Pseudo-lignin, which can be broadly defined as aromatic material that yields a positive acid-insoluble (Klason) lignin value, has been reported to generate from biomass polysaccharides during dilute acid pretreatment (DAP). To investigate the fundamental chemistry of pseudo-lignin, a series of state-to-art analytical techniques including GPC, FT-IR and ¹³C NMR were applied to characterize pseudo-lignin extracted from poplar α-cellulose and holocellulose after DAP. The results showed that pseudo-lignin is polymeric (Mn ~ 1000 g/mol; Mw ~ 5000 g/mol) and consists of carbonyl, carboxylic, aromatic, methoxy and aliphatic structures, which can be produced from both dilute acid-treated cellulose and hemicellulose. During DAP, the hydrolysis of polysaccharides, which leads to some release of monosaccharides, and their subsequent dehydration reactions to form furfural and 5-hydromethylfurfural (HMF) takes place. Further rearrangements of furfural and/or HMF can produce aromatic compounds, which undergo further polymerization and/or polycondensation reactions to form pseudo-lignin. More importantly, pseudo-lignin was revealed to bind with cellulase enzymes unproductively and significantly retard enzymatic conversion of cellulose. As compared to native lignin after DAP, the inhibition effect arise from pseudo-lignin is much stronger, which clearly indicates pseudo-lignin formation should be avoided during DAP. Process optimization study indicated that addition of dimethyl sulfoxide (DMSO) to the DAP reaction medium can effectively increase sugar recovery and reduce pseudo-lignin formation, even under high-severity pretreatment conditions. The pseudo-lignin suppression property of DMSO has been attributed to the preferential arrangement of DMSO in the vicinity of the C1 carbon of the HMF molecule, thereby protecting HMF from further reactions to form pseudo-lignin.

Polymer nanocomposites are an important research interest in the area of engineering and functional materials, including the search for more environmentally materials for renewable energy and materials. The ability to analyze and optimize morphology is crucial to realizing their potential, since the distribution of materials in the composite strongly influences its properties. This dissertation presents research into three different polymer nanocomposite systems with three different applications that underscore the need to understand and control the composite morphology to succeed. The first project details work on development of a copolymer compatibilizer to enhance the dispersion of the plant-derived biopolymer lignin in composite blends with polystyrene. The copolymer was designed with hydroxyl functionality that can form hydrogen bonds with lignin, and the effect of modulating the density of these groups was investigated, both on bulk dispersion and interfacial mixing. The second project presented concerns resolving the interfacial morphology of composite bulk heterojunction organic photovoltaic devices based on a polythiophene-based photoactive polymer and a modified carbon fullerene, which are archetypical of the highest performing cells yet produced. Neutron reflectivity was extensively employed to probe the interfacial width and degree of intermixing between the components to elucidate the morphological impact on device performance. The final project involves modifying nanoscale cellulose crystallites, dubbed nanowhiskers, by replacing a portion of the hydroxyl groups with acetate groups to improve their dispersion in polymethyl methacrylate. Neutron reflectivity was again employed to probe the interface between the two materials to observe and quantify intermixing.

Lignin is a major chemical component of plants and the second most abundant natural polymer after cellulose. The concerns and interests of agriculture and industry have stimulated the study of genes governing lignin content in plants in an effort to adapt plants to human purposes. Arabidopsis thaliana provides a convenient model for the study of the genes governing lignin content because of its short growth cycle, small plant size, and small completely sequenced genome. In order to identify the genes controlling lignin content in Arabidopsis accessions using Quantitative Trait Locus (QTL) analysis, a rapid micro-scale method of lignin determination is required. The acetyl bromide method has been modified to enable the rapid micro-scale determination of lignin content in Arabidopsis. Modifications included the use of a micro-ball mill, adoption of a modified rapid method of extraction, use of an ice-bath to stabilize solutions and reduction in solution volumes. The modified method was shown to be accurate and precise with values in agreement with those determined by the conventional method. The extinction coefficient for Arabidopsis lignin, dissolved using acetyl bromide, was determined to be 23.35 g-iLcm-1. This value is independent of the Arabidopsis accession, environmental growth conditions and is insensitive to syringyl/guaiacyl ratio. The modified acetyl bromide method was shown to be well correlated with the 72% sulfuric acid method once the latter had been corrected for protein contamination and acid-soluble lignin content (R² = 0.988, P < 0.0001). As determined by the newly developed acetyl bromide method and confirmed by the sulfuric acid method, lignin content in Arabidopsis was found to be a divergent property. Lignin content in Arabidopsis was found to be weekly correlated with growth rate among Arabidopsis accessions (R² = 0.48, P = 0.011). Lignin content was also found to be correlated with plant height among Arabidopsis accessions (R² = 0.491, P < 0.0001).

Universiẗat, Diss., 2006--Hamburg.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 86-89).

Thesis (Ph. D.)--Auburn University, 2008. / Vita. Includes bibliographical references (p. 223-241).

Thesis (M.Sc. (Microbiology))--Mahidol University, 1984.

Dissertation (Ph.D.)--Auburn University, 2004. / Abstract. Vita. Includes bibliographic references (p.163-173).

Thesis (Ph. D.)--Auburn University, 2008. / Abstract. Vita. Includes bibliographical references (p. 223-241).

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1992. / Vita. Abstract. Includes bibliographical references (leaves 177-190). Also available via the Internet.