Capitulo Lignina 2014.1-37

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BIOCHEMISTRY RESEARCH TRENDS
LIGNIN
STRUCTURAL ANALYSIS,
APPLICATIONS IN BIOMATERIALS
AND ECOLOGICAL SIGNIFICANCE
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LIGNIN
STRUCTURAL ANALYSIS,
APPLICATIONS IN BIOMATERIALS
AND ECOLOGICAL SIGNIFICANCE
FACHUANG LU
EDITOR
New York
Copyright 2014 by Nova Science Publishers, Inc.

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CONTENTS
Preface
Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
vii
Polyvalent Lignin: Recent Approaches in Determination
and Applications
Wanderley Dantas dos Santos, Rogrio Marchiosi,
Flvia Carolina Moreira Vilar, Rogrio Barbosa Lima,
Anderson Ricardo Soares, ngela Valderrama Parizotto,
Dyoni Matias de Oliveira and Osvaldo Ferrarese-Filho
The DFRC (Derivatization Followed by Reductive Cleavage)

Method and Its Applications for Lignin Characterization
Fachuang Lu and John Ralph
27
Structural Characterization of Lignin by Syringyl to Guaiacyl

Ratio and Molecular Mass Determination
Frantiek Kak, Jaroslav urkovi and Danica Kakov
67
Structural Characterization and Thermal Properties of

Enzymatic Hydrolysis Lignins
Jia-Long Wen, Sheng Yang, Shao-Long Sun, Tong-Qi Yuan
and Run-Cang Sun
Fully Biodegradable Composites of Poly(butylene Succinate)/
Enzymatic Hydrolysis Lignin: Structure, Thermal and
Mechanical Properties
Linli Xu, Lingdie Meng, Min Wu,
Jiangxin Geng and Yong Huang
Physicochemical Properties and Potential Applications
of Lignins from Various Sources
Araceli Garca, Xabier Erdocia,
Mara Gonzlez Alriols and Jalel Labidi
91
111
127
vi
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
Chapter 12
Chapter 13
Chapter 14
Contents
Kraft Lignins from Spent Cooking Liquors:
Structural and Biotechnological Application
Carmen Fernndez-Costas, Susana Gouveia,
Mara ngeles Sanromn and Diego Moldes
161
Novel Developments on the Valorization of Lignin-Containing

Paper Mill By-Products for the Preparation of Porous Biopolymers
Herv Deleuze and Marc Birot
193
Kraft Lignin As an Adsorbent to Remove Heavy Metal

Ions from Water
Marina iban and Mirjana Brdar
231
Lignin-Based Thermoplastic Composites

and Compatibilization Methods
Lei Hu, Tatjana Stevanovic and Denis Rodrigue
253
Esterified Kraft Lignin: A Potential Coupling Agent

for Wood Plastic Composites (WPC)
Nicolas Mariotti, Tatjana Stevanovic,
Denis Rodrigue and Xiang-Ming Wang
283
Comparison of Physicochemical and Thermal Properties

of Esterified and Non-Esterified Kraft Lignins for
Biocomposite Application
Diane Schorr, Papa Niokhor Diouf
and Tatjana Stevanovic
309
The Pyrolysis Behavior of Lignins:

Contemporary Kinetics Overview
Bojan . Jankovi
329
Lignin Controls on Soil Ecosystem Services:

Implications for Biotechnological Advances in Biofuel Crops
Shamim Gul, Sandra F. Yanni and Joann K. Whalen
375
Index
417
PREFACE
As one of the major and crucial components of plant cell walls, the lignin polymer
constitutes about 15 to 25% of woody plants and is the second most abundant renewable
bioresource on the earth. Lignins produced on a large scale from the pulping industry are
mostly burned to recover chemicals and energy. With the increased interest in converting
lignocellulosic biomass to fuels or chemicals, even more lignins could be available, offering
considerable opportunity to use this abundant aromatic natural resource for production of
chemicals and materials. This book aims to provide updated knowledge and research results
on selected topics including analytical methods, structural characterization of lignin
preparations, and applications of lignins (such as in bio-absorbents, biocomposites, and soil
conditioners).
Advancements in science and technology relating to lignin applications relies on vital and
adequate information about lignins themselves, which requires versatile and sophisticated
analytical methods specifically for lignins. Many methods have been developed for lignin
characterization. The 1992 book, Methods in Lignin Chemistry, edited by S. Y. Lin and C. W.
Dence, summarized most of the available analytical methods relating to lignins at that time.
Significant advances in lignin analytical methods have been made since then. In particular,
advanced NMR techniques in multi-dimensional NMR experiments, as well as improvements
in heteronuclear NMR, and the availability of high magnetic field instrumentation with
sensitive cryoprobes, can all be applied to tremendously improve our knowledge of lignin
structure, as illustrated in the recent book, Lignin and Lignans: Advances in Chemistry, edited
by C. Heitner, D. R. Dimmel, and J. A. Schmidt. Meanwhile, traditional degradative methods
for lignin analysis still play an important role in lignin-related research and new alternative
methods continue to emerge providing new insights into lignin structure and the associated
biosynthetic pathways. The Derivatization Followed by Reductive Cleavage (DFRC) method,
developed in 1997, is one example of a recent analytical methods for lignin characterization
with many unique features. It has been use widely in lignin-related fields and has been briefly
reviewed in the past; Chapter 2 in this book now presents the most comprehensive account of
the DFRC method and its applications.
viii
Fachuang Lu
Lignins composition, functionality, purity, molecular weight and degree of cross-linking,

