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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 stu-
dents 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 papermak-
ing. 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 produc-
tion 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 estab-
lished 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 chem-
istry 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 con-
tinued 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.
Chapter 1. Overview...............................................................................................1
Donald Dimmel
ix
x Contents
xi
xii Preface
Cyril Heitner retired from Paprican after a 36-year career. He received his BSc in
chemistry from Sir George Williams University in 1963, his MSc in physical organic
chemistry from Dalhousie University in 1966, and his PhD in organic photochemis-
try from McGill University in 1971. Dr. Heitner came to the institute as an Industrial
Postdoctoral Fellow in 1970 and joined the staff in 1972.
The first of Dr. Heitner’s scientific achievements were in the area of lignin modi-
fication to produce high-quality ultra-high-yield pulps. He discovered the effects of
sulfonation on lignin softening, which has a profound effect on fiber length distri-
bution and interfiber bonding of ultra-high-yield pulps. With R. Beatson, he was
xiii
xiv Editors
the first to determine the mechanism of lignin sulfonation in wood fiber. He and
D. S. Argyropoulos also discovered that decreasing the pH of the sulfonation from
9 to 6 increased the amount of well-developed thin and flexible fibers and decreased
the specific energy required. This discovery is now being used in most CTMP mills.
Dr. Heitner has made significant scientific contributions in the area of chromophore
chemistry of lignin-containing pulp and paper. He has developed a method for cal-
culating the UV-visible absorption spectra of paper from reflectance values of thin
(10g/m2) sheets of paper. Using this technique, he studied both bleaching and light-
and heat-induced reversion of lignin-containing pulps and paper. With J. A. Schmidt,
he determined that multiplicity of the excited state leading to the cleavage of the
phenacyl aryl ether bond using α-guaiacoxyacetoveratrone as a model was both sin-
glet and triplet. It had been assumed by researchers that this group undergoes bond
cleavage exclusively by the triplet excited state. This group also determined that an
important reaction pathway leading light-induced yellowing involved cleavage of the
β-O-4 aryl ether bond to a ketone and a phenol. This research has led to the devel-
opment of a yellowing-inhibitor system that is close to commercial development.
Contributors
Umesh P. Agarwal Raymond C. Fort, Jr.
Fiber and Chemical Sciences Research Department of Chemistry
USDA Forest Products Laboratory University of Maine
Madison, Wisconsin Orono, Maine
xv
xvi Contributors
CONTENTS
Introduction.................................................................................................................1
Occurrence..................................................................................................................2
Formation and Structure.............................................................................................2
Isolation and Structure Proofs.....................................................................................8
Reactivity....................................................................................................................9
Uses........................................................................................................................... 10
INTRODUCTiON
As the second most abundant natural polymer in our world, lignin has drawn the
attention of many scientists for several centuries. Due to its complexity, nonunifor-
mity, and conjunctive bonding to other substances, lignin has been difficult to isolate
without modification and difficult to convert into useful consumer products, and its
structure has been difficult to determine. The challenges presented in studying lignin
have resulted in a vast amount of published literature. The goal of this volume is
provide a resource that summarizes our present knowledge of lignin in certain key
areas. The most inclusive description prior to this volume is best summarized in
the book of K. V. Sarkanen and C. H. Ludwig, Lignin (Wiley-Interscience, 1971).
This overview chapter takes much of its material from the aforementioned book
and invites the reader to consult this book for greater depth. No references are pre-
sented in this first chapter; most discussion is supported by material in Sarkanen and
Ludwig’s book.
The biosynthesis of lignin is an important subject to understanding lignin struc-
ture, but it is not covered in this volume. It is a topic that deserves separate treatment,
is steeped in controversy, and would add approximately 50% more pages to an already
large volume. This volume focuses mainly on modern methods of lignin structure
proof, on lignin reactivity, and on one aspect of lignan use. This brief introductory
chapter is intended to familiarize the reader with a few basics, which are inherent to
the discussions of the later chapters.
