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
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