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TABLE OF CONTENTS

PREFACE...................................................................................................................................................3
ABBREVIATION.......................................................................................................................................3
1. Introduction........................................................................................................................................3
1.1. Definition.....................................................................................................................................3
1.2. The discovery of microcrystalline cellulose..............................................................................3
1.3. Microcrystalline cellulose in the market...................................................................................4
2. Preparation of microcrystalline cellulose.........................................................................................4
2.1. Cellulose sources.........................................................................................................................4
2.1.1. Lignocellulose, cellulose, alpha cellulose...........................................................................4
2.1.2. Cellulose (raw material) sources.........................................................................................5
2.2. Preparation of particles of microcrystals..................................................................................6
2.3. Hydrolysis mechanisms for microcrystalline cellulose isolation.............................................9
2.4. MCC production from sugarcane bagasse - sustainable process development:..................10
3. Classification of microcrystalline cellulose.....................................................................................12
4. Chemical structure and morphology of microcrystalline cellulose...............................................13
5. Functional properties of microcrystalline cellulose.......................................................................14
5.1. Physical properties...................................................................................................................14
5.2. Techno-functional properties of MCC in processed food......................................................14
5.3. Nutritional and health benefits of microcrystalline cellulose.................................................17
5.3.1. Safety of microcrystalline cellulose.........................................................................................18
5.3.2. Hypoglycemic, hypolipidemic effects and plasma cholesterol levels control..........................19
5.3.3. Prebiotic effect.........................................................................................................................20
5.3.4. Bowel movement and constipation..........................................................................................21
5.3.5. Obesity management................................................................................................................22
6. Application of microcrystalline cellulose in processed food..........................................................22
7. Gaps and implications for future research.....................................................................................24
8. Conclusions.......................................................................................................................................25
REFERENCES:........................................................................................................................................26

1
TABLE OF FIGURES
Figure 2.1. Chemical structure of Lignocellulose [14]................................................................................6
Figure 2.2. Molecular structure of cellulose showing the numbering of carbon atoms [17]........................6
Figure 2.3. Scheme of the common steps needed to produce MCC from cellulose source materials [17].. .8
Figure 2.4. Conventional Manufacturing of MCC [35]...............................................................................9
Figure 2.5. Schematic diagram of microcrystalline cellulose separation during acid hydrolysis [17]........11
Figure 2.6. Process of MCC production from sugarcane bagasse [46]......................................................12
Figure 2.7. Process of the MCC extraction from sugarcane bagasse with specific steps [47]....................13

2
TABLE OF TABLES

3
1. PREFACE
Cellulose, a fascinating biopolymer and the most common organic compound on earth, is
comprehensively reviewed. Details of its crystalline phases are given, starting with a description of
molecular and supramolecular structures, including the hydrogen bond systems. Currently, scientists are
paying attention to microcrystalline cellulose for its technological features and useful applications in food
and pharmaceuticals. In food and beverage industry, MCC has been extensively explored as a functional
ingredient in meat products, emulsions, beverages, dairy products, bakery, confectionary and filling.
Though widely used as control for many dietary fiber investigations, MCC has been shown to provide
positive effects on gastrointestinal physiology, and hypolipidemic effects, influencing the expression of
enzymes involved in lipid metabolism. These techno-functional and nutraceutical properties of MCC are
influenced by the hysicochemical of the material, which are defined by the raw material source and
processing conditions. Apart from these functional properties, this review also highlighted limitations and
gaps regarding the application of material in food and nutritional realms.
The content of the report consists of 7 parts:
Part 1 clarifies the definition of MCC, origin and commercial situation of MCC in the market.
Part 2 outlines the process for preparing MCC in industry.
Part 3 is the classification of microcrystalline cellulose in food as well as in pharmaceuticals.
Part 4 delineates the chemical structure and morphology of MCC.
Part 5 elucidates the functional properties of MCC: physical properties, techno-functional properties
together with nutritional and health benefits of microcrystalline cellulose.
Part 6 delivers some of the important uses of MCC in food processing industry.
Part 7 discusses the gap between research and practical application of MCC, from which draws
conclusions about significant role of MCC in food.

