Fractional Separation and Structural Characterization of Chlorophyll and Lignin from Perennial Ryegrass (L. perenne) and Cocksfoot Grass (D. glomerata)

Abstract One chlorophyll rich fraction and two lignin preparations were separated from perennial grass and cocksfoot grass by sequential three‐stage treatments with 80% ethanol containing 0.2% NaOH, 2.5% H2O2−0.2% EDTA containing 1.5% NaOH, and 2.5% H2O2−0.2% TAED containing 1.0% NaOH at 75°C for 3 h, respectively, which released 4.6 and 3.6% chlorophyll rich fraction, 2.3 and 5.8%, and 0.9 and 1.0% lignin preparations, except for releasing 8.0 and 10.4%, 79.1 and 77.0%, and 12.9 and 12.5% of the original hemicelluloses, respectively. The lignin fractions obtained from the two different grasses had very similar molecular weights and structural composition. The NMR spectra of the lignin preparations revealed the presence of p‐hydroxyphenyl, guaiacyl, and syringyl structures, and the lignin in chlorophyll rich fraction contained more guaiacyl and syringyl units than p‐hydroxyphenyl unit, whereas the reverse trend was found in the two lignin preparations. The lignin preparations are distinguished with straw and wood lignins by relatively higher contents of p‐hydroxyphenyl unit and lower amounts of condensed units (β‐5 and 5‐5′) and resinol units (β‐β). This difference in distribution of structural units indicated some structural heterogeneity between grass and straw/or wood lignin.

[1]  J. Weber,et al.  Thermal behaviour of Miscanthus grasses, an alternative biological fuel , 2007 .

[2]  R. Sun,et al.  Fractional and structural characterization of hemicelluloses from perennial ryegrass (Lolium perenne) and cocksfoot grass (Dactylis glomerata). , 2006, Carbohydrate research.

[3]  E. Wiśniewska,et al.  Cell wall polysaccharides in differentiating anthers and pistils of Lolium perenne , 2006, Protoplasma.

[4]  R. Hatfield,et al.  Cell wall composition in juvenile and adult leaves of maize (Zea mays L.). , 2006, Journal of agricultural and food chemistry.

[5]  R. Sun,et al.  Comparative study of organosolv lignins from wheat straw , 2006 .

[6]  J. Weber,et al.  Kinetic modelling of the pyrolysis of Miscanthus × Giganteus from the thermogravimetric analysis of its fractionated components , 2005 .

[7]  Paul Fowler,et al.  Extraction and characterization of original lignin and hemicelluloses from wheat straw. , 2005, Journal of agricultural and food chemistry.

[8]  R. Sun,et al.  Comparative study of lignins from ultrasonic irradiated sugar‐cane bagasse , 2004 .

[9]  J. Ralph,et al.  Lignins and ferulate-coniferyl alcohol cross-coupling products in cereal grains. , 2004, Journal of agricultural and food chemistry.

[10]  John Ralph,et al.  Plant biology and pathology / Biologie et pathologie végétales Genetic and molecular basis of grass cell-wall degradability. I. Lignin-cell wall matrix interactions ✩ , 2004 .

[11]  Zengyu Wang,et al.  Lignin deposition and associated changes in anatomy, enzyme activity, gene expression, and ruminal degradability in stems of tall fescue at different developmental stages. , 2002, Journal of agricultural and food chemistry.

[12]  M. Misra,et al.  Sustainable Bio-Composites from Renewable Resources: Opportunities and Challenges in the Green Materials World , 2002, Renewable Energy.

[13]  Wolfgang G. Glasser,et al.  Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials , 2002 .

[14]  D. Evtuguin,et al.  Structural characterization of the lignin from the nodes and internodes of Arundo donax reed. , 2000, Journal of agricultural and food chemistry.

[15]  J. Bolton,et al.  Determination of Ferulic and p-Coumaric Acids in Wheat Straw and the Amounts Released by Mild Acid and Alkaline Peroxide Treatment , 1998 .

[16]  M. Sain,et al.  Bleach activation of thermomechanical pulp , 1997 .

[17]  G. A. Jung,et al.  Chemical Composition of Parenchyma and Sclerenchyma Cell Walls Isolated from Orchardgrass and Switchgrass , 1991 .

[18]  J. U. Grobbelaar,et al.  Extraction of chlorophyll a from freshwater phytoplankton for spectrophotometric analysis , 1984, Hydrobiologia.

[19]  I. Morrison Changes in the lignin and hemicellulose concentrations of ten varieties of temperate grasses with increasing maturity , 1980 .

[20]  D. Himmelsbach,et al.  Carbon-13 nuclear magnetic resonance of grass lignins , 1980 .

[21]  Erich Adler,et al.  Lignin chemistry—past, present and future , 1977, Wood Science and Technology.

[22]  H. Nimz Beech Lignin—Proposal of a Constitutional Scheme , 1974 .

[23]  N. Blumenkrantz,et al.  New method for quantitative determination of uronic acids. , 1973, Analytical biochemistry.

[24]  R. Bailey,et al.  Chemistry and Biochemistry of Herbage , 1973 .

[25]  R. Sun,et al.  Quantitative determination of phenolic acids in the cell walls of shrubs and poplar wood , 2006 .

[26]  M. Casler Breeding forage crops for increased nutritional value , 2001 .

[27]  I. Kilpeläinen,et al.  Characterisation of Milled Wood Lignin from Reed Canary Grass (Phalaris arundinacea) , 1997 .

[28]  J. Ralph,et al.  A Biomimetic Route to Lignin Model Compounds via Silver (I) Oxide Oxidation. 1. Synthesis of Dilignols and Non-cyclic Benzyl Aryl Ethers , 1994 .

[29]  J. Ralph,et al.  A Biomimetic Route to Lignin Model Compounds via Silver (I) Oxide Oxidation. 2. NMR Characterization of Non-Cyclic Benzyl Aryl Ether Trimers and Tetramers , 1994 .

[30]  O. Faix,et al.  Determination of Phenolic Hydroxyl Group Content of Milled Wood Lignins (MWL's) from Different Botanical Origins Using Selective Aminolysis, FTIR, 1H-NMR, and UV Spectroscopy , 1992 .

[31]  B. Monties,et al.  Plant cell walls as fibrous lignocellulosic composites: relations with lignin structure and function , 1991 .

[32]  G. Hallegraeff Pigment Diversity in Freshwater Phytoplankton. I. A Comparison of Spectrophotometric and Paper Chromatographic Methods , 1976 .

[33]  Karl Freudenberg,et al.  Constitution and Biosynthesis of Lignin , 1968 .