The discussion presented in this chapter will be expanded with the material given
in Chapter 8. The layout of the volume is to present (i) a simple picture in this chapter;
(ii) detailed chemical and spectral structural studies in Chapters 2–7; (iii) a coherent
picture of lignin structure in Chapter 8; (iv) lignin/lignan reactions in Chapters 9–15,
and then (v) pharmacological properties of lignans in Chapter 16. Since some readers
will jump around from one chapter to another, we will (out of necessity) have some
1
2 Lignin and Lignans: Advances in Chemistry
repetition of material. In general, a reader will better understand the chemistry pre-
sented in later chapters by first reading the earlier chapters, especially Chapters 1
and 8.
OCCURRENCE
Nature is composed of minerals, air, water, and living matter. The latter contains
polymers. The most abundant natural polymer is cellulose. It, together with lignin
and hemicelluloses, are the principal components of plants. The principal function
of lignin in plants is to assist in the movement of water; the lignin forms a barrier for
evaporation and, thus, helps to channel water to critical areas of the plant.
Lignin is present in plants for which water conduction is important. Of greatest
interest is its presence in trees. The lignin content depends on the type of tree: about
28% for softwoods and 20% for hardwoods. The cellulose content is approximately
45% in the wood of both types, while the hemicellulose content is roughly 17% in
softwoods and 25% in hardwoods. Lignin structure can vary within the same plant,
e.g., primary xylem, compression wood, early versus late wood, etc.
Alcohol
CH2-OH
CH3O γ
Oxidation
CH2OH CH2OH
OCH3 OCH3
O O
C1-radical Cβ-radical
CH2OH CH2OH
CH CH
CH CH
O-4 CH CH CHOH
HOH
has two double bonds exiting the ring between C1 = Cα and C4 = O4. These quinone
methides are quite reactive and readily accept additions of nucleophiles to the C1 = Cα
double bond, resulting in regeneration of a much more stable aromatic ring, as shown
by the chemistries presented in Figures 1.4 through 1.8.
In addition to the formation of β–O–4 and α–O–4 ether bonds, as shown in
Figures 1.4 and 1.5, an ether linkage between C–5 and O–4 (a diphenyl ether) is
Overview 5
CH2OH CH2OH
CH CH H3CO
CH CH H H
O C C CH2OH
CH2OH CH2OH
CH3O CH3O
O CH O CH
O-4 CH CH2OH
CH
CH
CH3O CH3O CH
O O
C–β CH2OH
CH3O H3CO
O CH
etc. H H
CH O C C CH2OH
CH3O
O
CH CH
CH
CH CH
CH Enolization CH2OH
CH2OH
CH2OH
CH
CH CH3O
CH3O CH CH3O CH
OH
O O H CH
CH CH2OH
C-5
CH CH3O
CH3O
CH3O O CH O
O
CH2OH
Michael
C–β etc.
CH3O CH addition
O
CH
CH3O
OH
also present to a small extent in lignin. Several C–C linkages also exist; Figure 1.6
outlines the chemistry for the production of a β–5 linkage. The latter is an example
of a naturally occurring condensed structure. Another common C–C linkage in
lignin exists in biphenyl units, which occur by the coupling of two phenoxy radicals
at their C–5 positions. Coupling of a phenoxy radical at the C–1 position is also
possible, an example of which produces a β–C–1 linkage (Figure 1.7). After the
6 Lignin and Lignans: Advances in Chemistry
CH2OH CH2OH
CH2OH
A rO C H ArO CH
ArO CH CH2OH
CH2OH H CH2OH
HO CH O CH
HO CH H3CO CH
CH H2O H3CO CH
CH CH CHOH
O O
CH3O
O
OCH3 OCH3
C–1 OCH3
O O OH
C–β
H3CO CH2OH
O CH
CH2OH
CHOH
+ ArO CH
H +
CH
O OCH3
OH
CH2OH CH2OH
CH CH
CH CH
CH2OH CH2OH
CH CH
OCH3 Enolization
CH O OCH3 CH
O
C–3
CH3O CH3O
O O
C–β
initial coupling step, the side chain of one of the units is lost in order to regener-
ate aromaticity. The chemistry is facilitated by the relatively good stability of the
aldehyde leaving group.