which are highly dependent upon the origins of lignin and the methods used to prepare it,
largely determine its physicochemical properties and impinge on the subsequent potential
applications. The ratio of syringyl/guaiacyl (S/G) units is commonly used to describe a
lignins composition and to predict its reactivity under various processing conditions, whereas
the molecular weight and molecular weight distribution of lignin are important characteristics
that affect lignins chemical and physical properties. Chapter 3 proposes accurate and reliable
methods for analysis of nitrobenzene oxidation products from lignin (for S/G ratio
determination) by high performance liquid chromatography and for measurement of lignin
molecular mass (and its distribution) by size-exclusion chromatography. Structural
characterization and thermal properties of lignins from enzymatic hydrolysis of
lignocellulosics, lignins potentially available at large scale from bioethanol production, are
given in Chapter 4. Utilization of enzymatic hydrolytic lignins for making biodegradable
composites is described in Chapter 5. In Chapter 6, a detailed evaluation is provided on
physicochemical properties of lignins from various sources and processing methods.
Currently the most available industrial lignin is the kraft lignin produced as a byproduct of the
kraft pulping process to produce chemical pulp from wood. Therefore conversion of kraft
lignin into various chemicals, materials and liquid fuels has been and still is the focus of
research related to utilization of natural polymers. In the past, significant effort has been
devoted to research and development in this area with limited success. However, increasing
social concerns on the depletion of fossil oil reserves, and the greenhouse effect caused by
burning fossil fuels, revives research and innovation activities relating to the use of renewable
and carbon-neutral resources including lignocellulosic biomass. Compared to carbohydrates,
lignin is structurally more complicated and difficult to utilize effectively. Although there are
some lignin-derived products made commercially, mostly from lignosulfonates and used as
dispersants, the great potential of lignins (especially kraft lignin and hydrolytic lignin) as
renewable feedstocks has not been realized.
This book by no means covers all aspects related to lignin applications; it provides brief
reviews on selected applications of lignin (Chapter 1, general; Chapter 13, bio-oils; Chapter
14, soil ecosystems) and recent research results on lignin applications in the areas of
environmental science (Chapters 8 and 9), agricultural biotechnology (Chapter 7), and
materials science (Chapters 10-12). Specifically, Chapter 1 briefly reviews commonly used
methods for detection, characterization, and quantification of lignin as well as various
applications of lignins; Chapter 7, deals with kraft lignin structure and its enzymatic
modification for applications as biocides, biocomposites, and biosorbents; Chapters 8 and 9
present unpublished results from recent studies on using kraft lignin or porous lignin products
to remove pollutants from water; Chapters 10-12 discuss physicochemical and thermal
properties of modified kraft lignin, and potential applications of esterified kraft lignin in
making biocomposites; Chapter 13 is related to pyrolysis of lignins to produce fuels and
chemicals; Chapter 14 reviews the role of lignin in soil ecosystem services. Overall, this book
is expected to serve as a textbook for students and a reference for scientists in the field of
lignin chemistry and applications.
Preface
ix
I sincerely thank the contributing authors for their effort in presenting the updated
knowledge and advances in their respective fields. Kindest thanks are also extended to my
colleagues John Grabber and Jane Marita from the USDA Dairy Forage Research Center,
Maggie Phillips, Steven Karlen, and Alden Voelker from DOE Great Lakes Bioenergy
Research Center, University of Wisconsin-Madison, for their reviewing and proof-reading.
My special thanks are given to John Ralph for his constructive discussion and suggestions.
Fachuang Lu
Department of Biochemistry and Great Lakes Bioenergy Research Center,
The Wisconsin Energy Institute, University of Wisconsin-Madison
1552 University Avenue, Madison, WI 53726, USA
Tel: (608) 890-2552
fachuanglu@wisc.edu
In: Lignin
Editor: Fachuang Lu
ISBN: 978-1-63117-452-0
2014 Nova Science Publishers, Inc.
Chapter 1
POLYVALENT LIGNIN:
RECENT APPROACHES IN DETERMINATION
AND APPLICATIONS
Wanderley Dantas dos Santos, Rogrio Marchiosi,
Flvia Carolina Moreira Vilar, Rogrio Barbosa Lima,
Anderson Ricardo Soares, ngela Valderrama Parizotto,
Dyoni Matias de Oliveira and Osvaldo Ferrarese-Filho*
Laboratory of Plant Biochemistry, Department of Biochemistry,
University of Maring, Av. Colombo, Maring, PR, Brazil
ABSTRACT
Due to its limited presence in the plant kingdom, lignin has been classified as a
secondary metabolite even though it is effectively the second-most abundant biopolymer
after cellulose. While absent in bryophytes (mosses, hornworts and liverworts), lignin is
an essential component in the cell walls of tracheophytes. Its mechanical resistance and
hydrophobicity marked a tipping point in the success of the plants in land environments
and, as a result, the success of the whole continental ecosystem (including humans). The
mechanical strength of lignin is also the responsible for the rigidity required for largersized trees from which our ancestors built weapons, tools, boats and shelters. Even today,
lignocellulose is a universal raw material for construction, furniture and metallurgic
industries, as well as energy production. Furthermore, lignin is a component of plant
defense systems against biological attacks, and an important target of study for areas such
as livestock, forage digestibility and production of cellulosic ethanol. Lignin also hinders
the production of paper and cellulose, which has been traditionally addressed by using
chemical approaches. However, this model is not applicable to bioethanol production and
is important because the emergent bioenergy industry must be economically and
energetically sustainable. Lignin is a central question in any application involving plant
biomass. This chapter reviews the more common methods for detection, characterization
Corresponding Author address: Email: osferrarese@gmail.com.
W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

and quantification of lignin as well as biological and industrial applications of this
important polymer.
Keywords: Lignification, lignin detection, lignin characterization, lignin quantification,

