Hetero‐Telechelic Dye‐Labeled Polymer for Nanoparticle Decoration

Abstract

The synthesis of poly(methyl methacrylate) (PMMA) exhibiting one fluorescent dye (Texas Red) and one methyl disulfide end group is described. It is shown that the latter end group enabled the exchange of both oleic amine on gold nanoparticles (AuNP) and of oleic acid on CdSe/ZnS quantum dots (QD), allowing for a phase transfer of both types of nanoparticles (NP) from hexane into dimethylformamide due to the solubility provided by the PMMA chains. For AuNP, a fluorescence quenching of the dye was found due to fluorescence resonance energy transfer (FRET) from the dye to the AuNP, while QDs caused a fluorescence enhancement by FRET from the QD to the attached dyes. Due to the hetero-telechelic geometry of the polymer, the separation between NP and dye is governed by the end-to-end distance of the polymer.

RAFT Polymerization and Thiol Chemistry: A Complementary Pairing for Implementing Modern Macromolecular Design

“…Methyl disulfide end groups were found to coordinate to gold and semiconductor nanocrystals. [73,131] In combination with an activated ester R end group polymers carrying different bio-target end groups, each capable of selectively recognizing and binding a protein could be prepared. [130] Methane thiosulfonates have also proved to be useful reagents for the end group modification of ATRP polymers.…”

Quantum dot and π-conjugated molecule hybrids: nanoscale luminescence and application to photoresponsive molecular electronics

“…The hybridization of p-type p-conjugated molecules to the surface of n-type QDs can induce distinct luminescence and charge transport characteristics because of energy and/or charge transfer effects. 10,11 QDs and p-conjugated molecule hybrids with controlled luminescent properties can be used for new active materials for lightemitting diodes in flexible displays. In addition, hybrids with an enhanced charge transfer efficiency can be used for nanoscale photovoltaic devices.…”

End Group Reactions of RAFT-Prepared (Co)Polymers

“…Commonly, this is achieved by reacting a thiol with a reagent containing an electrophilic sulfur atom. Both the activation of thiols released from RAFT polymers with dipyridyl disulfide (DPDS) and subsequent exchange reaction with low-molecular-weight thiols, [181][182][183][184] as well as the reaction of macrothiols derived from RAFT-prepared (co) polymers with functional low-molecular-weight electrophilic sulfur reagents [70,71,[185][186][187][188][189] or cysteamine [190] producing disulfide bonds have been reported (Scheme 10).…”

“…[70,71,185,189,198] Functional MTS reagents can be readily prepared from functional halides and sodium MTS. [70,188] Terminal methyl disulfide groups have been shown to produce stable SAMs on planar gold and gold nanoparticles [188] and to coordinate to semiconductor nanocrystals.…”

“…[70,188] Terminal methyl disulfide groups have been shown to produce stable SAMs on planar gold and gold nanoparticles [188] and to coordinate to semiconductor nanocrystals. [185] The reaction of activated esters with amines has been simultaneously performed with thiol reactions at the RAFTpolymer end-groups. For example, Roth et al [186,188,198] combined a end-group pentafluorophenyl (PFP) ester with v-thiol-MTS chemistry.…”