UNIVERSITY OF THE EAST

CHAPTER II

Review of Related Literature

CELLULOSE
Krassig (1993) stated that, cellulose constitute the most abundant, renewable
polymer resource available today worldwide. For two general purposes, a polymer
raw material cellulose is being used. It has served mankind as a construction material
for many centuries, mainly in the form of paper and board or intact wood and textile
fibers such as cotton or flax. Cellulose as a starting material is versatile for chemical
conversions, production of artificials, cellulose-based threads and films as well as a
variety of stable cellulose derivatives used in many areas of industry and domestic
life. Invented in 1892 by Cross et al. (1893), by far the largest part of cellulose-based
artificial fibers have been manufactured for about the last century by the so-called
viscose process. With an output of about 3 million tons annually worldwide, this
process is being practiced today. Prepared by reaction of cellulose with aqueous
sodium hydroxide and CS2 and its decomposition by spinning in an acid bath It
makes use of the formation of cellulose xanthogenate, i.e., a water-soluble, less-stable
anionic ester.

According to Payen (1838), a unique place in the annals of polymers were

occupied by cellulose. Thousands of years ago, empirical knowledge of dying
cellulose fibres, burning wood, preparing charcoal, and the biodegradation of
cellulose by rotting was already acquired. Payen recognized, as early as 1838,
cellulose as a definitive substance and coined the name cellulose. Before its polymeric
nature was recognized and well understood, cellulose as a precursor for chemical
modifications has been already used.

As Balser et.al., (1986) said that, the only inorganic cellulose ester of
commercial interest today is the cellulose nitrate. Regenerated cellulose filaments
were obtained by spinning cellulose dissolved in cuprammonium hydroxide in an
aqueous bath.
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Staudinger and Daumiller (1937) stated that, the origin of cellulose chemistry as
a branch of polymer research can be traced back to the fundamental experiments of H.
Staudinger in the 1920s and 1930s on the acetylation and deacetylation of cellulose;
these experiments resulted in the concept of polymer-analogous reactions. According
to this concept, functional groups of macromolecules - in the case of cellulose
predominantly hydroxyl groups -can undergo the same kind of reactions as the
corresponding low-molecular compounds. Further, in determining the rate and final
degree of conversion it was observed that the supramolecular structure of the polymer
may play an important, as well as the distribution of the functional groups, which has
been well recognized for cellulose.

Concept of Cellulose

To produce paperboard and paper, cellulose is mainly used. A wide variety of

derivative products were being converted from smaller quantities such as cellophane
and rayon. As an alternative fuel source conversion of cellulose from energy crops
into biofuels such as cellulosic ethanol is under investigation. Wood pulp and cotton
is the main source where cellulose are obtained for industrial purposes. Some animals,
particularly ruminants and termites, can digest cellulose with the help of symbiotic
micro-organisms that live in their guts, such as Trichonympha. In human nutrition,
cellulose is a nondigestible constituent of insoluble dietary fiber, acting as a
hydrophilic bulking agent for feces and potentially aiding in defecation. (Updegraff
D.M (1969). "Semimicro determination of cellulose in biological materials".
Analytical Biochemistry)

Applications of cellulose

Physiological Function

Sitte et.al (1991) proved that, cellulose is the main component of plant cell
walls. Protection of cells and formation of structures are as such the main functions of
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cellulose during plant life. The defined cell shapes and position of cells to each other
are the basis for plant morphology. Therefore, cellulose is essential for plant life as we
know it. Even structures based on old cell walls from already dead cells are crucial
functional units of higher plants (xylem). The main building blocks of the primary cell
wall of plants consist of different components, e.g., pectins, hemicelluloses,
celluloses, and proteins. In the primary cell wall, the non-cellulosic components
dominate; on this basis, the mechanical stability of the primary cell wall is low. While
in later on formed structures of the cell wall and units important for plant
morphogenesis the fibrillar structure of cellulose stabilizes the plant organism. The
later on formed structures of the cell wall and cell units important for plant
morphogenesis were stabilized by the fibrillar character of cellulose. The primary cell
wall swells and forms jelly-like structures. (To the groups of hemicelluloses belong
glucanes of the (1-3) -β- as well as (1-4) -β-gluco-, and galactomannanes and mainly
xylanes.