lignin application
INTRODUCTION
About 430 million years ago, plants started their challenging journey for conquest of the
continents. This conquest of land remained limited to wet regions until the emergence of
tracheas and fibers capable of transporting water to the upper parts of more robust plants.
Such anatomical adaptations became possible only after the appearance of lignin, a polymer
of phenolic compounds that confers strength to vascular tissues used for water transport [1].
These communities of herbs and trees in forest ecosystems provided a rich and stable
environment for heterotrophic evolution, which included primates and hominids. Our
ancestors and cousins have been using wood for tools and firewood since the middle of the
Pleistocene, about one million years ago [2, 3]. Fire was one of the first human experiences
using non-human energy, a mark of the civilization. Fire offered protection and increased the
diversity and nutritional power of foods, which seems to have been fundamental to the spread
of man out of Africa [4].
Based on the importance of plant biomass for building, clothing, tools, fire, livestock and
agriculture in human history it would be absurd not to consider lignocellulosic biomass as the
most important source of energy and crude matter for early civilizations. However, since the
industrial revolution, fossil fuels, steel and concrete have replaced biomass as a primary
source of energy and raw material.
Oil and coal have become the primary sources of energy because of their ready
abundance and versatility [5] though the Era of Oil is likely coming to an end. In 1956, M.
King Hubbert, chief geology consultant for Shell Co. accurately foresaw a peak in the
production rate of conventional crude oil in USA which would occur in less than 20 years [6].
The precision of Hubberts calculation might arguably be an exception when compared with
the oil curves from other regions and may not be accurate in predicting all possible
technological improvements in surveying and exploring new sources of unconventional oil
such as shale, bituminous sand and deep water [7, 8]. However, even considering
technological advances, there is an inescapable truth in Hubberts logic: oil is a finite resource
and there is increasing evidence that we are living during a plateau in oil production with a
low probability of recovery [9]. Moreover, the release of CO2 from the burning of fossil fuels
threatens to unbalance the environment in ways which may be more dangerous to the world
economy than the decrease in oil production itself [10].
Petroleum will not be able to sustain our level of growth forever. At this time, nuclear
energy is also incapable of substituting for oil in meeting our current energy requirements, in
addition to being a non-renewable energy source [11]. Thus, a massive investment in new
pathways to convert solar energy into useful fuels and crude materials is the last chance to
sustain civilization. Plant-derived fuels such as ethanol and biodiesel are renewable resources
having a high potential for replacing fossil fuels [11, 12]. Currently, the main sources of
biofuels are: 1) ethanol produced by fermentation of soluble sugars such as sucrose and
Polyvalent Lignin
hydrolyzed starch, and 2) biodiesel produced from the transesterification of plant oil.
Scientific and technological developments have been devoted to creating a second generation
of liquid biofuels from lignocellulose. The main focus is upon the hydrolysis of cellulose, a
major component of plant residues, which is the simplest to ferment as it is composed
exclusively of glucose residues. Other polysaccharides such as hemicelluloses and pectins,
are rich in sugars that cannot be fermented by Saccharomyces cerevisiae (common
fermenter), although they can be fermented by other yeast strains or genetically modified
organisms [11].
Lignin comprises the third part of lignocellulose. Recalcitrant to conventional conversion,
lignin is a rich source of energy and its conversion to liquid fuels can be accomplished by
thermochemical methods [13]. However, lignin confers resistance to enzymatic digestion of
polysaccharides and must be chemically removed to improve the saccharification.
Alternatively, highly lignified tissues can be separated for lignin extraction, while lesslignified tissues can be used to saccharification. Apart from a source of energy, lignin has
been explored as a versatile crude material for a wide range of applications, which can serve
to reduce the costs of cellulosic ethanol. This chapter describes the most frequently applied
methods for detection, characterization and quantification of lignin as well as biological and
industrial applications.
LIGNIN COMPOSITION
In tracheophytes, up to 40% of photosynthetic energy is devoted to lignin synthesis
indicating the importance of lignin to plants and the carbon cycle. Overall, plant fibers
contain ~45% carbon, 6% hydrogen and 49% oxygen while lignin is composed of ~65%
carbon, 6% hydrogen and 29% oxygen. This distribution reveals the reduced state of lignin
carbons, which reflects on its high calorific content.
Lignin is formed by free radical polymerization of mainly three hydroxycinnamic
alcohols, which vary in their degree of methoxylation [14], in addition to a diverse set of
other minor components. These three precursors or monolignols are p-coumaryl, coniferyl
and sinapyl alcohols. After polymerization, these monolignols are converted to structural
units called p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units respectively (Figure 1).
The proportion of each lignin monomer (or unit) can vary throughout the cell wall layers as
well as cell wall types, growth stages and plant species. For example, lignins from ferns and
straws have less than 10% methoxyl groups, and those from grass culms such as bamboo,
sugarcane and coniferous wood, have 14 to 16% methoxyl groups, while lignins from
hardwoods contain up to 23% methoxyl groups.
The content of lignin in wood also varies widely, softwoods containing 25 to 50% lignin
and hardwoods containing 20 to 25%. Due to its complexity and heterogeneity in plants and
tissues, it is very difficult to accurately measure the lignin content in different materials [15].
Moreover, the numerous linkages between the monomers and other cell wall components
makes extraction of lignin a clear challenge which, in turn, is crucial for accurate
quantification.
Figure 1. A simplified scheme for the synthesis of lignin. PAL, phenylalanine ammonia-lyase; C4H,
cinnamate 4-hydroxylase; 4CL, 4-coumarate:CoA ligase; HCT, p-hydroxycinnamoylCoA:shikimate/quinate p-hydroxycinnamoyl transferase; C3H, p-coumarate 3-hydroxylase;
CCoAOMT, caffeoyl-CoA 3omethyltransferase; CCR, cinnamoyl-CoA reductase; CAD, cinnamyl
alcohol dehydrogenase; F5H, ferulate 5-hydroxylase; COMT, caffeic acid 3omethyltransferase; POD,
peroxidase. H, p-hydroxyphenyl; G, guaiacyl; S, syringyl.
LIGNIN ANALYSES
Lignin analyses can be divided into three main and distinct groups: detection,
characterization and quantification. Figure 2 summarizes the three groups as well as the most
current methods used for these purposes.
Detection Methods
Lignin detection aims to determine the presence or absence of this heteropolymer and
also the abundance of structural units in a given sample. Two widely used methods are the
Wiesner and Male reactions.
Polyvalent Lignin
Figure 2. Current methods for detection, characterization and quantification of lignin.
Wiesner Reaction
Phloroglucinol has been widely used by botanists to detect lignin in plant tissues and a
solution of phloroglucinol in strong hydrochloric acid is known as Wiesner reagent. In this
reaction, p-hydroxycinnamaldehyde end groups condense with phloroglucinol-HCl to give a
characteristic visible color which can vary from red to yellow (Figure 3). Reactions with
syringaldehyde, coniferaldehyde and coniferyl and sinapyl alcohols yield red chromophores
while vanillin, p-hydroxybenzaldehyde and anisaldehyde produce yellow chromophores [16].
Although the Wiesner reagent is only sensitive for one specific kind of lignin component, this
procedure is still often used to detect lignin in plant cell walls [17].
Figure 3. The Wiesner reaction.
Male Reaction
In the Male reaction, a sequential treatment with potassium permanganate, HCl and
ammonium hydroxide gives colors that vary from black to beige [18]. Potassium
permanganate-HCl converts the guaiacyl (G) and syringyl (S) units into catechol and
methoxycatechol, respectively while the concentrated ammonium hydroxide reacts with the
catechols, generating the respective o-quinones (Figure 4). The brown color generated from
gymnosperms is due to the presence of the G monomer in the lignin, while in angiosperms,
the S unit gives a red color [16].
Histochemical stains have been widely used for lignin detection, however the results
require careful analysis due to potential interference from non-lignin compounds or staining
reaction errors [19].
Figure 4. The Male reaction.
Ultraviolet Spectroscopy
In addition to the Wiesner and Male reactions, another method used for lignin detection
involves ultraviolet (UV) spectroscopy, which is a simple and easy method to detect it. The
ability of lignin to absorb light in the UV region comes from the high conjugation degree of
the aromatic nucleus, while hydroxyl and ether groups contribute significantly to maximum
absorption around 280 nm (Figure 5). However, it is necessary to note that spectral absorption
is sample dependent as lignin structure and composition differ between plants and tissues
[20].
Figure 5. The ultraviolet (UV) spectrum of 500 L mL-1 lignin obtained from sugarcane bagasse.
Polyvalent Lignin
Characterization Methods
Lignin characterization is difficult because it is not possible to isolate intact lignin
polymer. Lignin is highly hydrophobic and is not extracted from plant tissues by either
aqueous or organic solvents [21]. The characterization of lignin identifies the monolignol, the
types of linkages between monomers and the cell wall components.
Analyses for lignin characterization are grouped into degradative or non-degradative
procedures (Figure 2). Cupric oxide (CuO) oxidation, nitrobenzene oxidation, thioacidolysis,
derivatization followed by reductive cleavage (DFRC method), and Pyrolysis-Gas
Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) are degradative techniques. Fourier
Transform Infrared Spectrometry (FT-IR), Fourier Transform Raman Spectroscopy (FTRaman), and Nuclear Magnetic Resonance (NMR) are non-degradative procedures.
Degradative Techniques
CuO Oxidation
In this procedure, lignin is oxidized in an alkaline cupric oxide (CuO) solution [22].
Degradation of lignin releases p-hydroxybenzaldehyde from p-hydroxyphenyl (H), vanillin
from guaiacyl (G) and syringaldehyde from syringyl (S). The products of CuO oxidation are
easy separated and quantified by high-performance liquid chromatography (HPLC) at 290 nm
using the corresponding standards (Figure 6). Yields vary from 25 to 35% total lignin,
depending upon the plant material.
Figure 6. HPLC chromatogram of phydroxybenzaldehyde (H), vanillin (G) and syringaldehyde (S)
standards.
Nitrobenzene Oxidation
Under similar alkaline reaction conditions, lignin is oxidized with a nitrobenzene solution
which releases the same kinds of phenolic aldehydes (p-hydroxybenzaldehyde, vanillin and
syringaldehyde) in similar proportions and yields as for CuO oxidation. HPLC is used to
separate and quantify these products (Figure 6).
The reaction with nitrobenzene is more aggressive than CuO oxidation and by-products
can be produced, though both methods have limitations. Cleavage of the alkyl side chains
does not allow for analysis of the interunit linkages of lignin. In addition, the release of
phenolic aldehydes from materials other than lignin moieties (p-coumaric and ferulic acids,
for example) can affect the accurate determination of lignin monomer composition [16].
Thioacidolysis
The thioacidolysis degradation procedure is widely used because it cleaves various
linkages in lignin. This method also provides information about lignin constituents, though
monomeric and dimeric products can be observed. The condensed dimers are released by
cleavage of alkylaryl ether bonds in lignin. In this procedure, the sample is treated with boron
trifluoride etherate in combination with dioxanethanethiol at high temperature. The
monomers can be analyzed by gas chromatography after silylation while dimeric products can
be analyzed after removal of sulfur substituents by Raney-nickel reduction [23]. The yield of
thioacidolysis degradation can reach 50% total lignin, depending upon the plant material.
DFRC Method
In general, the three techniques described earlier are used to estimate the phydroxyphenyl (H), guaiacyl (G) and syringyl (S) ratios, which are important to evaluate the
lignin monomer composition in different plant materials.
The most frequent interunit linkages in lignin are arylglycerol--aryl ethers (Figure 7)
and arylglycerol--aryl ethers [24]. Derivatization followed by reductive cleavage (DFRC
method) is based on two highly selective reactions able cleave the ,-ether bonds to produce
acetylated lignin monomers [25, 26]. In general, the method provides data similar to those
from thioacidolysis degradative technique. The yield of DFRC degradation can reach 97% for
models and about 30% for lignins. It is a simple, selective and powerful method to provide
detailed information about lignin structure and its monomeric composition [25-27]. A
comprehensive review about this method and its applications is included in chapter 2 of this
book.
Figure 7. Arylglycerol--aryl ether: the main interunit linkage in lignin.
Polyvalent Lignin
Pyrolysis-GC/MS
For pyrolysis gas chromatography/mass spectrometry (Pyrolysis-GC/MS), lignin is
rapidly heated in the absence of oxygen and volatile products separated by GC and
