Publications on Lignin

 

1.   Determination of lignin by size exclusion chromatography using multi angle laser light scattering by Aarti V. Gidh; Stephen R. Decker; Todd B. Vinzant; Michael E. Himmel; Clint Williford (pp. 102-110). Published 17 April 2006 in J Chromatography, 1114(1): 102-10.

 

A method was developed using high-performance size exclusion liquid chromatography (HPSEC) with multi-angle laser light scattering (MALLS), quasi-elastic light scattering (QELS), interferometric refractometry (RI) and UV detection to characterize and monitor lignin. The combination proved very effective at tracking changes in molecular conformation of lignin molecules over time; i.e. changes in molecular weight distribution, radius of gyration, and hydrodynamic radius. Until this study, UV detection (280nm) had been the primary lignin determination method for chromatography. Three different HPLC columns were used to study the effects of pH, flow conditions, and mobile phase compositions (dimethyl sulphoxide, water, 0.1M NaOH, and lithium bromide) on the chromatography of lignin. Since light scattering accuracy is highly dependent on solute concentration, both the UV and RI detectors were calibrated for use as concentration detectors. Shodex Asahipak GS-320 HQ column with 0.1M NaOH (pH 12.0) run at 0.5ml/min was found to give the highest separation and most consistent recovery. The study also revealed that the lignin aggregated at pH below 8.5. This aggregation was detected only by MALLS and was not observed on UV or RI detectors. It is very important to take this loss in apparent concentration due to aggregation into consideration before collecting reliable depolymerization data.

Keywords: Lignin; Light scattering; Method development; HPLC; Aggregation

2.   Fungal-Induced Redistribution of Kraft lignin Molecular Weight by Multi-Angle laser Light Scattering by  Aarti V. Gidh; Stephen R. Decker; Todd B. Vinzant; Michael E. Himmel; Clint Williford, published in Chemical Engineering Communications, publisher Taylor and Francis Ltd, Volume 193, Number 12, 2006, pp. 1546-1561(16)

Culture broths from Phanerochaete chrysosporium and Trametes cingulata , combined with co-factors such as hydrogen peroxide, dithiothreitol, copper, iron, and manganese ions were examined for the ability to modify lignin structure. High-performance size exclusion chromatography (HP-SEC) coupled to multi-angle laser light scattering (MALLS) detection was used to determine the effect of several white rot fungi, pH values, enzymes, and co-factors on the molecular weight distribution of treated kraft lignin. The analytical procedure tracked changes in molecular weight distribution, radius of gyration, and hydrodynamic radius. Results showed changes in the molecular weight distribution of lignin components when treated with combinations of factors. The induced cultures showed more lignin depolymerization for the specific lignin samples in which they were initially grown. The distribution in the radius of gyration became narrower with time, indicating that molecular conformation changed to a more uniform molecular shape. H 2 O 2 and DTT showed the most significant changes in lignin molecular weight distribution.

Keywords: Aggregation; Depolymerization; Fungi; Light-scattering; Lignin; Ligninase

3.   Detailed Analysis of Modifications in Lignin After Treatment With Cultures Screened for Lignin Depolymerizing Agents by Aarti Gidh, Dinesh Talreja, Todd B. Vinzant, Clint Williford, and Alfred Mikell, in Applied Biochemistry and Biotechnology, Spring 2006, Volume 131, Issue 1-3, pps. 829-843, (ISSN:0273-2289)

 

Termites, beetles, and other arthropods can digest living and decaying wood plus other lignocellulosic plant litter. Microbial sources like other wood-eating insect guts and wastewater treatment sludge were screened for lignin depolymerization. Near infrared spectroscopy and atomic force microscopy (AFM) along with high-performance liquid chromatography (HPLC), were used to track changes in functional groups, size, shape, and molecular weight of lignin molecules during incubations. Odontotaenius disjunctus (Betsy beetle) guts dissected whole or separately as midgut, foregut, and hindgut, consumed corn stover but did not show lignin depolymerization. The sludge-treated lignin did show some reduction in molecular weight on the HPLC, particle size (350–650 nm initially to 135–220 nm by day 30) and particles per field on AFM. pH and the presence of nutrients had a substantial effect on the extent of depolymerization. Cultures in lignin and nutrients showed higher growth than cultures with lignin only. Colony characteristics within the beetle gut and the sludge were also evaluated.


Keywords:  Lignin; beetles; NIR; HPLC; AFM; depolymerization

 

4.  Characterization of lignin using multi-angle laser light scattering and atomic force microscopy by A.V. Gidh , S.R. Decker, C.H. See, M.E. Himmel , and C.W. Williford, in
Analytica Chimica Acta., 555(2), p. 250

 

Small differences in the isolation techniques of lignin can result in significant changes in its molecular structure and configuration. Light scattering (evaluated at 18 different angles in a plane), Atomic Force Microscopy (AFM) and Near Infrared Spectroscopy (NIR) proved very effective for evaluating the characteristics of lignin. Zimm plots were generated using Zimm, Debye and Berry formalisms to evaluate the weight average molecular weight (MW), radius of gyration (r"g), hydrodynamic radius (r"h) and second virial coefficient (A"2). Two types of lignin and nine different solvents were used for the study, to analyze the conformation of lignin molecules in different solvents expected to be used in lignin degradation and subsequent analysis. Absolute MW and r"g decreased and the dn/dc increased when the solvent used for lignin was changed from water to sodium hydroxide. The two types of lignin also exhibited different values for all the above estimated parameters. This study also highlighted the differences between the unlyophilized and lyophilized lignin in terms of aggregation, pH dependence and stability over time. This aggregation has never been seen on a ultraviolet (UV) or refractive index (RI) detector that has been used so far for liquid chromatography (LC) reducing the reliability of lignin depolymerization data obtained without light scattering.