So far we have considered examples of coupling of all but one of the phenoxy
radical density sites (O–4, C–1, C–3, C–5, and C–β [Figure 1.2]). Lignin linkages
involving the C–3 site have not been observed. Coupling at this position likely
occurs, but the process does not lead to a stable product (Figure 1.8). There is no
good way for the aromatic ring to be regenerated with the methoxyl group present
at C–3, since it is a poor leaving group. Consequently, the coupling likely reverses
back to the individual radical species, which find other ways to couple, such as
those shown in Figures 1.4 through 1.7. Since the building block sinapyl alcohol
Overview 7
C
H CO
C 3 C H3CO
C O C O
C H3CO O
O OCH3
(H)
O
C C
C O
C H3CO
OCH3 OCH3 C
C O O OCH3
O O
(H) (H)
5–5 Biphenyl
β–1 1,2-Diarylpropane β–β α–Oγ
β–5 Phenylcoumaran Softwood 18%
Hardwood 10% Soft - & hardwoods ~ 7% Soft - & hardwoods ~ 2%
Softwood 11%
Hardwood 6% (some free, as shown)
(some part of an
8-membered ring)
has methoxyl groups on both C–3 and C–5, coupling to both these positions will be
inhibited and there will be little in the way of condensed structures formed. On the
other hand, lignin derived from building block p-coumaryl alcohol, which has no
methoxyl groups on C–3 and C–5, will have significantly more highly condensed
structures. The proportion of condensed structures in a given lignin plays a major
role in determining its reactivity, since C–C linkages are much less reactive than are
C–O (ether) linkages.
Chapter 8 has much more detail on the structural units and linkage frequencies
that exist in lignin. There are several variations of those presented here. However, of
all the options that exist for generating interunit linkages, the β–O–4 linkage is the
most predominant type in both softwoods and hardwoods (Figure 1.9). The second
most abundant types involve linkages to the C–5 position (with linkages to Cβ−, C5−,
or O4-positions).
Figure 1.10 presents a partial representation of a softwood lignin. The main chain
is shown by the combination of coniferyl alcohol units 1–10. Branching is shown by
the units A and C attached to the main chain. The linkage types are color coded:
dashed lines = more reactive ether bonds, dotted lines = low reactive C–C and O–4/
C–5 ether bonds, and dashed and dotted lines = the generally reactive α–O–4 and
α–O–γ bonds. It should be pointed out that this picture is an oversimplification; the
picture will be further refined as the reader delves into the various chapters. The
message intended to be conveyed now is that lignin is a complex cross-linked poly-
mer made up of different monomer units, linked in a variety of ways. Lignin exhibits
a wide polydispersity, meaning that it has no characteristic molecular weight; values
of 400 to more than a million weight average molecular weight have been reported.
8 Lignin and Lignans: Advances in Chemistry
HO
OH
B O
HO O 4 OH
OCH3 HO
H3CO O
A
H3CO CH2OH C 3 H3CO 5
O CH H3CO OCH3
O OH
HO CH O
CH2OH O
1 2 HO
H3CO O OCH3
O OCH3 OH 6
O
HO OH 9 OH
O
OCH3
7
10
H3CO
OCH3
H O 8 O O
O
H
OCH3
REACTiViTY
The topic of lignin/lignan reactivity is the principal focus of Chapters 9 through 15.
The correlation of molecular orbital calculations with lignin reactivity is taken up in
Chapter 9. The geometry of a molecule markedly affects its energy and reactivity.
Molecular orbital calculations give insight into lignin geometry, specifically confor-
mational preferences, with respect both to ground states and to reaction intermedi-
ates. In addition, the calculations can pinpoint reactive sites by computing charge
(and radical) densities of intermediates.