subsequently identified by MS [16]. This procedure requires a small amount of sample, is
highly sensitive in addition to being simple and rapid since the lignin does not need to be
isolated [28]. However, it releases only 20% of the total lignin, which makes this procedure
disadvantageous for lignin quantitation.
Non-Degradative Techniques
Fourier Transform Infrared Spectrometry (FT-IR)
This technique is used to obtain an infrared absorption spectrum of a material (solid,
liquid or gas), relies on the absorption of energy from an illuminating laser and collects
spectral data in a wide spectral range. FT-IR identifies different linkages in a complex sample
due to the atomic interactions with electromagnetic radiation in a process of molecular
vibration and is appropriate for a rapid characterization of lignin in situ. Among other
advantages of the FT-IR method are high sensitivity and need for small amounts (nanograms)
of dried sample [29].
Fourier Transform Raman Spectroscopy (FT-Raman)
Raman spectroscopy also relies on molecular vibration spectra and is complementary to
FT-IR for lignin analysis. In this procedure, it is possible to detect weak bonds and linkages
by FT-IR in addition to information about bond types in a complex sample [30]. Similar to
the FT-IR technique, FT-Raman identifies sample amounts in the range of nanograms and is
capable of analyzing lignin from individual plant cell walls. More recently, other Ramanbased analyses have been developed such as Micro Raman, Raman Imaging, Resonance and
Preresonance Raman and Surface Enhanced Raman, which provide more information about
sample structure with potential applications to lignocellulosic investigations [16].
Nuclear Magnetic Resonance (NMR)
Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful tool used for lignin
analysis, especially for providing detailed information on polymer structure. In NMR, the
sample is placed in a strong static magnetic field and excited by radiofrequency pulses.
Active nuclei such as 1H, 13C or 31P, resonate at a specific frequency providing a spectrum
which describes the neighborhood of the nucleus in addition to atom arrangements, allowing
the chemical structure and molecular conformation to be resolved.
Through the years, NMR analyses have evolved from simple hydrogen NMR to 3D NMR
and, more recently, solid-state NMR which does not require lignin isolation from other cell
wall components.
Although the technique yields valuable information about monomer composition and
bond types in the lignin molecule, NMR spectroscopy is not suitable for lignin quantification
due to overlapping signals that appear on the final NMR spectrum [31].
10
Quantification Methods
Lignin quantification is a basic procedure applied in almost all areas of research and by
business companies where the main raw material is lignocellulosic. However, the
quantification of this polymer is difficult, not only because of lignins varying monomeric
composition, but also its covalently linkage to cell wall carbohydrates, proteins, phenolics and
other compounds [21]. Over time, several methods have been developed and improved to
quantify lignin in various plant tissues [32], and although widely used, no consensus exists on
which method best represents the real amount of lignin in a sample [16, 32, 33].
Methods of lignin quantification can be divided into two groups: gravimetric and
spectrophotometric. Gravimetric methods are based on the separation of lignin followed by
weighing while spectrophotometric methods involve the exclusion of possible interfering
compounds, solubilization and determination of lignin by light absorbance. The main
gravimetric methods are 1) Klason, 2) acid detergent and 3) potassium permanganate
oxidation. The main spectrophotometric methods are 1) thioglycolic acid and 2) acetyl
bromide.
Gravimetric Methods
Klason
Klason is the oldest and most common method used for lignin quantification. It is based
on partial digestion of the sample in 72% sulfuric acid, where the cell wall polysaccharides
are dissolved leaving lignin (also called Klason lignin) as the unique insoluble residue [34].
The acid hydrolysis is separated in two phases. The first consists in the treatment of the
biomass with 72% H2SO4 at room temperature. In the second stage, distilled water is added to
dilute the solution to approximately 3% H2SO4 followed by heating at 120C until complete
hydrolysis. Initially developed for gymnosperms species, the Klason method is the global
standard method in the pulp and paper industries.
The advantages of this method are reproducibility (if standard conditions are strictly
followed), simple and easy to handle equipment, and low cost. However, the technique has
serious limitations arising from the presence of interfering compounds not belonging to lignin
such as ash, phenol aldehyde polymers, tannins, Maillard polymers, cutin, waxes and protein
can result in the overestimation of Klason lignin [35]. When applied to herbaceous samples,
the Klason method seems to be most negatively affected by the high protein content and
concentrations of cutin and waxes which are usually present in the leaves of forage plant [32].
It is also important to note that a fraction of lignin, especially from hardwood samples, is
soluble in sulfuric acid and must be estimated by UV spectrophotometry [22].
Acid Detergent Lignin
The acid detergent lignin method developed by Van Soest [36] is widely used in animal
and agricultural studies for analysis of protein-rich forage samples in an attempt to minimize
errors found with the Klason method. In this procedure, crude sample is initially treated with
an acid detergent solution such as acetyl trimethylammonium bromide, to form acid detergent
fibers which are then treated with 72% acid sulfuric, forming an insoluble residue called acid
Polyvalent Lignin
11
detergent lignin [35]. Although the acid detergent lignin method removes part of the protein
content and other interfering substances, lignin is partially solubilized by the acid detergent
solution leading to an underestimation of the total lignin content [37]. In tropical grasses, the
loss rate of soluble lignin can reach 50% and also values from 2 to 4 times lower were found
when compared the acid detergent lignin to the Klason method [38, 39]. These results suggest
that Klason is better than the acid detergent lignin method for grasses, although the lower loss
of lignin with this method depends of the type of material and cell wall preparation [40, 41].
Potassium Permanganate
The potassium permanganate method is used to obtain the Kappa number, which
indicates the residual lignin content or bleachability of wood pulp [42]. In this procedure, the
lignin concentration is expressed as the amount of oxidant per unit weight of pulp, and the
results can be converted to Klason lignin using conversion factors [22]. Since there is a direct
correlation between Kappa number and Klason lignin content, this method is traditionally
used by the pulp and paper industry. The potassium permanganate method was originally
developed by Van Soest and Wine [43] to quantify lignin in forage and herbaceous samples,
and applied in animal nutritional science to correlate lignin content with digestibility [33]. It
deals with acid detergent sample preparations to obtain the acid detergent fiber which is
oxidized by the potassium permanganate solution. After oxidation, the insoluble residue is
washed, dried, weighed and the lignin content calculated as the loss in weigh from the initial
acid detergent fiber. The potassium permanganate method is an alternative to the sulfuric acid
method. It has some advantages such as the possibility to determine cellulose content at the
same sample, and it is a fast method which employs less corrosive chemical compared to the
sulphuric method [43]. Nevertheless, the permanganate solution can oxidize phenolic and
unsaturated compounds (e.g., tannins, pigments, proteins) which are not removed by the acid
detergent preparation step, and may lead to an overestimation of the final lignin content [33].
Spectrophotometric Methods
Thioglycolic Acid
Once solubilized, lignin can be spectrophotometrically measured [34]. Thioglycolic acid
is able to acid-displace covalent bonds between lignin and cell wall components leading to
formation of thioether benzyl alcohol groups, also known as lignothioglycolic acid (LTGA)
(Figure 8). After the reaction with thioglycolic acid, the LTGA is extracted from the cell wall
with a NaOH solution, precipitated by the addition of concentrated HCl and subsequently
dried at 60oC. The LTGA complex is soluble in alkali solution and absorbs at 280 nm. This
procedure was initially developed for wood samples, but has been employed to isolate and
quantify lignin in plant species such as Glycine max, Nicotina tabacum and Oriza sativa [4448]. The authors report that this method excludes phenolic compounds that do not belong to
the lignin polymer and also eliminates interference from polysaccharides. However,
thioglycolic acid reacts specifically with the ether bonds of lignin, which links monomers
through their propanoid moieties. Because of this, the thioglycolic acid method can
underestimate the real content of lignin. Furthermore, the formation of soluble lignin that
remains in the acid solution is a source of discrepancy [32].
12
Figure 8. The thioglycolic acid reaction (adapted from Hatfield and Fukushima, 2005).
Acetyl Bromide
The acetyl bromide method also relies on lignin solubilization and spectrophotometric
determination, but unlike the thioglycolic acid procedure, reaction with 25% acetyl
bromide/acetic acid solution for 30 min both extracts and solubilizes lignins, which makes
this a rapid technique and with less probability of experimental errors. By this method, acetyl
derivatives of unsubstituted OH groups within the lignin polymer and the bromide
replacement of -carbon OH groups produce acetylate/brominated lignin that is soluble in
acetic acid (Figure 9). The acetyl bromide method is more appropriate for small samples; the
formation of non-lignin products is low and this technique has been assumed to yield precise
absorbance values, which reflect the real lignin content [49]. Notwithstanding, questions
about its accuracy have been raised with respect to the complete solubilization of lignin in the
acetyl bromide/acetic acid solution, as well as polysaccharide degradation to furfurals, which
can potentially interfere with the lignin value [50, 51]. Lignin solubilization in the acetyl
bromide solution seems to be suitable to lignin quantification and does not require addition of
any further chemical, as speculated for the perchloric acid, in an attempt to improve cell wall
degradation [51]. However, spontaneous carbohydrate degradation can occur during the
procedure and, in an effort to minimize interference, proposed adjustments include lowering
the temperature to 50C and increasing the reaction time to 2 h [51].
The formation of furfurals can differ between samples and changes in temperature, and
reaction time may not be necessary depending on lignin content of the sample. In order to
address this problem, our research group evaluated the accuracy of the most commonly used
methods for lignin determination comparing/contrasting the amount and quality of lignin (S:G
ratio) as well as the amount and quality of polysaccharides [15]. After finding widely variable
amounts in lignin content measured by the different methods, the potential causes of the
discrepancies among methods were investigated. The data indicated that the Klason method
underestimated the lignin content in lignin-poor tissues, the thioglycolic method
underestimated lignin content due to an incomplete extraction and loss of solubilized lignin
throughout the process of extraction while the acetyl bromide method provided a reproducible
Polyvalent Lignin
13
determination of lignin in all tissues. The acetyl bromide method used in the experiments
followed the same conditions of temperature (70C) and reaction time (30 min) reported in
the 1972 paper that introduced this technique for the scientific community. The production of
furfurals was proportional to the amount of polysaccharides (inversely proportional to lignin
content), but their interference was significant only in tissues with less than 15% lignin. When
compared to other methods, the practicality and reliability of the acetyl bromide method
indicates it is the preferred method for lignin quantification [15].
Figure 9. The acetyl bromide reaction (adapted from Hatfield and Fukushima, 2005).
LIGNIN APPLICATIONS
Approximately one million tons of lignin are generated from pulping and papermaking
processes every year, but only 1-2% is used in specialty products [52]. This is because lignin
is considered a waste product and is mainly used as a fuel for pulping boilers or in the
conversion of biomass to ethanol, where the lignin is used as a fuel source for driving the
fermentation process [53]. The pulping process itself may change the properties of the lignin
obtained. The pulping processes utilized most frequently to obtain lignin from biomass are the
sulfite and Kraft methods [54]. Kraft lignin accounts for about 89% of the production of
chemical pulps, is obtained by pulping in an alkaline medium and is insoluble in water [55].
The sulfite process produces sulfonated lignins which are soluble in water containing suitable
counter ion (Na+, Ca2+, Mg2+ etc) due the presence of a sulfonic acid linked to the backbone
of lignin. Currently, a new class of sulfur-free lignins can be obtained by solvent
pulping/organosolv processes and soda pulping of agricultural crop residues [52]. Sulfur-free
lignins are water insoluble at neutral or acidic pH, but soluble in alkaline solutions or organic
solvents. Figure 10 shows the most common biological and industrial applications of lignin.
14
Figure 10. The most common biological and industrial applications of lignin.
Biological Applications of Lignin

