Investigation and control of alkylsilane stationary phase structure in reversed phase liquid chromatography is presented. Raman spectroscopy is used to probe the alkyl chain conformational order and interchain coupling as a function of various chromatographic conditions. A new method is further developed to fabricate alkylsilane stationary phases with controlled surface coverage. The alkyl chain conformational order and interchain coupling of a series of high-density docosylsilane (C22) bonded stationary phases is shown as a function of temperature, surface coverage, polymerization method, common solvents and solutes. The conformational order of C22 stationary phases is compared to that of octadecylsilane (C18) stationary phases to understand the chain length effect on stationary phase structure. The conformational order information as indicated by Raman spectral order indicators for a C22 phase are correlated with the capacity factor and separation efficiency for each solute studied to gain insight into the retention mechanism. These studies help to understand the origin of stationary phase shape selectivity and the separation process in general. Based on these results, the molecular pictures at the stationary phase/solvent interface are proposed. The effect of pressurized solvent environments on two C18 phases is studied to obtain direct evidence for changes in stationary phase structure due to pressure. These changes are compared to effects of solvation relative to air in the same solvents. In addition, Raman spectral order indicators are identified for perdeuterated alkyl-containing system. This study provides a foundation for studying stationary phase structure in complex systems comprised of long alkyl-containing solutes.A further development of a new method is presented as well for synthesizing alkylsilane stationary phases with precisely controlled surface coverage by using a displaceable surface template monolayer of n-alcohol. A mechanism for this process is proposed based on the studies of n-alcohol concentration and chain length effect on the stationary phase surface coverage. The utility of these new stationary phases as chromatographic support is demonstrated. The shape selectivity for these new phases is comparable to or better than similar phases prepared by conventional methods.

The conversion of switchgrass lignin, a renewable source for chemicals and fuels, is investigated using reactions such as depolymerization, hydrodeoxygenation and alkylation. First, the lignin is converted into oils containing phenol, substituted guaiacols and other smaller lignin fragments using formic acid and Pt/C through a batch process. A long reaction time was observed to crucial to yield oils with the highest fraction of lower molecular weight compounds with the lowest O/C and highest H/C molar ratio. Second, the zeolite catalyzed gas phase alkylation of phenol, a model compound for the lignin oil, with propylene was investigated. Zeolite pore topology and acid strength were shown to influence the selectivity for the target product, 2-isopropylphenol. This work shows that the conversion of lignin to useful products is possible and suggests some future work to consider before it can be implemented practically.

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