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Isolation and Characterization of Lignin from Populus ISOLATION AND CHARACTERIZATION OF LIGNIN FROM POPULUS by Jaclyn Jeanette Stewart B.Sc, The University of British Columbia A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES (Forestry) THE UNIVERSITY OF BRITISH COLUMBIA April 2005 © Jaclyn Jeanette Stewart, 2005 Abstract Wood chemistry, and in particular lignin chemistry, impacts chemical pulp yield and quality. In this research, a thorough lignin chemical structure was elucidated and related to pulp properties of natural aspen clones and genetically modified hybrid poplar. The chemical differences among phenotypically distinct naturally grown aspen clones indicated that considerable variability exists in the concentration of carbohydrates, lignin, and extractive. Lignin monomer ratio was determined using thioacidolysis and nitrobenzene oxidation, and varied from 74.4 to 80.3% syringyl units. The ease of chemical pulping was very strongly correlated with the mol % S derived from nitrobenzene oxidation. Two clones (10-1 and 16-2) that revealed the greatest differences in Kraft pulping efficiencies (difference of yield and Kappa) were subject to extensive lignin analyses. The peak molecular weight of sample 10-1 lignin was shown to be significantly higher than sample 16-2 lignin. These two samples were also employed for in-depth NMR analysis in order to determine side chain linkages, functional group differences, and aromatic carbon nature. It was shown that the structure of the residual lignin generated by ball milling was consistent with Kraft pulp efficacy; the phenolic hydroxyl content and methoxyl content were both higher for sample 16-2 than for sample 10-1. A similar study, employing highly selective and controlled genetically modified lignin, involved in-depth lignin analysis. Hybrid poplar expressing the Arabidopsis ferulate 5-hydroxylase gene under the control of a cinnamate 4-hydroxylase promoter was the model sample. As expected, the modified lignin had an increase in syringyl content as measured by thioacidolysis and methoxyl analysis. In addition to this monomer ratio shift, the molecular weight of the lignin was reduced in the modified lignin, which may further enhanced chemical pulping efficiency. This is the first report of a dramatic molecular weight decrease due to up-regulation of a gene in the lignin biosynthetic pathway. ii Table of Contents Abstract ii Table of Contents • iii List of Tables vi List of Figures vii List of Abbreviations x Acknowledgements xii Chapter 1 - Introduction 1 1.1 Plantation Forestry: Rationale and Tree Selection 1 1.2 Wood Chemistry and Cell Wall Structure 5 1.2.1 Lignin 5 1.2.2 Cellulose 8 1.2.3 Hemicellulose 8 1.2.4 Cell Wall Ultrastructure 9 1.2.5 Cell Types 10 1.3 Kraft Pulping 11 1.3.1 Kraft Pulping Reactions 13 1.3.2 Pulp Conventions 16 1.3.3 Factors Affecting the Rate of Delignification 17 1.3.4 Structural Effects 17 1.3.5 Effects of Lignin Composition 19 1.4 Selection of Trees for Improved Pulping Performance 21 1.5 Lignin Structural Analysis 22 1.6 Wet Chemistry Methods for Lignin Studies 24 1.6.1 Degradation Methods 24 1.6.2 Methoxyl Analysis 26 1.7 Spectroscopic Methods 27 1.7.1 Nuclear Magnetic Resonance Spectroscopy 27 1.8 Overview and Objectives 31 1.9 Bibliography 33 Chapter 2 Isolation and Characterization of Lignin from Natural Aspen Clones 37 2.1 Introduction 37 2.2 Methods and Materials 40 2.3 Results and Discussion 46 iii 2.3.1 Wood Composition 46 2.3.2 Kraft Pulping 47 2.2.3 Lignin Monomer Ratio 48 2.3.4 Molecular Weight Determination 50 2.3.5 Nuclear Magnetic Resonance Spectroscopy 52 2.4 Conclusion 59 2.5 Tables and Figures 60 2.5 Bibliography 81 Chapter 3 Elucidating the Effects of Lignin Monomer Composition on Chemical Pulping Efficacy in C4H:F5H Transformed Hybrid Poplar 83 3.1 Introduction 83 3.2 Materials and Methods 86 3.3 Results and Discussion 90 3.3.1 Wet Chemistry Methods 90 3.3.2 Molecular Weight Determination 91 3.3.3 Nuclear Magnetic Resonance Spectroscopy 93 3.4 Conclusion 100 3.5 Tables and Figures 101 3.6 Bibliography 116 Chapter 4 118 4.1 Conclusions and Future Work 118 4.2 Bibliography 121 Appendix A - Supplementary Tables and Figures for Chapter 2 122 Appendix B - Supplementary Tables and Figures for Chapter 3 135 Appendix C - Detailed Materials and Methods 138 C.l Harvesting Aspen Clones 138 C.2 Modification of C4H-F5H Hybrid Poplar 139 C.3 Determination of Moisture Content 140 C.4 Quantitative Determination of Extractives 140 C.5 Determination of Methoxyl Content 142 C.6 Determination of Monolignol Composition by Degradation - Thioacidolysis 143 C.7 Determination of Monolignol Composition by Degradation - Nitrobenzene