The increased global demand for food requires greater efficiency in agriculture, which
has resulted in the extensive use of agrochemicals to control pests such as insects, fungi and
weeds. However, 90% of herbicides applied to control an infestation will not reach the target,
but they will contaminate air, water and foods [52] affecting the human health and
environment [53]. Furthermore, the efficiency of pesticides is associated with the applied
concentrations and contact times with the pest. If the pesticide is rapidly degraded when
exposed to environmental conditions, its effectiveness is also drastically reduced.
The utilization of controlled release formulations (CRFs) of pesticides emerged as an
attempt to resolve the problems of environmental pollution and loss of activity. The CRFs
allow the release of pesticides at a given rate and maintain the concentration within optimal
limits for a given period of time. When developing CRFs, the material utilized for pesticide
encapsulation should be degradable by microbial decomposers or by environmental factors
such as light, water, heat, oxidation, wind and rain. The materials most widely utilized for the
encapsulation of pesticides are natural polymers (starch, ethyl cellulose, lignin and alginate)
which are preferred to synthetic polymers due to their low cost and biodegradability. They are
classified according to the degree of biodegradation: 1) starch and systems based on amylose;
2) other polysaccharides; 3) proteins; 4) rubber and waxes; 5) synthetic polymers; 6)
miscellaneous lignins, resins and biopolymers modified by substitution [56].
Among these matrices, cellulose and lignin, which are the most abundant. Lignin
degrades more slowly than polysaccharides. Because of this, Kraft lignin has been used for
encapsulation of a large number of pesticides (2,4-D [57], bromacil [58], diuron [59], and
fluometuron [60]), particularly those with high mobility in soil and those which are
considered groundwater pollutants (chloridazon and metribuzin) [61].
Polyvalent Lignin
15
Of the available methods for producing lignin-based CRFs, the formation of a solid
matrix is the simplest and most advantageous [55]. Certain pesticides have the ability to
dissolve Kraft lignin when heated to the melting point, though if dissolution is not possible, a
melting agent (glycerol) is added. After cooling, a matrix is formed from which the pesticide
is slowly released by diffusion. In the other methods, the active ingredient is bonded to lignin
or retained in materials modified by cross-linking. Therefore, there are two possible
mechanisms for releasing pesticides in formulations based on lignin: 1) diffusion of the active
ingredients through the matrix, and 2) hydrolysis of ester bonds formed between the phenolic
groups in the lignin and carboxyl groups of the active ingredient during the formulation
process [58]. The first mechanism applies to the diuron (from commercially available pine
Kraft lignin) [59] and both mechanisms can be found in lignin based CRF for 2,4-D[57].
In a recent study, chlordazon and metribuzin (herbicides) were incorporated into granules
of different sizes composed of pine Kraft lignin and the release kinetics in water and soil
mobility were evaluated [61]. The CRF granules were produced by mixing each herbicide
with pine Kraft lignin at a 1:1 ratio (w:w) under melting conditions and the resulting matrix
are triturated and sieved to obtain granules of different sizes (0.5 to 3.0 mm). The CRF
granules reduced the release rate of both herbicides in water compared to conventional
formulations and a reduction in the quantity of herbicides in soil leachates was also observed,
demonstrating that the utilization of CRFs might reduce environmental pollution caused by
these herbicides. Release rate was found to be dependent on granule size, with the larger
granules releasing at lower rates. Very similar results were obtained for the encapsulation of
Isoproturon, Imidacloprid and Cyromazine (all systemic pesticides) with pine Kraft lignin
[62]. Additives are often added to CRFs because they improve the physical properties of the
formulations and affect the kinetics of release. For example, the addition of urea to CRFs
allows the use of a minimum amount of pesticide due to the solvation of lignin. Furthermore,
urea is an inexpensive and environmentally safe soil fertilizer. The addition of urea increased
the release of Diuron from pine Kraft lignin matrix [59] due to the formation of pores
resulting from the rapid dissolution of urea.
Lignin, besides being an anti-oxidant compound and good sorbent for pesticides, also
absorbs UV light. This feature is the basis for the enhancement of biological pest control used
as an alternative to chemical control. The use of natural pathogens for insect control dates to
1839, when V. Audouin reported the case of a sericulturist that noted the death of defoliant
larvae days after discarding silkworms infected with fungus in the vicinity of infested trees
[63]. Granuloviruses and nucleopolyhedrovirus constitute a large group of viruses that
included the major pathogens for a variety of insects and have been used in developing of
microbial pesticides. Although they are less harmful to the environment than chemical
pesticides and suitable for integrated pest management, their very sensitivity to UV light
(280-320 nm) limits the development of commercially viable microbial pesticides. In one
study, it was found that granuloviruses encapsulated with sodium lignin were more stable in
sunlight during field tests conducted on infested apple trees [64]. Therefore, a lignin-based
matrix can provide protection from UV light for some types of virus used to control
agricultural pests. Although lignin-based formulations have been effective only with high
virus dosages, virus encapsulation appears to be an alternative to frequent virus reapplications
due to short residual activity.
16
Industrial Applications of Lignin

