Utilizing advanced polymerization techniques for simplifying polymer grafting from silica colloidal crystal substrates

Charu K Yerneni, Purdue University

Abstract

Polyacrylamide has been well established as a biocompatible material when Polyacrylamide gel electrophoresis (PAGE) came into existence in the 1960s. Under aqueous buffer conditions it becomes non-adsorptive to proteins and due to its molecular level pore forming nature could be used in size based biomolecule separations. Since then considerable research has been done to explore the non-adsorptive nature of polyacrylamide on a platform or substrate. Attempts were made to grow polyacrylamide chains from silica as a substrate which can then be used in various protein separation techniques. Based on an ionic polymerization method which was used for gel casting in PAGE, polymers were grown on silica gel. Though considerable thickness could be achieved, polymerization was not just confined to the surface. Therefore a rigid polymer brush layer could not be achieved. Atom transfer radical polymerization (ATRP) method showed the solution to this problem. Polymer brush layers with acceptable thickness could now be achieved for growing polyacrylamide from silica gel. Yet it still suffered from several disadvantages such as the need of an inert atmosphere for polymerization and limited thickness. Many developments have taken place in the past decade which led to improvements in substrate and polymerization methods. This research used non porous sub-micron silica as the substrate and AGET ATRP (Activator generated electron transfer atom transfer radical polymerization) for surface grafting polyacrylamide. Non porous submicron silica has been shown to be a better stationary phase substrate for protein separations than conventional substrates. AGET ATRP enables polymerization to be performed under ambient conditions and in water based solutions which gives thicknesses much higher than conventional ATRP. Data from various analytical techniques showed that within the experimental range the polymerization is linear and has decent control. This means silica nanoparticles coated with polyacrylamide of varying thickness can be produced by varying the reaction time. Linear polymerization kinetics was studied using IR spectroscopy, elemental analysis, ellipsometry, GPC etc. All of them closely agree with each other. Attempts were made to expand the applicability of this novel way of material synthesis. HILIC is known as a premium separation mode for polar analytes. Glycoproteins form an important class of analytes which need better separation columns. Polyacrylamide coated nonporous colloidal silica is shown here to be a better column packing material. Combined results show that AGET ATRP can be a better and simpler alternative to ATRP for grafting polyacrylamide onto silica based substrates. Future efforts can possibly lead to the expansion of the applicability of this method for making materials for many other separation methods.

Degree

Ph.D.

Advisors

Wirth, Purdue University.

Subject Area

Analytical chemistry|Inorganic chemistry|Polymer chemistry|Nanotechnology|Materials science

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