Ǥ Ǥ Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2010 by Taylor and Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Printed in the United States of America on acid-free paper 10 International Standard Book Number: 978-1-57444-486-5 (Hardback) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright 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registered trademarks, and are used only for identification and explanation without intent to infringe Library of Congress Cataloging-in-Publication Data Lignin and lignans : advances in chemistry / editors, Cyril Heitner, Don Dimmel, John A Schmidt p cm Includes bibliographical references and index ISBN 978-1-57444-486-5 (hardcover : alk paper) Lignin Lignans I Heitner, Cyril, 1941- II Dimmel, Don III Schmidt, John A IV Title TS933.L5L48 2010 572’.56682 dc22 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com 2010006628 Dedications We dedicate this book to the memories of Gordon Leary and Karl- Erik Eriksson, who both contributed chapters to this book Gordon Leary coauthored Chapter 12, “The Chemistry of Lignin-Retaining Bleaching: Oxidative Bleaching Agents” with John Schmidt He made many seminal contributions to our understanding of wood and lignin chemistry over a career that spanned more than 40 years His approximately 90 publications described research on wood, lignin, bleaching, pulping, light-induced yellowing of paper and lignin, quinone methides, lignincarbohydrate bonding, and the characterisation of lignin by NMR Shortly after receiving his PhD in 1965 from Canterbury University (New Zealand), Gordon pioneered the modern era of lignin photochemistry In several elegant publications in Nature, he proposed quinones as the primary chromophores formed in photochemical yellowing of mechanical pulps and suggested a mechanism for their formation These publications have become classic references cited in all publications on the photochemistry of wood fiber components Much of the progress in the understanding of the reaction pathways of lignin yellowing and methods to stop this yellowing have their foundations in Gordon’s pioneering research With his colleague R.W Newman, Gordon published numerous papers on the use of NMR to characterize lignin in wood and in the various morphological regions of the wood fiber This research has contributed to our knowledge of the structure of proto-lignin and the changes in lignin caused by the various extraction techniques Gordon’s status as a leading wood chemist was recognized by various administrative appointments, the first as director of the Chemistry Division of the Department of Scientific and Industrial Research (DSIR), the equivalent of Canada’s National Research Council or Australia’s Commonwealth Scientific and Industrial Research Organization (CSIRO) He held this position from 1981 until the dismantling of DSIR in 1992 The Chemistry Division was the largest division in DSIR, with a very diverse range of activities After his career at DSIR, Gordon joined the Pulp and Paper Research Institute of Canada (Paprican) in September 1992 to carry out research into the bleaching of mechanical pulps In recognition of his scientific achievements, he was elected a principal scientist (Paprican’s highest scientific ranking) by his peers He was later appointed executive director of the Canadian Mechanical Pulps Network of Centres of Excellence, a nationwide research association dedicated to enhancing the properties and value of mechanical pulps In 1996 it included researchers from 15 universities, the National v vi Dedications Research Council of Canada, and Paprican; its annual budget of about $C8 million supported the work of approximately 65 university professors and 120 graduate students and postdoctoral fellows The excellence of the scientists in this network was augmented by Gordon’s exceptional leadership During Gordon’s tenure as executive director, the Canadian Mechanical Pulps National Network represented a renaissance in Canadian pulp and paper research Gordon left Paprican and the Network in 1996 to become the manager of the Pulp and Paper business unit at the Alberta Research Council (ARC) in Edmonton, which specialized in mechanical pulps, sensors, nonwood fibers, and papermaking He built up the ARC laboratories, pilot plant, and staff from a skeleton of only eight staff and little more than a refiner and pulp-testing equipment By the time he retired, this unit had 24 staff and pilot facilities for pressurized refining, chip production and impregnation, papermaking, pulp and paper testing, coating, print quality evaluation, and sensor development Under Gordon’s leadership, ARC successfully developed a range of sensors for improved control of mill processes The sensors were based mainly on spectroscopy or image sensing, and a number of them are operating in various mills In 2001 he established a separate unit (Aquantix) to manufacture and market white water sensors for bleaching, dissolved solids and pitch control The group had also an active technology development program in pulping and papermaking with fibers from agricultural