Utilization of Lignin in the Production of Carbon Fiber
Carbon fibers have been used as reinforcing materials since the 1950s. The carbon fibers
are synthesized by a carbonization process, where a precursor fiber is thermally treated. The
high stiffness, high tensile strength, high modulus, and low weight of carbon fibers makes
them ideal for use in sports equipment, construction, aircraft and the automotive industry
[65]. Indeed, the use of carbon fibers in the automotive industry has reduced the weight of
vehicles with a consequent reduction in fuel consumption and CO2 emission [66]. On the
other hand, carbon fibers are produced from polyacrylonitrile (PAN), petroleum and coal
based materials and rayon. The high cost of raw materials associated with the high cost of
production, makes carbon fibers a very expensive material (20 times more expensive than
steel) which limits wide use in automotive industry. Furthermore, some of these are
nonrenewable materials. Nevertheless, approximately 50,000 tons of carbon fibers are used
annually world-wide [67] and new cheaper and renewable precursors that can replace
petroleum are desirable.
A high-volume of lignin is obtained from paper production that, besides being
underutilized, is a low-cost renewable material. In order to reduce the production cost for
carbon fibers, researchers have incorporated lignin into these fibers. Kayacarbon (Nippon
Kayaku Co in Japan) was the first lignin-based carbon fiber manufactured and the only one
commercially available. Kayacarbon fibers were produced from lignosulfonate with polyvinyl
alcohol added as a plasticizer, however, the low quality of these fibers led to discontinuation
of its manufacture. More recently, some specifications required for the use of lignin as a
precursor for carbon fiber manufacture were recognized in a study at the Oak Ridge National
Laboratory [68]. Considering the abundance of lignin in nature and the increase in lignin
production as a residue of the emergent cellulosic ethanol industry, lignin might be the key to
overcome the cost-limiting factors of carbon fibers.
Utilization of Lignin in Plastics
Plastics (from Greek plastikos meaning able to be molded in different forms) are
primarily thermoplastic or thermosetting synthetic organic polymers derived from petroleum
that can be used to produce a wide variety of objects [69]. Although plastics, especially
polyolefins, have desirable properties such as low cost and durability, they are not easily
degraded by biotic and abiotic factors. This is due to their barrier properties (that prevent the
attack by enzymes secreted from microorganisms) and high molecular weights (which limits
entry into the cells of microorganisms for degradation by intracellular enzymes) [70].
Furthermore, as plastics were recently created by man, evolution has not had sufficient time
to select for enzymes capable of degrading them [71].
In this context, the incorporation of lignin into plastics in order to increase their
biodegradability has shown good results. The Jack pine Kraft lignin obtained from black
liquor by precipitation with acid was used for the first time to produce 85% Kraft lignin-based
plastic containing 12.6% 90,000 molecular weight polyvinyl acetate, 1.6% diethyleneglycol
dibenzoate and 0.8% indene [72]. The results show that Kraft lignin-based thermoplastics
have high tensile strength that varies linearly with the molecular weight. The results also
Polyvalent Lignin
17
suggest that Kraft lignin-based plastics can be extrusion-molded, as determined by melt-flow

