Quantitative insights on de/repolymerization and deoxygenation of lignin in subcritical water.

The objective of the study was to investigate alkali lignin polymerization/depolymerization pathways in subcritical water (SW) without additives. Following a SW treatment at 200, 250, 275 and 300 °C, the products were subjected to a comprehensive suite of analyses addressing the product speciation and molecular weight (MW) distribution. The MW reduction (1.4 times) in the solid products following the SW treatment indicated a surprisingly reduced impact of cross-linking/repolymerization at 300 °C and lower temperatures. This was further confirmed by thermal carbon analysis (TCA) showing a reduction in pyrolytic charring after the SW treatment. The TD-Py gas chromatography analysis of the SW treated lignin indicated that the solid residue is less oxygenated than the initial lignin (23 vs. 29% as confirmed by elemental analysis). Thus, deoxygenation rather than re-polymerization appears to be the main process route in the absence of catalysts within the temperature range considered.

Simple and sensitive dilute-and-shoot analysis of carotenoids in human plasma.

Carotenoids in human plasma are used as biomarkers of vegetable and fruit intake. Large sample volumes and intensive sample processing make measurement of these species cumbersome. We developed a dilute-and-shoot method for the quantitation of α-carotene, ß-carotene, ß-cryptoxanthin, lycopene and lutein/zeaxanthin using 10 µL of plasma. Plasma was injected into methanol containing internal standard and deproteinized by centrifugation. The carotenoids in the supernatant were separated using a YMC C-30 column and quantified by tandem mass spectrometry. The linearity for carotenoids ranged from sub-fmol to approximately 300 fmol on-column. Spike recovery experiments were used to correct for matrix effects. The method was validated using the human plasma standard NIST SRM 968e. Over 400 sample analyses were performed using the same guard and analytical columns. This method represents an improvement over current techniques because of the small sample size needed, ease of sample preparation, and improvement in the determination of carotenoid content.

Biodegradation of lignin by fungi, bacteria and laccases.

Indulin AT biodegradation by basidiomycetous fungi, actinobacteria and commercial laccases was evaluated using a suite of chemical analysis methods. The extent of microbial degradation was confirmed by novel thermal carbon analysis (TCA), as the treatments altered the carbon desorption and pyrolysis temperature profiles in supernatants. Laccase treatments caused only minor changes, though with increases occurring in the 850°C and char precursor fractions. After fungal treatments, lignin showed a similar change in the TCA profile, along with a gradual decrease of the total carbon, signifying lignin mineralization (combined with polymerization). By contrast, bacteria produced phenolic monomers without their further catabolism. After 54days of cultivation, a 20wt% weight loss was observed only for fungi, Coriolus versicolor, corroborating the near-80% carbon mass balance closure obtained by TCA. Compositional changes in lignin as a result of biodegradation were confirmed by thermal desorption (TD)-pyrolysis-GC-MS validating the carbon fractionation obtained by TCA.