Allyl group-containing polyvinylphosphonates as a flexible platform for the selective introduction of functional groups via polymer-analogous transformations

Abstract

A rich functionalization chemistry was established starting from defined, allyl group containing polyvinylphosphonates.

Cytocompatible Triblock Copolymers with Controlled Microstructure Enabling Orthogonally Functionalized Bio-polymer Conjugates

“…For this purpose, the amino acid l -cysteine ( 6 ) is chosen as a thiol, which can also be used for coupling different modified amino acid sequences and thus opens the possibility of peptide functionalization of polyvinyl phosphonates. , For the modification, the radical reaction of polyvinyl phosphonate P5 and substrate 6 is initiated by the water-soluble initiator 4,4′-azobis­(4-cyanopentanoic acid) (ACPA). In contrast to previous studies, only 1.2 equiv of cysteine is used for each allyl group present in the polymer to prevent thiol-yne click side reactions with unreacted propargyl groups. The success of the synthesis is determined by the NMR analysis of the purified polymer after dialysis.…”

“…50,51 For the modification, the radical reaction of polyvinyl phosphonate P5 and substrate 6 is initiated by the water-soluble initiator 4,4′-azobis(4-cyanopentanoic acid) (ACPA). In contrast to previous studies, 35 only 1.2 equiv of cysteine is used for each allyl group present in the polymer to prevent thiol-yne click side reactions with unreacted propargyl groups. The success of the synthesis is determined by the NMR analysis of the purified polymer after dialysis.…”

“…Our group has successfully achieved well-defined, high molecular-weight polyvinyl phosphonates via living rare-earth metal-mediated group transfer polymerization (REM-GTP). − This method enables excellent control over the polymer microstructure in terms of copolymer composition and the creation of block structures with various functional monomers while maintaining a narrow polydispersity. Besides, various modification options are available, including end-group functionalization with different initiators functionalized with azides, allyl groups, or other protected reactive groups. ,− Moreover, modifying polymers through postpolymerization functionalization or incorporating diverse functional monomer units is feasible. , Furthermore, amphiphilic block copolymers containing polyvinyl phosphonates have been studied for their micellar formation, loading and release behavior, and modification options. ,,− Postpolymerization functionalization also allows the attachment of different biologically active substrates to the polymer. The successful synthesis of a polymer–biomolecule conjugate involving folic acid or cholesterol has been achieved via thiol-ene click chemistry on a vinyl-containing polymer end group, followed by investigations on the localization of these polyvinyl phosphonate conjugates in HMEC-1 cells. , …”

“…21,31−34 Moreover, modifying polymers through postpolymerization functionalization or incorporating diverse functional monomer units is feasible. 35,36 Furthermore, amphiphilic block copolymers containing polyvinyl phosphonates have been studied for their micellar formation, loading and release behavior, and modification options. 20,23,37−39 Postpolymerization functionalization also allows the attachment of different biologically active substrates to the polymer.…”

Azide‐Modified Poly(diethyl vinylphosphonate) for Straightforward Graft‐to Carbon Nanotube Functionalization

“…Poly(diethyl vinylphosphonate) (PDEVP) is an interesting candidate for functionalization of carbon nanotubes, as it is a water‐soluble polymer with a tunable lower critical solution temperature (LCST) [ 1 ] and can act as a versatile platform as there are different structural derivatives of the vinylphosphonates reported, which are highly interesting for MWCNT functionalization. An allyl‐containing PDEVP derivate has been introduced recently, allowing for sidechain modification of the polymers, [ 2 ] as well as an organic radical polymer obtained via attachment of 2,2,4,4‐tetramethylpiperidinyloxyl (TEMPO)‐units to the vinylphosphonate backbone. [ 3 ] Especially the latter would be highly interesting for the proposed functionalization, as it could offer a covalent attachment of a redox‐active polymer to an highly electrical conductive carbon support, thus overcoming organic radical batteries main issues of low active mass and dissolution in the batteries electrolyte.…”