RESUMO
Here we report the preparation of poly(oligonucleotide) brush polymers and amphiphilic brush copolymers from nucleic acid monomers via graft-through polymerization. We describe the polymerization of PNA-norbornyl monomers to yield poly-PNA (poly(peptide nucleic acid)) via ring-opening metathesis polymerization (ROMP) with the initiator, (IMesH2)(C5H5N)2(Cl)2RuCHPh.1 In addition, we present the preparation of poly-PNA nanoparticles from amphiphilic block copolymers and describe their hybridization to a complementary single-stranded DNA (ssDNA) oligonucleotide.
Assuntos
Oligonucleotídeos/química , Ácidos Nucleicos Peptídicos/química , DNA/química , DNA de Cadeia Simples/química , Espectroscopia de Ressonância Magnética , Nanopartículas/química , Polimerização , Polímeros/químicaRESUMO
In this paper we compare and contrast three approaches for labelling polymers with functional groups via ring-opening metathesis polymerization (ROMP). We explored the incorporation of functionality via initiation, termination and propagation employing an array of novel initiators, termination agents and monomers. The goal was to allow the generation of selectively labelled and well-defined polymers that would in turn lead to the formation of labelled nanomaterials. Norbornene analogues, prepared as functionalized monomers for ROMP, included fluorescent dyes (rhodamine, fluorescein, EDANS, and coumarin), quenchers (DABCYL), conjugatable moieties (NHS esters, pentafluorophenyl esters), and protected amines. In addition, a set of symmetrical olefins for terminally labelling polymers, and for the generation of initiators in situ is described.
RESUMO
A general method for synthesizing alpha-hydroxy N-acylindoles in one-pot via an acid-catalyzed condensation of a convertible isonitrile with water and various aldehydes is presented. These intermediates were incorporated into poly(alpha-hydroxy acid) copolymers bearing residues with functionalizable side chains, which could be further modified through Cu(I)-catalyzed azide-alkyne cylcoaddition reactions. This versatile synthetic strategy provides access to side chain functionalized poly(alpha-hydroxy acid) copolymers from readily available aldehydes, making it potentially useful as an approach to synthesize biodegradable polymers with new, tunable properties.