Synthesis of controlled polymeric cross-linked coatings via iniferter polymerisation in the presence of tetraethyl thiuram disulphide chain terminator

Abstract

A "grafting from" approach has been used for controlled deposition of cross-linked polymers by living radical polymerisation. Borosilicate glass was modified with N,N-diethylaminodithiocarbamoylpropyl(trimethoxy)silane, in order to confine the iniferter reactive groups solely at its surface, then placed in solution with monomers and cross-linker. The polymerisation was initiated by UV irradiation. Formation of the cross-linked polymers was studied in terms of time course of the reaction, type of monomers incorporated and influence of oxygen. Grafted surfaces were characterised by AFM, FT-IR, ellipsometry and contact angle measurements. The ability to control the grafted layer improved dramatically when the chain terminator agent, N,N-N',N'-tetraethyl thiuram disulphide (TED) was added. Upon irradiation TED increases the concentration of passive capping radicals and decreases the possibility of recombination of active macro-radicals, thus prolonging their lifetime. In the absence of TED the thickness of produced coatings was below 10 nm. TED added at different concentrations assisted in the formation of grafted layers of 10-130 nm thickness. Iniferter chemistry in the presence of TED can be used for growing nanometre-scale polymer layers on solid supports. It constitutes a robust general platform for controlled grafting and offer a general solution to address the needs of surface derivatisation in sensors technology.

Iniferter‐mediated grafting of molecularly imprinted polymers on porous silica beads for the enantiomeric resolution of drugs

“…Porous silica particles (SiliCycle®) were from Teknokroma (Barcelona, Spain) whose average diameter, pore size and surface area were 10 μm, 10 nm and 432 m 2 g À1 respectively. The iniferter N, N ′-diethylaminodithiocarbamoylpropyl(trimethoxy)silane (DDCPTS) was synthesized as reported elsewhere (Bossi et al, 2010). Reagents required for its synthesis, that is sodium diethyl dithiocarbamate trihydrate and chloropropyl trimethoxysilane ≥97%, were obtained INIFERTER-MEDIATED GRAFTING OF MIP ON POROUS SILICA BEADS from Sigma-Aldrich (Madrid, Spain).…”

Strategies for Molecular Imprinting and the Evolution of MIP Nanoparticles as Plastic Antibodies—Synthesis and Applications

“…The first one is the formation of solid nanocore (seed particle) while the second stage is the grafting of the imprinted shell [107]. The solid core can be formed from diverse materials containing additional functionalities suitable for anchoring e.g., catalytic groups capable of initiating polymer grafting [108,109]. This approach allows formation of recognition sites at the surface of MIP beads [107,110] improving analyte transfer [111,112].…”

Fluorescent monomers as building blocks for dye labeled polymers: synthesis and application in energy conversion, biolabeling and sensors

“…98 Together with MAA and EGDMA, An2 could be grafted from a modified glass surface. 99 For this purpose, borosilicate glass slides were modified with N,N-diethylaminodithiocarbamoylpropyl(trimethoxy)silane followed by subsequent polymerization using the iniferter polymerization technique. It was found that the N,N-tetraethyl thiuram disulphide chain terminator enhanced the control over the polymerization.…”