waste Even in his “retirement,” Gordon continued to contribute to wood and lignin chemistry as a member of the editorial boards of Holzforschung, Appita, and PAPTAC In 2005, he served as program chair for the 13th International Symposium on Wood and Pulping Chemistry in Auckland, New Zealand, and was recognized for his lifetime achievements at the 2007 edition of this conference in Durban, South Africa He continued to work as a visiting researcher in the Westermark group in Umea, Sweden, on what we would now recognize as the concept of the forest biorefinery Gordon possessed a rare combination of scientific, administrative, and leadership ability But even this does not fully capture the man known to his friends, colleagues, and family and to those whom he mentored To complete the picture, we need to add a sense of wonder about the natural world and scientific inquiry and a generosity of spirit towards his fellow humans These remained undiminished by the tedium that often accompanies exacting experiments or never-ending committee meetings Gordon enriched the lives of everyone that had the pleasure of working with him Karl-Erik Eriksson, who wrote Chapter 14, “Lignin and Lignan Biodegradation,” received his BS in chemistry and PhD in biochemistry in 1958 and 1963, respectively, from the University of Uppsala, Sweden He then completed his DSc in biochemistry in1967 at the University of Stockholm He joined the Swedish Forest Products Research Laboratory (STFI) in Stockholm as a research assistant in 1958; in 1964 he was promoted as department head for Biochemical, Microbial, and Biotechnical Research, working closely with Börje Steenberg He received a Fullbright Fellowship from 1968 to 1969 that Dedications vii allowed him to pursue postdoctoral studies at the California Institute of Technology with Norman Horowitz Karl-Erik pioneered the purification and characterization of fungal enzymes involved in lignocellulose degradation He invented several processes using fungal enzymes to solve problems in pulp and paper manufacturing and recycling, published more than 280 research articles, and gave more than 250 lectures at universities, professional meetings, and companies His success was due in part to his early career with scientists whose discoveries laid the foundations of modern approaches to protein purification–column chromatography using hydroxylapatite (Tiselius) and Sephadex (Flodin, Ingelman, Porath), as well as isoelectric focusing (Vesterberg) He was awarded along with T Kent Kirk the 1985 Marcus Wallenberg Prize, for investigations into the fundamental biochemistry and enzymology of wood degradation by white-rot fungi, which arose from his work on fungal enzymes Karl-Erik coauthored the book Microbial and Enzymatic Degradation of Wood and Wood Components with longtime friends and colleagues Robert Blanchette and Paul Ander in 1991 In 1988, Karl-Erik joined the faculty of the University of Georgia as Eminent Scholar of Biotechnology and Professor of Biochemistry He also served as an adjunct professor at the Institute of Paper Science and Technology (IPST) in Atlanta from 1990 to 1999 On his retirement from the University of Georgia in 1999, he was named Professor Emeritus He was a member of the Royal Swedish Academy of Engineering Sciences since 1978, sitting on its board as chairman of its Forestry and Forest Industry Sciences section from 1982 to 1985 He was elected to the World Academy of Art and Science in 1987, and was named a TAPPI Fellow in 2002 Karl-Erik had numerous engagements consulting on behalf of United Nations Agencies and the governments of several countries, using his expertise in biotechnological applications of enzymes to industrial processing of biomaterials He was also highly sought after as a consultant for companies around the world In addition to his scientific career, Karl-Erik founded a construction company and later cofounded the company Enzymatic Deinking Technologies (EDT) to exploit technology developed in his laboratory After returning to Sweden, he became the board chairman of SweTree Genomics AB He also served on the boards of directors of several additional companies Karl-Erik challenged the many students and researchers who passed through his laboratory to expand their horizons and continue learning throughout their lives, in the same way he would challenge himself He was a kind, wonderful, and talented man with a big appetite for life We hope that this volume proves a fitting tribute to Gordon’s and Karl-Erik’s legacy Contents Preface .xi Editors xiii Contributors xv Chapter Overview .1 Donald Dimmel Chapter Determing Lignin Structure by Chemical Degradations 11 Catherine Lapierre Chapter Electronic Spectroscopy of Lignins 49 John A Schmidt Chapter Vibrational Spectroscopy 103 Umesh P Agarwal and Rajai H Atalla Chapter NMR of Lignins 137 John Ralph and Larry L Landucci Chapter Heteronuclear NMR Spectroscopy of Lignins 245 Dimitris S Argyropoulos Chapter Functional Groups and Bonding Patterns in Lignin (Including the Lignin-Carbohydrate Complexes) 267 Gösta Brunow and Knut Lundquist Chapter Thermal