index measurements.
An interesting study was conducted in order to produce a plastic/moldable lignin without
the need for synthetic resins [73]. For this, softwood Kraft lignin (Indulin AT, Mead
Westvaco) was modified by reaction with benzyl chloride and the benzylated lignin was
injection-molded into bars and discs at 180C. The results showed that the benzylated lignin
had similar properties to common plastics and wood-plastic composites.
Utilization of Lignin in Phenolic Resins

Phenolic resins are derived from the reaction of formaldehyde and phenol, wherein water
is produced as a by-product [74]. Phenol is conventionally synthesized from benzene and
propylene [75], in a three-step procedure named the cumene-based co-product acetone
process [53]. Phenolic resins are widely used in the construction of oriented strand-board,
furniture coatings (Formica), manufacture of pulleys, cable pans, and friction products such
as automotive brake pads. However, phenolic resin components are derived from
petrochemicals, nonrenewable materials that could be replaced by lignin (which contains
large amounts of phenolic groups) for the production of alternative environmentally-friendly
materials.
In a study, methanol-soluble lignin extracted from soda-lignin (Harima Chemicals) was
incorporated into phenolic resins used in the manufacture of brake friction materials [76].
Phenolic resins containing 25-75% lignin (w:w) were produced by polymer blend methods
(solvent blend and in situ polymerization). Results showed that the incorporation of lignin
improved the fade resistance, as the products of lignin degradation did not become liquid on
the friction surface since they were cross-linked by the heat of friction.
In another report, residues rich in activated lignin obtained from lignocellulosic ethanol
production (ER) were utilized at 10 to 70% to replace phenol in the production of ligninphenol-formaldehyde (LPF) adhesive [77]. The LPF adhesives were prepared by mixing and
heating lignin, phenol and formaldehyde for 1 h at 80C and (among other parameters) the
amount of free phenol, free formaldehyde and bonding strength were evaluated. The results
showed that increased substitution reduced the free phenol, increased the free formaldehyde
and reduced bonding strength in LPF adhesives, especially at 70% lignocellulosic ethanol
residues. The incorporation of lignin into phenolic resins can be economically feasible,
considering that approximately 30.6% of the global phenol production, an estimated $107
billion, is used in the synthesis of such materials [53].
Utilization of Lignin in Epoxy Resins
The most widely used epoxy resins are diglycidyl ethers of bisphenol-A obtained through
the reaction of bisphenol A with epichlorohydrin [78]. Currently, these resins are used in
fiberglass and carbon fiber materials, buildings (industrial floor coatings and concrete crack
repair), the inner lining of beer and soft drink containers, and in the making of costume
jewelry and prototypes (models and molds). The presence of hydroxyl groups in the lignin
structure allow for its use in replacing the bisphenol-A in the synthesis of epoxy resins, in
addition to providing greater stiffness and better thermal properties to the resin [79]. Indeed,
significant amounts of lignin (<50% w:w) have been incorporated into epoxy resins without
affecting their electrical and mechanical properties [53]. In this context, the incorporation of
lignin into printed wiring boards (PWB) by IBM researchers is an interesting technological
18
innovation. The incorporation of lignin (obtained from Kraft pulping mills in the United
States and Europe or organosolv pilot-scale pulping mill in Canada) into PWB reduced the
total energy required for production by 40%, without modifying physical and electrical
properties. The incorporation of lignin into PWB may also have an important environmental
role. Epoxy resins are synthesized from petroleum derivatives which, besides being
unrecyclable, when incinerated contribute to the increase in the atmospheric CO2, and
consequently to global warming. As raw material, the use of lignin reduces the demand for
petroleum derivatives and the environmental impact associated to incineration. The total
energy requirement for production of PWB includes its process, transport and material
resource. The main energy sources used are natural gas, petroleum, coal, and non-fossil fuels
(electricity and wood energy used in the pulp and paper industry). During the production of
organosolv lignin/epoxy and kraft lignin/epoxy resins the requirement for non-fossil energy
increased from 0.7 to 1.24 and 2.33 GJ per 100 Kg of solids resins, respectively. On the other
hand, the total fossil energy requirement decreased from 17.1 to 10.6 and 9.76 GJ during the
production of the Kraft lignin/epoxy and organosolv lignin/epoxy resins, respectively [77].
Utilization of Lignin in Polyurethane Foams

Polyurethanes are produced by the reaction of an isocyanate (di or polyfunctional) with a
polyol (such as polyethylene adipate) in the presence of other reagents such as catalysts, chain
extenders, blowing agents, and surfactants. Polyurethane foams are utilized in the
manufacture of mattresses, upholstery, car seats, dashboards, bumpers, shoes, and insulation
for refrigerators, freezers, and refrigerated trucks. Due to the phenolic structure of lignin, it
can be used to replace the polyols used in the manufacture of polyurethanes. Hardwood
organosolv ethanol lignin (HEL) (Lignol Innovation, Vancouver, Canada) and hardwood
Kraft lignin (HKL), prepared from the black liquor (Westvaco, Covington, VA), were used to
replace petroleum-based polyols in the production of rigid polyurethane foams (RPFs) [80].
The foams had satisfactory structure and strength when HKL or HEL was added. However,
the greater miscibility of HEL with the polyol (compared to HKL) allowed their use in higher
proportions (25-30%) compared with HKL (19-23%), without affecting the properties of the
foam. Polyurethane foams lose weight during exposure to elevated temperatures due to the
generation of toxic volatile compounds, an undesirable feature. A reduction in weight loss
was improved by producing foams containing soda-lignin from yellow poplar (Liriodendron
tulipifera), which emitted 34 times less volatile compounds than conventional foams [52].
Utilization of Lignin in Concrete
Concrete is a mixture of Portland cement, water, fine aggregate (sand) and coarse
aggregate (gravel) which may also contain chemical additives. When mixed, a quantity of
water greater than that required to hydrate its components is used and during hardening of the
concrete, the excess water remains, leading to the formation of cavities which reduce the
strength of the concrete. Concrete properties, such as strength, permeability and drying, may
be improved by addition of water-reducing agents whose main function is to increase the
fluidity of concrete by dispersing cement particles in paste [81].
Several compounds, such as sulfonated melamine formaldehyde condensates and
naphthalene formaldehyde condensates, has been used for this purpose [82]. However, the
wide utilization of these compounds is impaired by high cost and the toxicity of naphthalene.
Polyvalent Lignin
19
Moreover, there is a growing demand for replacing water-reducers (such as naphthalene)