The greater reactivity of the various functional groups in lignin, as compared
to those in carbohydrates, is the key to producing chemical pulps that are used in
making high-quality paper products. Here the goal is to retain carbohydrate wood
components and remove lignin components. The two primary steps in chemical pulp
production are pulping (Chapter 10) and bleaching (Chapter 11). Chemical pulp-
ing largely involves alkaline processes that initiate reaction at the lignin’s phenolic
hydroxyl groups and give rise to cleavage of many of the aryl ether bonds; such
chemistry is not possible with carbohydrates, since they lack both of these func-
tionalities. Pulping can go only so far with this kind of chemistry; some lignin will
still be resistant. This is where bleaching comes in. Here the chemistry involves
breakdown of the lignin aromatic units, again a feature not present in carbohydrates.
While this all seems simple enough, the reality is that there are many complexities,
which will be the topics in Chapters 10 and 11.
Lignin does not have to be totally, or even partially, removed to give rise to
paper products. Examples include pulps produced by the mechanical defibration
of logs and steamed and/or chemically treated chips. Such pulps still contain
significant quantities of lignin and suffer from lower bleachability and yellowing
due to thermal- and light-induced oxidation. However, such pulps can be produced
with double the yield and one-quarter the pollution than that obtained by chemi-
cal pulping. In addition, it is advantageous to use lignin-rich pulps because of
higher bulk that permits lower basis weight and larger printing surface per ton of
paper. Chapters 12 and 13 report on the advances in the chemistry of oxidative
and reductive lignin-retaining bleaching. Brightness is one of the most important
parameters that determine value. The oxidation and reduction of colored chro-
mophores in lignin-containing pulp (stone and refiner groundwood), sometimes
in sequence, increases the value of the paper produced. Chapter 14 reports on the
photochemical processes of lignin and lignin model compounds, most of which
cause yellowing of high-brightness lignin-containing papers. Lignin contains both
moieties that absorb light to produce free-radicals, and react with oxygen, and moi-
eties that react with photo-induced radicals. Also, there are lignin groups that sen-
sitize the formation of reactive singlet oxygen (1O2), which in turn react with the
various groups in lignin to cause color production and contribute to β–O–4 aryl
etheir cleavage.
An evolving area is the use of biodegradation as a means to facilitate lignin
removal (Chapters 15 and 16). Useful biodegradation chemistry again takes advantage
of existing reactivity differences between lignin and carbohydrates. The employed
enzymes often have high specificity for phenolic structures.
10 Lignin and Lignans: Advances in Chemistry
USES
By far, the principal use for lignin is as fuel in the production of pulp used for paper
and corrugated board. High-quality paper products require that the lignin be sepa-
rated from the cellulose in wood. The pulping process produces a pulp rich in cellu-
lose and a liquor rich in degraded lignin. The liquor is partially evaporated and burnt
in a furnace. Inorganic pulping chemicals are recovered, and the energy generated
is used in the pulp production. Lignin has a high calorie content, which makes it an
excellent fuel. In essence, the lignin in wood provides the energy needed to make the
cellulose-rich pulp. This sentence can be changed to the following: Bleaching follows
pulping when high-brightness products are desired. The lignin-derived fragments in
the bleaching liquors have no value and disposal of these liquors is a problem.
For many decades, researchers have tried to find applications for uses of lignin
derived from pulping liquors. This highly altered, complex lignin presents real chal-
lenges with respect to finding commercially valuable end uses. However, the future
use of plants (including wood) as sources of chemicals, rather than just for making
paper products, will generate large quantities of a new kind of lignin. Some plants
are now being processed for ethanol fuel production (from their carbohydrate com-
ponents); commercial uses of the lignin by-product will greatly enhance the process-
ing costs.
Chapter 17, Pharmacological Properties of Lignans, is the only chapter in this
volume that specifically addresses uses and characteristics of lignans. This chapter
describes the activity of a wide variety of lignans derived from medicinal plants and
used in traditional and folk medicines. The chapter also reports on the physiological
changes in tumors in the digestive, reproductive, and endocrine systems caused by
lignans and how these effects can be incorporated into various therapies.
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