposomes, and polymeric carriers for low-molecular-weight drugs. Cleavable PEGs are favored over their inert analogues because of superior pharmacodynamic and/or pharmacokinetic properties of their formulations. However, synthetic routes to acetal-containing PEGs published up to date either require enormous efforts or result in ill-defined materials with a lack of control over the molecular weight. Herein, we describe a novel methodology to implement a single acetalde…
Secondary Structure-Driven Self-Assembly of Thiol-Reactive Polypept(o)ides
2021
Secondary structure formation differentiates polypeptides from most of the other synthetic polymers, and the transitions from random coils to rod-like α-helices or β-sheets represent an additional parameter to direct self-assembly and the morphology of nanostructures. We investigated the influence of distinct secondary structures on the self-assembly of reactive amphiphilic polypept(o)ides. The individual morphologies can be preserved by core cross-linking via chemoselective disulfide bond formation. A series of thiol-responsive copolymers of racemic polysarcosine-block-poly(S-ethylsulfonyl-dl-cysteine) (pSar-b-p(dl)Cys), enantiopure polysarcosine-block-poly(S-ethylsulfonyl-l-cysteine) (pSa…
Multifunctional Fe(III)-Binding Polyethers from Hydroxamic Acid-Based Epoxide Monomers.
2019
Multiple hydroxamic acids are introduced at poly(ethylene glycol) (PEG) via copolymerization of ethylene oxide with a novel epoxide monomer containing a 1,4,2-dioxazole-protected hydroxamic acid (HAAGE). AB- and ABA-type di- and triblock copolymers as well as statistical copolymers of HAAGE and ethylene oxide are prepared in a molecular weight range between 2600 and 12 000 g mol-1 with low dispersities (Ð < 1.2). Cleavage of the acetal protecting group after the polymerization is achieved by mild acidic treatment, releasing multiple free hydroxamic acids tethered to the polyether backbone. The chelation properties of different polymer architectures (statistical versus diblock and ABA triblo…
HPMA copolymers as surfactants in the preparation of biocompatible nanoparticles for biomedical application.
2012
In this work we describe the application of amphiphilic N-(2-hydroxypropyl)methacrylamide (HPMA)-based copolymers as polymeric surfactants in miniemulsion techniques. HPMA-based copolymers with different ratios of HPMA (hydrophilic) to laurylmethacrylate (LMA; hydrophobic) units were synthesized by RAFT polymerization and postpolymerization modification. The amphiphilic polymers can act as detergents in both the miniemulsion polymerization of styrene and the miniemulsion process in combination with solvent evaporation, which was applied to polystyrene and polylactide. Under optimized conditions, monodisperse colloids can be prepared. The most promising results could be obtained by using the…
Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary H…
2015
The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer …
Poly(Ethylene Glycol) Dimethacrylates with Cleavable Ketal Sites: Precursors for Cleavable PEG-Hydrogels.
2017
The authors introduce poly(ethylene glycol) (PEG) based macromonomers containing acid-labile ketal moieties as well as terminal methacrylate units that are amenable to radical polymerization. The synthesis of PEGs of different molecular weights (ranging from 2000 to 13 000 g mol-1 with polydispersities <1.15) with a central ketal unit (PEG-ketal-diol) and their conversion to PEG-ketal-dimethacrylates (PEG-ketal-DMA) is introduced. Degradation rates of both PEG-ketal-diols and PEG-ketal-DMA are investigated by in situ 1 H NMR kinetic studies in deuterated phosphate buffer. Hydrogels containing 0, 5, or 10 wt% of PEG-ketal-DMA and 100, 95, or 90 wt% of PEG-DMA, respectively, are synthesized a…
Peculiar behavior of degenerative chain transfer polymerization of a phosphonated methacrylate
2009
Living/controlled radical polymerization of dimethyl(methacryloyloxy)methyl phosphonate (MAPC) has been attempted using degenerative transfer to produce block copolymers. RAFT polymerization of this monomer is sensitive to very low level of oxygen and in any case limited to low monomer conversion. Reverse iodine transfer polymerization (RITP) leads to higher monomer conversion with a limited amount of living polymer (55% by H NMR), precluding an efficient synthesis of block copolymers. A PMMA-b-PMAPC diblock copolymer was therefore synthesized by iodine transfer polymerization (ITP) of MAPC from a PMMA-Imacro-chain transfer agent prepared by RITP. The diblock copolymer, purified by selectiv…
Plasma Polymer Membranes for Immobilising Metalloporphyrins
2013
Atmospheric pressure dielectric barrier discharge formation of organosilicon thin films loaded with zinc 5,10,15,20-tetraphenylporphyrin (Zn(TPP)) was investigated for different deposition conditions. UV–visible spectroscopy and scanning electron microscopy revealed the effects of the metalloporpyhrins injection parameters and the plasma polymerisation conditions can affect the dispersion of the metalloporphyrins and the morphology of the coatings. The stability of the embedded Zn(TPP) molecules was investigated by orbitrap mass spectrometry.
Kinetic analysis of "living" polymerization processes exhibiting slow equilibria. 6. Cationic polymerization involving covalent species, ion pairs, a…
1996
The kinetics of cationic polymerization is studied theoretically in accordance with a three-state mechanism which consists of two successive equilibria: the ionization/ion collapse equilibrium between covalent species and ion pairs, and the subsequent dissociation/association equilibrium between ion pairs and free ions. The number- and weight-average degrees of polymerization and the polydispersity index (PDI), Pw/Pn, are derived. The molecular weight distribution of the polymer generated from this mechanism is generally broader than that of polymers formed via a two-state mechanism, i.e. with only one equilibrium either between covalent species and ion pairs or between covalent species an…