Search results for "Reversible addition−fragmentation chain-transfer polymerization"

Size Tunable Core Crosslinked Micelles from HPMA-Based Amphiphilic Block Copolymers

2017

A variety of core crosslinkable hydroxypropylmethacrylamide-based block copolymers are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, which are composed of hydroxypropyl-methacrylate as hydrophilic block combined with a statistical hydrophobic block from laurylmethacrylate and the photo crosslinkable monomer. It is discovered that the self-assembled micellar aggregates from these systems vary strongly in size depending not only on the velocity of the polarity switch (nanoprecipitation or slow dialysis) but also on the solvent from which they were dialyzed. In this way micellar aggregates with an Rh varying between 15 and 80 nm can be prepared from the…

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…

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…

2018

The design of multifunctional polymer-based vectors, forming pDNA vaccines, offers great potential in cancer immune therapy. The transfection of dendritic immune cells (DCs) with tumour antigen-encoding pDNA leads to an activation of the immune system to combat tumour cells. In this work, we investigated the chemical attachment of DEC205 antibodies (aDEC205) as DC-targeting structures to polyplexes of P(Lys)-b-P(HPMA). The conjugation of a synthetic block copolymer and a biomacromolecule with various functionalities (aDEC205) requires bioorthogonal techniques to avoid side reactions. Click chemistry and in particular the strain-promoted alkyne-azide cycloaddition (SPAAC) can provide the req…

Squaric Ester-Based, pH-Degradable Nanogels: Modular Nanocarriers for Safe, Systemic Administration of Toll-like Receptor 7/8 Agonistic Immune Modula…

2021

Small-molecular Toll-like receptor 7/8 (TLR7/8) agonists hold promise as immune modulators for a variety of immune therapeutic purposes including cancer therapy or vaccination. However, due to their rapid systemic distribution causing difficult-to-control inflammatory off-target effects, their application is still problematic, in particular systemically. To address this problem, we designed and robustly fabricated pH-responsive nanogels serving as versatile immunodrug nanocarriers for safe delivery of TLR7/8-stimulating imidazoquinolines after intravenous administration. To this aim, a primary amine-reactive methacrylamide monomer bearing a pendant squaric ester amide is introduced, which i…

Pentafluorophenyl Ester-based Polymersomes as Nanosized Drug-Delivery Vehicles

2015

In this work, activated ester chemistry is employed to synthesize biocompatible and readily functionalizable polymersomes. Via aminolysis of pentafluorophenyl methacrylate-based precursor polymers, an N-(2-hydroxypropyl) methacrylamide (HPMA)-analog hydrophilic block is obtained. The precursor polymers can be versatile functionalized by simple addition of suitable primary amines during aminolysis as demonstrated using a fluorescent dye. Vesicle formation is proven by cryoTEM and light scattering. High encapsulation efficiencies for hydrophilic cargo like siRNA are achieved using dual centrifugation and safe encapsulation is demonstrated by gel electrophoresis. In vitro studies reveal low cy…

Synthesis of Reactive Telechelic Polymers Based on Pentafluorophenyl Esters

2008

A diazo initiator and a chain transfer agent (CTA), both containing a pentafluorophenyl (PFP) activated ester, were synthesized. In a RAFT polymerization using the functionalized chain transfer agent (PFPCTA), methyl methacrylate (MMA), diethylene glycol monomethyl ether methacrylate (DEGMA), poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), and lauryl methacrylate (LMA) could successfully be polymerized into homopolymers and diblock copolymers with good control over molecular weight, very high conversions, and narrow molecular weight distributions. Polymers derived from the PFP-CTA possessed an activated ester at the R-end of the polymer chain, which could be reacted with amines…

Reactive surface coatings based on polysilsesquioxanes: defined adjustment of surface wettability.

2009

We have investigated a generally applicable protocol for a substrate-independent reactive polymer coating that offers interesting possibilities for further molecular tailoring via simple wet chemical derivatization reactions. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylate) hybrid polymers have been synthesized by RAFT polymerization, and stable reactive surface coatings have been prepared by spin-coating on the following substrates: Si, glass, gold, PMMA, PDMS, and steel. These coatings have been used for a defined adjustment of surface wettability by surface-analogous reaction with various amines (e.g., glutamic acid to obtain hydrophilic surfaces (Theta(a) = 18 degrees) or per…

Functionalization and patterning of reactive polymer brushes based on surface reversible addition and fragmentation chain transfer polymerization

2012

We present the synthesis of reactive polymer brushes prepared by surface reversible addition–fragmentation chain transfer polymerization of pentafluorophenyl acrylate. The reactive ester moieties can be used to functionalize the polymer brush film with virtually any functionality by simple post-polymerization modification with amines. Dithiobenzoic acid benzyl-(4-ethyltrimethoxylsilyl) ester was used as the surface chain transfer agent (S-CTA) and the anchoring group onto the silicon substrates. Reactive polymer brushes with adjustable molecular weight, high grafting density, and conformal coverage through the grafting-from approach were obtained. Subsequently, the reactive polymer brushes …

Substrate-Independent Stable and Adherent Reactive Surface Coatings and their Conversion with Amines

2007

To create stable, adherent and reactive surface coatings, a hybrid polymer composed of poly(methylsilsesquioxane) (PMSSQ) and poly(pentafluorophenyl acrylate) PFPA with a M n of 32000 g/mol was prepared by a RAFT polymerization procedure. These hybrid polymer has been used for coating experiments. The PFPA part enabled a variable functionalization of the coating afterwards. The stability on various substrates (e.g. glass, PMMA, steel) was tested in an ISO tape test. These reactive surface coatings were modified using different amines, such as amino-terminated PEG, dodecyl amine and N-isopropyl amine. The conversion was analyzed by FT-IR and contact angle measurements.