ABBREVIATION
DP: Degree of Polymerization; DF: Dietary fiber; GIT: Gastrointestinal tract; GRAS: Generally regarded
as safe; LODP: level of degree of polymerization; MCC: Microcrystalline Cellulose; NCC:
nanocrystalline cellulose; ND: not detected; o/w: oil-in-water (emulsion); SCB: Sugarcane bagasse;
SCFA: short chain fatty acid; SEM: scanning electron microscope; TEM: transmission electron
microscope; v/v: volume per volume; w/o: water-in-oil (emulsion); w/o/w: water-in-oil-in-water
(emulsion); w/v: weight per volume.

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1. INTRODUCTION
1.1. Definition
Microcrystalline cellulose (MCC) is a purified, partially depolymerized cellulose having the formula
(C6H10O5)n [1]. MCC is distinguished from native purified starting material by the measure of its DP
(usually less than 400 glucose units) [2]. Pharmaceutically, pharmacopoeial MCC is defined by a DP
below 350 glucose units, compared to DPs in the order of 10,000 units for the original native cellulose [3].
As a matter of precaution, the Committee repeated the advice given in 1995, according to which, the MCC
particles with size lower than 5µm must not be more than 10% of the total particles [4].

1.2. The discovery of microcrystalline cellulose


Interestingly, the discovery of MCC commenced from a failed experiment [5]. The authors tried to employ
a Waring Blender (laboratory-quality blender that helps mix, stir, or homogenize using the variable speed)
to break up hydrolyzed cellulose to smaller particles in water. They thought the sharp blades of the
Waring Blender would sliver off very small fragments of the agglomerated microcrystals in the
hydrolyzed cellulose, and the obtained microcrystalline fragments would settle out of water. Instead, they
obtained a stable colloidal suspension, which is known commercially as Avicel. In 1964, FMC
Corporation introduced Avicel® PH to the pharmaceutical industry as an ingredient for direct
compression tableting where the “PH” designation indicates that the product is suitable for pharmaceutical
use. Since then, an exponential number of researchers have focused their work on such material [6], [7].
MCC is characterized by a high degree of crystallinity, and the values typically range between 55% and
80% [8].

1.3. Microcrystalline cellulose in the market


It is well known that the morphology, physicochemical properties and mechanical characteristics of MCC
exhibit variations according to the origin of the raw material and the extraction process. Currently, MCC
is a material available in the market with more than 60 years of history and the price of MCC (≈$4/kg),
which is comparable to or less than some other engineering should be fillers (glass or aramid) [9]. Over
half a century later, MCC is produced worldwide by more than 10 companies [10].

The application areas of MCC are huge, encompassing many industrial sectors such as food,
pharmaceutical, cosmetics, cement, and plastic industries. Consequently, the global market for MCC,
particularly in North America has witnessed tremendous growth with positive future prospects. In 2015, a
report by Transparency Market Research Analysis indicated that the global market for the MCC is
expected to reach $1.08 billion USD by 2020, with the pharmaceutical and the food sectors as the biggest
beneficiaries. Thus, in terms of value, its market is expected to witness a compound annual rate of growth
of 7.2% between 2015 and 2020 [11].

2. PREPARATION OF MICROCRYSTALLINE CELLULOSE


2.1. Cellulose sources
2.1.1. Lignocellulose, cellulose, alpha cellulose
Lignocellulose is plant biomass (plant cellulose) that consists of cellulose, hemicelluloses1, and lignin2.
Celluloses and hemicelluloses correspond to approximately 70 % of the entire biomass and are tightly
linked to the lignin through covalent and hydrogenic bonds that make the structure highly robust and
resistant to any kind of hydrolysis [12] (Figure 2.1). The most important lignocellulosic materials are
wood and agricultural wastes, such as straw of various kinds and sugar cane bagasse [13].

1
Hemicellulose acts as a bonding agent between lignin and cellulose. Its covalent linkage to lignin and its noncovalent interaction
with cellulose may be important in maintaining the integrity of the cellulose in situ and helping to protect the fibers against
degradation by cellulases [118][119].
2
Lignin covalently bonds to hemicellulose and is responsible for much of the mechanical strength of wood [120].
5
Figure 2.0.1. Chemical structure of Lignocellulose [14].