According to Henriksson et al. 2000, the cellulose molecules in the primary cell
walls have high degrees of polymerization between 2000 and 15,000 anhydroglucose
units in long, non-branched molecules. The cellulose chains are twisted along the axis
of the glucanchains (180 degrees) and stabilized by hydrogen bonds between the
chains. As a result, the rings of the pyranoses lie approximately in the same level,
forming ligaments. The smaller chains have lengths around 8 µm. These chains
associate to elementary fibrils having a diameter of about 5-30 nm. In the secondary
cell walls, the fibrils associate to microfibrils with diameters of about 5-30 nm. These
microfibrils have an organization in crystal lattices, bringing a high stability into the
cell walls of plants. These associated cellulose fibrils bring the main contribution to
the high mechanical strength of the plant cell walls. The tensile strength of plant cell
walls has a basis not only in the association of the chains by hydrogen bonds but also
in sticking together with other components of the primary cell wall, such as proteins,
pectines, and hemicelluloses. For further increasing the stability of plants, lignin is
incorporated into the plant architecture. The portion and distribution of the different
components of cell walls define the final properties of the plant parts and tissues.
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Rose et al. (1997) have found that specific proteins, are able to induce the
extension of isolated plant cell walls in vitro and to disrupt the non-covalent
interactions between hemicelluloses and cellulose microfibrils which is so-called
expansins. This process maybe an integral part to plant cell expansion since the
primary cell walls acts as the main factor for cell enlargement. Within this primary
cell wall, the role of different components using expansins can be studied. Moore et
al., (1997) said that by ethylene and other phytohormones, some of these reactions
and substance formations will be regulated. The microtubule arrays are of high
importance because of their involvement in the orientation of cellulose microfibrils.
The plant interphase tubulins play an important role in these processes and have
influences on structuring the microfibrils within the cell-wall system.

Industrial uses

Cellulose for industrial use is mainly obtained from wood pulp and cotton. The kraft
process is used to separate cellulose from lignin, another major component of plant
matter.

Paper products: Cellulose is the major constituent of paper, paperboard, and card
stock.

Fibers: Cellulose is the main ingredient of textiles made from cotton, linen, and other
plant fibers. It can be turned into rayon, an important fiber that has been used for
textiles since the beginning of the 20th century. Both cellophane and rayon are known
as "regenerated cellulose fibers” they are identical to cellulose in chemical structure
and are usually made from dissolving pulp via viscose. A more recent and
environmentally friendly method to produce a form of rayon is the Lyocell process.

Consumables: Microcrystalline cellulose (E460i) and powdered cellulose (E460ii)

are used as inactive fillers in drug tablet and a wide range of soluble cellulose
derivatives, E numbers E461 to E469, are used as emulsifiers, thickeners and
stabilizers in processed foods. Cellulose powder is, for example used in Parmesan
cheese to prevent caking inside the package. Cellulose occurs naturally in some foods
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and is an additive in manufactured foods, contributing an indigestible component used

for texture and bulk, potentially aiding in defecation

Science: Cellulose is used in the laboratory as a stationary phase for thin layer
chromatography. Cellulose fibers are also used in liquid filtration, sometimes in
combination with diatomaceous earth or other filtration media, to create a filter bed of
inert material.

Energy crops: The major combustible component of non-food energy crops is

cellulose, with lignin second. Non-food energy crops produce more usable energy
than edible energy crops (which have a large starch component), but still compete
with food crops for agricultural land and water resources. Typical non-food energy
crops include industrial hemp (though outlawed in some countries), switchgrass,
Miscanthus, Salix (willow), and Populus (poplar) species.

Biofuel: TU-103, a strain of Clostridium bacteria found in zebra waste, can convert
nearly any form of cellulose into butanol fuel.