derived from petroleum, due to the shortage of oil and global warming [83].
Although lignosulfonates (main component in the liquid waste from chemical pulp mills)
have been used in concrete for decades, their water-reducing capacity is small, at best
reducing the water used only by 8 to 10% [84]. Considering that only 10% of the 50 million
tons of lignosulfonates produced annually are used [85], researchers are introducing
modifications in order to improve their water-reducing properties. In this context, calcium
lignosulfonate from sulfite pulping (from Guangzhou Papermaking Co. Ltd, China) was
modified by oxidation and sulfonation to improve its water-reducing property [85]. The
results showed a stronger wetting capacity for modified lignin compared to non-modified
lignin. Furthermore, the lignin-based concrete exhibits flexibility and compressive strength
comparable to that produced with formaldehyde condensates, which indicates calcium
lignosulfonate could be used as a water-reducer. Currently, there are several companies that
produce lignin derivatives for use as lignin-based concrete admixtures (Borregaard
LignoTech, Pure Lignin Environmental Technology, LignoTech South Africa, LignoTech
Brazil, Domtar and LoroyMan among others).
Utilization of Lignin in Asphalt Admixtures

The aging of asphalt pavement is directly related to its hardening due to oxidation.
Retarding the oxidative aging of pavement would maintain the elastic properties, preventing
cracking due to loads and temperature. Asphalt cement is composed of asphaltenes, saturates,
naphthalene and polar aromatics, with each fraction interacting with the others to provide
different properties to the asphalt. Exposure to atmospheric oxygen leads to the generation of
oxygen-containing functional groups which can cause aggregation among asphalt molecules
due to the formation of hydrogen bonds and van der Waals interactions [86]. Although many
chemical agents (such as styrene-butadiene-styrene and styrene-b-butadiene) have been used
to prevent the oxidative aging of asphalt, the majority do not yield satisfactory results. On the
other hand, promising results have been obtained by the addition of lignin to asphalt mixtures
as the hydroxyl groups attached to the benzene rings can act as antioxidants. In a study, two
types of coniferyl-alcohol lignin were mixed with asphalt at 130C and subjected to different
temperatures (130 and 150oC) in order to evaluated the anti-oxidant effect [86]. The results
show that coniferyl-alcohol lignin had significant antioxidant activity at 130C that was lost
when the temperature reached 150C due to its oxidation to vanillin and glycolaldehyde. The
authors concluded that coniferyl-alcohol lignin can be used as an antioxidant for asphalt
mixtures under conditions where the lignin does not undergo oxidation.
Other Applications
Lignin has been used to immobilize proteins, increasing the lifetime of enzymes [87].
Researchers at the University of Kansas (USA) used calcium lignosulfonate (CaL) obtained
from Borregaard Lignotech (USA) to improve the cohesion of soil particles in unpaved roads.
According to the researchers, more than 70% of the 98,000 miles of roads in Kansas are
unpaved roads, and erosion caused by wind and traffic are frequent problems. According to
the authors, lignin represents an environmentally-friendly solution compared to the use of
other soil stabilizers such as ash or ground Portland cement type I, which are soil
contaminants [88]. Beyond dust control for roads, lignin has been similarly used in coal
mines and coal transportation.
20
Lignin depolymerization is also important for the production of chemicals such as

guaiacol, vanillin, catechol, pyrocatechol, and syringol [89]. Furthermore, lignin improves the
performance of energy storage devices (batteries) [90] and Wood pellets with better fuel
value can be produced by addition of lignin [91]. Additionally, sulfonated lignins are used as
thickeners, producing greases with higher lubricating properties which increase corrosion
protection and provide greater resistance to tool wear [92].
CONCLUSION
Human history could be divided into Ages, named according to the main raw material
that enriched life and resulted in technological advances - the Stone Ages (Paleolithic,
Mesolithic and Mesolithic) and Metal Ages (Copper, Bronze and Iron Ages). Of course, the
fast and concomitant advances in agriculture, politics, writing and engineering make this
simplification more difficult and imprecise. However, at the end of the 19th century, a
remarkable change occurred. Our ancestors had made use of simple machines [93] and energy
from animals/fire for some time, but steam engines joined them together. Even more
important, throughout the Industrial Revolution, coal-powered steam machines were used to
remove water from mines in order to produce more coal. In other words: a machine was used
to produce energy. Since then, the technological advances have been marked not only by the
production of consumer goods, but also by the production of more and more energy.
Remarkably: fossil energy as oil, coal and gas. Since all our technological symbols (steel,
plastic, electronics or cars) are essentially dependent on fossil fuels, it would be reasonable to
name our time as the Age of Fossil Fuels.
However, due either to global warming or the increasing cost of oil, this Age is giving
signs that it is coming to an end [94]. It quite clear that biomass is the only source of energy
that can replace oil [11]. This review shows that biomass is able to serve as much more than
fuel. Lignin cannot be directly converted into liquid fuel and does impose an additional
barrier to the production of ethanol from cellulose. On the other hand, lignin can (partially)
substitute (with advantages) for other raw materials in the production of items iconic of
modern civilization, from plastics and steel to the production of carbon fibers and epoxy
resins.
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BIOCHEMISTRY RESEARCH TRENDS

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Additional e-books in this series can be found on Novas website

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Copyright 2014 by Nova Science Publishers, Inc.

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The DFRC (Derivatization Followed by Reductive Cleavage)

Structural Characterization of Lignin by Syringyl to Guaiacyl

Structural Characterization and Thermal Properties of

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Novel Developments on the Valorization of Lignin-Containing

Kraft Lignin As an Adsorbent to Remove Heavy Metal

Lignin-Based Thermoplastic Composites

Esterified Kraft Lignin: A Potential Coupling Agent

Comparison of Physicochemical and Thermal Properties

The Pyrolysis Behavior of Lignins:

Lignin Controls on Soil Ecosystem Services:

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Lignins composition, functionality, purity, molecular weight and degree of cross-linking,

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Corresponding Author address: Email: osferrarese@gmail.com.

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

Keywords: Lignification, lignin detection, lignin characterization, lignin quantification,

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

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Figure 2. Current methods for detection, characterization and quantification of lignin.

Figure 3. The Wiesner reaction.

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

Figure 4. The Male reaction.

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

Figure 7. Arylglycerol--aryl ether: the main interunit linkage in lignin.

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

Biological Applications of Lignin

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W. Dantas dos Santos, R. Marchiosi, F. Carolina Moreira Vilar et al.

Industrial Applications of Lignin

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suggest that Kraft lignin-based plastics can be extrusion-molded, as determined by melt-flow

Utilization of Lignin in Phenolic Resins