Cellulose, the ubiquitous renewable natural biopolymer on Earth, is considered to be one of the most
important organic compounds produced in the biosphere. It is biosynthesized by a number of living
organisms ranging from lower to higher plants, sea animals, bacteria and fungi [15],[16]. Structurally,
cellulose is a linear carbohydrate polymer with long chains of β-(1→4)-linked D-anhydroglucopyranose
moieties repeating units (Figure 1.2). Since cellulose is made up of sugar monomers, it is called a
polysaccharide. The size of cellulose molecules is commonly conveyed as degree of polymerization (DP),
which states size in terms of the number of anhydroglucose units per cellulose chain. In nature,the DP of
cellulose chains ranges from 100 for MCC to 15,000 for native cotton in relation to their isolation method.

Figure 2.0.2. Molecular structure of cellulose showing the numbering of carbon atoms [17].

Alpha cellulose is one of three forms of cellulose 3. Alpha cellulose has the highest degree of
polymerization and is the chief constituent of paper pulp and chemical dissolving-grade pulp [18].
2.1.2. Cellulose (raw material) sources
The raw materials are categorized into two groups; wood and non-wood sources.
 The wood sources include hardwood, softwood and cotton linter. [19]
 The non-wood sources are mainly lignocellulosic materials, especially agricultural residues.

3
Based on solubility in alkali cellulose plants can be divided into three groups: alpha cellulose, beta cellulose and gamma cellulose
[121]. Alpha-cellulose is the pulp fraction resistant to 17.5% and 9.45% sodium hydroxide solution. Beta-cellulose
(hemicellulose) is the soluble fraction which is reprecipitated on acidification of the solution; gamma-cellulose (hemicellulose) is
that fraction remaining in the solution [122].
6
Table 2.1. Chemical composition of cellulose-containing materials [17].

Plants materials usually rich in alpha cellulose (woody sources and cotton linters) are mainly used as the
raw material for the production of the micro scale crystalline material because the cellulose strands are
structurally arranged with layers of the cellulose chains bonded together by a cross-linking polymer
(lignin) and strong hydrogen bonding [20][21][10].
However, competition among many areas such as furniture, pulp and paper industries, building products,
as well as the combustion of wood for energy and the employment of cotton for textile industry, renders
them challenging to provide all sectors with the required quantities of wood and cotton at a suitable price.
Besides that, wood and cotton are not available in many regions, thus tuning its options to non-woody
cellulose. For example, MCC can be extracted from groundnut shell, cereal straw, bagasse and corn cob,
bamboo, sugar beet pulp, luffa cylindrical, orange mesocarps, jute, rice and bean hulls, hemp stalks and
rice husks, newsprint, oil palm biomass, fodder grass, wastepaper, filter paper and cotton waste. Esparto
grass and soybean hulls have also been investigated as potential sources of MCC. Bacterial cellulose (e.g.
Gluconacetobacter xylinus) has been used as the starting material for research on MCC production as well
[17].
The chemical constituent (celluloses, hemicelluloses and lignin) of the raw material differs considerably in
chemical proportions and structural organization (table 2.1); crystalline regions that are sandwiched by
two amorphous regions. Microcrystalline cellulose obtained from various types of cellulose sources of
miscellaneous provenance using various extraction methods and conditions commonly differ in molecular
weight, particle size, crystallinity, surface area, moisture content, porous structure, etc [17].
2.2. Preparation of particles of microcrystals
MCC is usually manufactured by the following process: wood pulp made of needle-leaf trees or return
pulp made of cotton-seed fiber is partially hydrolyzed and washed after removing the amorphous region
and impurities to purify the MCC [22].
MCC can be dried to a pure, fine-particle form for powdered grade or co-processed with a water-soluble
polymer to deliver a colloidal form [17]. Figure 2.3 displays the different steps which are usually
followed to produce MCC from its feedstock using different procedures. For lignocellulosic materials, it
7
involves firstly the removal of lignin, hemicellulose, etc. and isolation of cellulosic fibers (pretreatment).
Secondly, a controlled hydrolysis treatment (generally acid hydrolysis) to remove the paracrystalline
regions of the cellulose polymer; and finally, post-treatments were performed to recover the final MCC
product.
Pretreatment (purification): to obtain purified cellulose (the starting material for MCC production).
The purification step is largely dependent on the type of raw material source of the cellulose. For example,
the pretreatment for plants sources such as wood, partially or completely removes hemicellulose, lignin
and other impurities to obtain pure cellulose fiber. In the cases of algal and bacterial celluloses, culturing
methods, and subsequent purifications are usually employed to eliminate the wall matrix, bacteria and the
other media to obtain the starting material. Extensive works have been done detailing the description of
these pretreatments to obtain pure cellulose for MCC production within the available references in the
following: bacteria [23], [24], wood [25], lignocellulosic materials/agricultural residues (eg, oil palm fruits
bunch and front [26], banana stems hull, rice straw, corn husk/comb [27], bamboo [28], etc) [29], algae
[30].
From technological point of view, lignin content evaluation is an important parameter to well optimize the
pretreatment process required to isolate a pure cellulose pulp. Indeed, lignin is considered the hardest
chemical compound to be eliminated from lignocellulosic materials. However, there are various methods
for the extraction of cellulose from plants using chemical, physical, biological and combined processes
[31], [32], [33]. These processes have often been employed as a pretreatment to facilitate the hydrolysis
procedure for the production of MCC.