Building material: Hydroxyl bonding of cellulose in water produces a sprayable,

moldable material as an alternative to the use of plastics and resins. The recyclable
material can be made water and fire-resistant. It provides sufficient strength for use as
a building material. Cellulose insulation made from recycled paper is becoming
popular as an environmentally preferable material for building insulation. It can be
treated with boric acid as a fire retardant.

Miscellaneous: Cellulose can be converted into cellophane, a thin transparent film. It

is the base material for the celluloid that was used for photographic and movie films
until the mid-1930s. Cellulose is used to make water-soluble adhesives and binders
such as methyl cellulose and carboxymethyl cellulose which are used in wallpaper
paste. Cellulose is further used to make hydrophilic and highly absorbent sponges.
Cellulose is the raw material in the manufacture of nitrocellulose (cellulose nitrate)
which is used in smokeless gunpowder.
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GLUCOSE

In plants, the synthesis of starch occurs by utilizing ADP-glucose as the

glucose donor for the elongation of α-1,4 –glycosides chains. In photosynthetic
bacteria the synthesis of glycogen follows a similar pathway. The first committed step
in these pathways is the synthesis of ADP-glucose in a reaction catalyzed by ADP-
glucose pyrophosphorylase. Generally, this enzyme is allosteric ally regulated by
intermediates of the major carbon assimilatory pathway in the respective organism. In
oxygenic photosynthesizes, is mainly regulated by 3-phosphoglycerate (activator) and
inorganic orthophosphate (inhibitor), interacting in four different patterns. Recent
reports have shown that in higher plants, some of the enzymes could also be redox
regulated. In eukaryotes, the enzyme is a heterotetramer comprised of two distinct
subunits, a catalytic and a modulatory subunit. The latter has been proposed as related
to variations in regulation of the enzyme in different plant tissues. Random and site-
directed mutagenesis experiments of conserved amino acids revealed important
residues for catalysis and regulation. Prediction of the secondary structure suggests
that it shares a common folding pattern to another sugar-nucleotide
pyrophosphorylases, and they evolved from a common ancestor.

Glucose transport capacity of C. cryptic increases in an exponential manner

over 24 hours after transfer of the cells from light to complete darkness with little
simultaneous increase in cell number. The transport system is rapidly inactivated
when cells are transferred back to continuous light. Most of the inactivation takes
place while there is still little changes in cell number. When grown on a continuous
light regime, the capacity for glucose transport per cell depends on the light intensity.
At intensities sufficient to saturate photosynthesis the glucose transport system is only
about 5% that of dark-grown cells, while cells grown at intensities close to the light
compensation point have about 30% of the capacity of dark-grown cells. The action
spectrum for inactivation of glucose transport is identical to that for photosynthesis.
Cells, whether grown under continuous light, in the dark in the presence of glucose, or
kept in the dark without glucose, contain high levels of glucokinase and
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phosphofructokinase. The glucose transport system is highly specific for glucose;

only galactose inhibits the uptake of glucose by about 50% when present at 10 times
the concentration of glucose. The glucokinase is even more specific for glucose and is
not inhibited by galactose. The phosphofructokinase is inhibited by high
concentrations of ATP in cells grown under all conditions. Cycloheximide inhibits the
induction of glucose transport in the dark, but not the inactivation of the system in the
light.

The present work suggests that self-control relies on glucose as a limited

energy source. Laboratory tests of self-control. (a) acts of self-control reduced blood
glucose levels, (b) low levels of blood glucose after an initial self-control task
predicted poor performance on a subsequent self-control task, and (c) initial acts of
self-control impaired performance on subsequent self-control tasks, but consuming a
glucose drink eliminated these impairments. Self-control requires a certain amount of
glucose to operate unimpaired. A single act of self-control causes glucose to drop
below optimal levels, thereby impairing subsequent attempts at self-control.

BIOFUEL

According to Convento (2007), Biofuel is said to be the common term for

transport fuel that can be manufactured from renewable material of plant or animal
origin and are utilized as substitutes or extender for fossil fuels.

