Oxidizable coupling agents: Introduction of surface functionality

The synthesis and grafting to glass or quartz of alkylalkoxysilane coupling agents (RSi(OR′) 3 ) that are susceptible/responsive to oxidation is described. Hydrosilylation of the inexpensive polyolefin squalene occurred efficiently once or twice with the silane HMe 2 SiOSiMe 2 (CH 2 ) 2 Si(OEt) 3 to give a silane coupling agent 3 that possesses several alkene groups. Once grafted to a silica surface Q-Sq using traditional means, the coupling agent was oxidized and further processed in several different ways. First, epoxidation using soluble peracids led to polyepoxides that could be further hydrolyzed to give polyalcohol surfaces Q-Sq-PAA-H 2 O . Alternatively, ozonolysis with gaseous O 3 led to the ozonides Q-Sq-O 3 , which could be decomposed to give either aldehyde/ketone Q-Sq-O 3 -redu , or ketone/carboxylic acid groups Q-Sq-O 3 -H 2 O 2 , respectively, bound to the surface. The aldehyde/ketone groups were characterized by condensation with dinitrophenylhydrazine to give the highly colored hydrazones Q-Sq-O 3 -redu-DNPH . These studies demonstrate the ready portability of organic chemistry to silica (or related) surfaces using judiciously chosen silane coupling agents and the possibility of controlling surface functionalization by postgrafting oxidation.