Properties of Isolated and in situ Lignin 301 Hyoe Hatakeyama and Tatsuko Hatakeyama Chapter Reactivity of Lignin-Correlation with Molecular Orbital Calculations 321 Thomas Elder and Raymond C Fort, Jr ix x Contents Chapter 10 Chemistry of Alkaline Pulping 349 Donald Dimmel and Göran Gellerstedt Chapter 11 Chemistry of Pulp Bleaching 393 Göran Gellerstedt Chapter 12 The Chemistry of Lignin-Retaining Bleaching: Oxidative Bleaching Agents 439 Gordon Leary and John A Schmidt Chapter 13 The Chemistry of Lignin-Retaining Reductive Bleaching: Reductive Bleaching Agents 471 Sylvain Robert Chapter 14 Lignin Biodegradation 495 Karl-Erik L Eriksson Chapter 15 Biopulping and Biobleaching 521 I. D Reid, R Bourbonnais, and M. G Paice Chapter 16 The Photochemistry of Lignin 555 Cyril Heitner Chapter 17 Pharmacological Properties of Lignans 585 Takeshi Deyama and Sansei Nishibe Index 631 Preface Lignin, a constituent in almost all dry-land plant cell walls, is second only to cellulose in natural abundance The purpose of this book is to provide an up-to-date compendium of the research on selected topics in lignin and lignan chemistry The structure and reactions of lignin have been studied for more than 100 years, and the extensive output of this research has been summarized in several comprehensive review texts The first, The Chemistry of Lignin, written by F. E Brauns in 1952, was followed by a supplemental volume in 1960 by F. E Brauns and D. A Brauns Both Y Hachihama and S Jyodai in 1946 and I. A Pearl in 1967 have written monographs with the same title By the late 1960s, lignin chemistry had become so complex and covered such a large range of chemical and physical disciplines that authored chapters became the only way to provide authoritative coverage of all aspects of the field In 1971, two prominent wood chemists, Kyösti V Sarkanen and Charles H Ludwig, edited the multiauthor reference textbook Lignins Some of the contributors to this landmark text are still active in lignin research This book has been used by both students and research scientists as the bible of lignin science Since the 1971 publication of Lignins, more than 14,000 papers have been published on the chemistry and physics of lignin There has been immense progress in every area of lignin science For example, advances in the understanding of the enzymology of lignin biodegradation led to the development of bioprocesses for the production of papermaking pulp This has the potential for environmentally compatible industrial processes A reliable determination of molecular weight distribution of lignin has come into its own since 1971 Also, there have been new processes developed in the area of pulping and bleaching New areas of research have been developed in the field associated with environmentally friendly elemental chlorine– free and total chlorine–free bleaching processes When the 1971 edition of Lignins was published, spectroscopy of lignin was limited to degraded soluble lignins The techniques of solid-state spectroscopy used today to characterize lignin in the plant fiber wall had not been developed Today, UV-visible, infrared, and NMR spectroscopy are routinely used to characterise the changes in solid-state lignin in situ during and after various industrial processes During the last 39 years, there have been considerable advances in the photochemistry of lignin There is now a large body of research on the reaction pathways leading to the oxidative degradation and the formation of coloured chromophores This book is by no means a comprehensive treatise The advances in the biosynthesis of lignin and lignans since 1971 have not been included in this volume This should be the subject of a second book on the advances in lignin and lignan chemistry The editors thank the contributing authors for their dedicated effort in documenting the latest advances in their respective fields Their cooperation and patience is greatly appreciated In addition, we would like to thank those who spent countless hours reviewing the content and accuracy of each chapter An effort was made by the xi xii Preface editors to present a somewhat consistent writing style by exhaustively editing each chapter We would like to thank the authors for their cooperation in this endeavor We appreciate the kind support of FPInnovations, Paprican Division, and the Institute of Paper Science and Technology Finally, the editors would like to thank their families for their cooperation in giving up time together to complete this book ... wood, lignin, bleaching, pulping, light-induced yellowing of paper and lignin, quinone methides, lignincarbohydrate bonding, and the characterisation of lignin by NMR Shortly after receiving his... treatise The advances in the biosynthesis of lignin and lignans since 1971 have not been included in this volume This should be the subject of a second book on the advances in lignin and lignan chemistry. .. Yield in Vanillin V and Syringaldehyde S is Expressed in µmoles/g of Lignin Milled Wood Lignin from Cotton Wood Steam Explosion Lignin from Aspen Organosolv Lignin from Mixed Hardwood Kraft Lignin