Written in The Republic Act 9367 (Biofuels Act of 2006), Biofuels refers to
fuels “made from biomass and primarily used for motive, thermal and power
generation, with quality specifications in accordance with the Philippine National
Standards (PNS).” These mainly refer to biodiesel, fuel made from plant oils, and
bioethanol, fuel from starchy agricultural crops/grains or sugarcane. Both are used as
source of energy.
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Convento (2007) also said that, The Biofuels Act of 2006 in the Philippines
greatly influenced the fuel trend into biofuels. Thus, Biofuel received considerable
attention.

In addition to that, The Biofuels Act of 2006 made the Philippine government
establish a biofuel program which envisions reducing the countries dependence on
imported crude, to increase economic activity and employment in the provinces and to
cut down on the country’s greenhouse gas emission level, thus allowing it to meet
global environmental standards on air pollution.

Convento (2007) added, Research on biofuel is subdivided into two major

classifications, the biodiesel and bioethanol. Bioethanol is an alcohol made from
sugar, starch and products containing sugars and starches through a process of
fermentation and distillation, and used as a substitute or supplement for gasoline.
bioethanol is defined as ethyl alcohol derived from agricultural crops or sugars for use
in gasoline engine while biodiesel is defined as monoalkyl esters derived from
agricultural oils for use in diesel engine. The Philippines commonly utilized
sugarcane for bioethanol while coconut oil and jatropha oil for biodiesel. Biodiesel,
on the other hand, can be produced from any plant oils or animal’s fats that are
chemically reacted to be converted to esters and used as a substitute or supplement for
petroleum diesel.

Many biofuels were already developed and used in many parts of the world. A
lot of researches and attempts in the development and improvement of biofuels in the
Philippines were done using raw materials that are feasible and available in the
country. Studies were conducted with the use of coconut oil and jatropha oil and other
oil materials 3 for biodiesel production. Also, numerous studies were conducted in
producing bioethanol from different locally available biomass for gasoline-blend
applications. Research has to be continued to further improve and establish the biofuel
research in the Philippines. An extensive literature review is essential, and an in-depth
analysis is needed to further improve the biofuels research in the Philippines.
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According to Gondi (2015), Peel is a major by-product during processing of

mango fruit into pulp. Ethanolic extract of mango peel was analyzed for its bioactive
compounds, evaluated for α-amylase and α-glucosidase inhibitory properties, oral
glucose tolerance test, antioxidant properties, plasma insulin level and biochemical
parameters related to diabetes. In addition to gallic and protocatechuic acids, the
extract also had chlorogenic and ferulic acids, which were not reported earlier in
mango peel extracts.

Potera (2004) said that, the United States presently produced three billion
gallons of ethanol from corn annually.

Potera (2004) added, they studied the suitability of waste mango fruit juice for
ethanol production. We concentrated mainly on maximize the high-quality juice
extracted by improving the extracting techniques and optimize the fermentation
process to improve the volumetric productivity of ethanol.

Fadri (2012) implied, garbage and wastes in this modern era have always been
a major concern of every country for it is the root cause of major problems such as
pollution.

Furthermore, according to the Department of Natural Resources, about 35, 000

tons of garbage is generated daily in the Philippines. And about half of this garbage is
biodegradable waste. Production of Ethanol from Musa Acuminata (Lacatan) and
Musa Paradisiaca (Saba) Peelings can be used to produce ethanol unripened bananas
are composed of starch; but as the natural ripening proceeds, the starchy material is
converted into sugar. Ethanol can be produced from a variety of feedstock such as
sugar cane, cotton and also bananas which contains sugar, an important element in
ethanol production.

Jagessar and Fraser (2014) articulated, Ethanol doesn’t have significant

environmental impact as fossil fuel combustion. It has low air polluting effect and low
atmospheric photochemical reactivity, further reducing impact on the ozone layer
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Bio-ethanol can be used for a variety of purposes, of which blending withgasoline to

produce gas alcohol to power automobiles is on the increase