Polyhydroxyl and Polyphosphorylcholine Functionalized Silica for Hydrophilic Interaction Liquid Chromatography Synthesis, Characterization and Application

This thesis focuses on the development of new stationary phases for use in hydrophilic interaction liquid chromatography using TRIS‐based and phosphorylcholine typed monomers and porous silica particles as starting substrates. In this thesis, several ways of polymerizing highly hydrophilic mono‐ mers onto pore surfaces of silica supports are described, based on several “grafting from” schemes. “Controlled/living” radical polymerizations including atom transfer radical polymerization (ATRP) and iniferter‐mediated polymerization in conjunction with conventional free radical polymerization are demonstrated to be successful tools for grafting different hydrophilic monomers (polyhydroxyl and phosphorylcholine [meth]acrylamide/acrylates) onto the silica surfaces. Reaction solvents are proven to play an essential role to achieve efficient graft polymerization of activated silica surfaces with these amphiphilic vinylic monomers, which is difficult because of their restricted access to the activated surface in solvents that can be used because of solubility constraints. Two tentacle TRIS‐based polymer grafted silica, namely TRIS‐WAX – TRIS functionality bonded to silica via a C–N–C imine bond and TRIS‐Amide – TRIS bonded to silica via an amide bond, prove to be useful as stationary phases for hydrophilic interaction chromatography (HILIC).The TRIS‐WAX exhibits a mixed mode hydrophilic partitioning and weak anion exchange (HILIC/WAX) retention mechanism while retention by hydrophilic partitioning is the dominant mechanism on the neutral TRIS‐Amide phase which lacks weak anion exchange (WAX) properties. Interestingly, both these phases have selectivities that are radically different from most commercial HILIC stationary phases. Finally, a method is demonstrated for synthesizing a stratified (graft‐copolymerized) silica material based on N,N′‐methylenebisacrylamide and 2‐methacryloyloxyethyl phosphorylcholine (MPC) using a “controlled/living” photoiniferter‐mediated polymerization from the N,N‐diethyldithiocarbamate iniferter moiety immobilized silica surfaces. This polymerization method proves to be successful for graft‐blockcopolymerization of different highly hydrophilic monomers onto the activated surfaces of porous silica. In this way, silica surfaces are grafted with a cross‐linked amide‐based hydrogel, on top of which a tentacle zwitterionic phosphorylcholine‐typed layer is synthesized. The resulted material proves to be useful for HILIC separations and possesses different selectivity for the tested organic acids compared to that of commercial ZIC‐cHILIC stationary phase.