Oxidation 145 C.8 Carbohydrate and Acid Soluble & Insoluble Lignin Analysis 146 C.9 Kraft Pulping Trials 148 iv C. 10 Determination of Pulp Residual Lignin 148 C.ll Ball Milled Wood 150 C. 12 Isolation of Lignin from Ball Milled Wood 151 C. 13 Molecular Weight Measurements 152 C. 14 Elemental Analysis 152 C.15 Acetylation of Ball Milled Wood 153 C.16 Acetylation of Lignin 153 C. 17 Traditional Acetylation Method 153 C. 18 Nuclear Magnetic Resonance Spectroscopy Experiments 154 C. 19 Lignin Hydroxyl Content 155 C.20 Bibliography 156 v List of Tables Table 1.1. NMR chemical shift ranges for common functional groups present in lignin 29 Table 2.1. Mole percent syringyl (% S) units in various substrates, wood, MWL, REL, and Kraft pulp, based on thioacidolysis 66 Table 2.2. Comparison of mole % syringyl units as determined by thioacidolysis and nitrobenzene oxidation of extractive-free ground wood samples 67 Table 2.3. Elemental analysis and expanded C9 formula for MWL for 10-1 and 16-2 68 Table 2.4a. Signal assignment in the NMR spectrum of non-acetylated MWL 69 Table 2.4b. Signal assignment in the NMR spectrum of acetylated MWL 70 Table 2.4c. Lignin structural unit calculations 71 Table 2.5. Summary of NMR results relevant to the Kraft pulping mechanism 77 Table 3.1. Thioacidolysis yield and S:G monomer content for isolated lignin fractions 102 Table 3.2. Elemental analysis and expanded C9 formula for MWL for wild-type and C4H-F5H lignin 103 Table 3.3a. Signal assignment in the NMR spectrum of non-acetylated MWL 107 Table 3.3b. Signal assignment in the NMR spectrum of acetylated MWL 108 Table 3.3c. Lignin substructures determined by NMR 109 Table Al. Kraft pulp yield and Kappa numbers 122 Table A2. Elemental Analysis of wood and lignin fractions 123 Table B1. Elemental Analysis of wood and lignin fractions 137 vi List of Figures Figure 1.1. Species yield variation in short-rotation species planted in Canada 2 Figure 1.2. A schematic of a portion of hardwood lignin showing the most frequent monomers and important linkages. See Figure 2.12 for more lignin subunits 7 Figure 1.3. Stylized drawing of wood cell wall layers depicting the middle lamella (ML), primary cell wall (P), secondary cell wall layers (Si, S2, S3), and the warty layer (W) 10 Figure 1.4. Major cell types in softwoods and hardwoods 11 Figure 1.5. Kraft pulping mechanism of a P-O-4 ether linkage in lignin 14 Figure 1.6. The formation of a stilbene unit from a p-1 lignin substructure under alkaline conditions 15 Figure 1.7. Precursors to lignin monomers. Coniferyl alcohol gives rise to the guaiacyl structures, and sinapyl alcohol gives rise to the syringyl monomers 19 Figure 1.8. Proposed mechanism of P-ether cleavage from thioacidolysis 25 Figure 2.1. Isolation, purification, and acetylation of various lignin fractions 60 Figure 2.2. Total wood composition of the six natural aspen clones from northern BC, Canada. 61 Figure 2.3. Individual neutral wood sugar composition of the six natural aspen clones from northern BC, Canada 62 Figure 2.4. Total lignin content of the six natural aspen clones from northern BC, Canada 63 Figure 2.5. Percent individual extractives classes of the total extractives of six natural aspen from northern BC, Canada. Error bars represent the standard deviation of three replicates 64 Figure 2.6. Pulp yield and residual Kappa number of pulp (H-factor 1100) from six natural aspen clones from northern BC, Canada 65 Figure 2.7a. Quantitative 13C NMR spectrum for MWL samples 72 Figure 2.7b. Quantitative 13C NMR of AcMWL 73 Figure 2.8. Quantitative 13C NMR spectra of aspen clonal acetylated REL samples 75 Figure 2.9. Molecular weight distributions for acetylated aspen MWL samples 76 Figure 2.10. Molecular weight distributions for acetylated aspen CEL 77 Figure 2.11. Molecular weight distributions for acetylated aspen REL 78 vii Figure 2.12. Lignin substructures (Capanema et al. 2004) 79 Figure 2.13. HMQC spectrum of sample 10-1 and 16-2 MWL 80 Figure 3.1. Isolation, purification, and acetylation of various lignin fractions 101 Figure 3.2. Gel-permeation chromatograph of acetylated MWL (AcMWL) from wild-type and C4H-F5H poplar 104 Figure 3.3. Gel-permeation chromatograph of acetylated CEL (AcCEL) lignin from wild-type and C4H-F5H poplar 105 Figure 3.4. Gel-permeation chromatograph for acetylated REL (AcREL) lignin from wild-type and C4H-F5H 106 Figure 3.5a. Quantitative 13C NMR spectra of non-acetylated MWL. Expanded region is shown in Figure 3.5b 110 Figure 3.5b. Quantitative 13C NMR spectra of non-acetylated MWL in the region from 157 to 140 ppm : Ill Figure 3.6. Quantitative l3C NMR spectra of acetylated REL 113 Figure 3.7.
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