Figure 2.0.3. Scheme of the common steps needed to produce MCC from cellulose source materials [17].

Hydrolysis treatment:

8
The hydrolysis treatment is generally followed by neutralization, washing and drying processes. Currently,
the common manufacturing process is performed by spray-drying the neutralized aqueous slurry obtained
from the hydrolysis of cellulose procedure (figure 2.4) [34]. The main commercial grades are achieved by
controlling the drying steps to well manage the particle size distribution, the moisture content, binding
ability, etc. MCC is commonly dried from the slurry by spray-drying method. By varying spray-drying
conditions, the degree of agglomeration and moisture content can be manipulated, in order to obtain
particular particle sizes [1].

Figure 2.0.4. Conventional Manufacturing of MCC [35].

Regarding the isolation of crystalline cellulosic region, in the form of MCC, a common process widely
used is based on acid hydrolysis because it requires shorter reaction time than other processes.
For the acid hydrolysis technique, the acid causes the cellulose (usually purified/bleached pulp) to undergo
partial depolymerization to form microcrystalline cellulose [36]. The hydrolysis process is stopped when
the desired level of degree of polymerization (LODP) is attained [2], [37]. The LODP is raw material spe-
cific and typically found in the 180–350 ranges, as in the cases of 180–210 range for hardwood pulps,
210–250 softwood pulps [10], 182 for Bambusa vulgaris [28] as an example of non-wood biomass.
Numerous researchers had investigated the influence of processing conditions on the physicochemical,
thermal and mechanical properties. The temperature and time of hydrolysis procedure, nature and
concentration of acid as well as the fiber-to-acid ratio play the important roles in the particle size,
morphology, crystallinity, thermal stability and mechanical properties of MCC [38], [39], [40] . The acid
hydrolysis processes with HCl and H 2SO4 from various cellulosic sources to produce MCC are tabulated
in table 2.2. El-Sakhawy and Hassan isolated MCC from agricultural residues using HCl or H 2SO4 and
explored the effect of acid on the properties of the produced MCC [40]. They demonstrated that the kind
of acid used had no effect on both the crystallinity and crystallite size.

9
Table 2.2. Different acid hydrolysis procedures to produce MCC from various sources [17].

2.3. Hydrolysis mechanisms for microcrystalline cellulose isolation


Broadly, cellulose microfibrils are composed of crystalline 4 regions and disordered or paracrystalline 5
domains located at the surface and along their main axis. The microfibrils which make up the alpha
cellulose consist of paracrystalline and crystalline phases at nanometer range. The paracrystalline area is
an amorphous mass of cellulose chains whereas the crystalline regions comprise tight bundles of
microcrystals in a rigid linear arrangement. The crystalline regions are called cellulose crystallites and
they are formed by cellulose chains due to van der Waals interactions and hydrogen bonding. The
diameter of these crystallites is of the same order as the diameter of the cellulose microfibrils [41].
MCC is conventionally prepared by treating alpha cellulose with an excessive amount of mineral acids.
Upon contact with acidic solutions, the paracrystalline or amorphous regions are preferentially cleaved;
whereas the crystalline domains that have a higher resistance to acid attack remain essentially intact.
Figure 2.5 illustrates the preferential action of the amorphous regions of cellulose microfibrils, resulting
in MCC fibers (shorter and more crystalline fragments). It is worth mentioning that the diameter of these
MCC fibers (which usually varies from around 30 nm to 20 µm in diameter and up to hundred microns in
length) is widely determined by their source and the isolation process [17].

4
A crystalline structure is any structure of ions, molecules, or atoms that are held together in an ordered, three-dimensional
arrangement [123]. In perfectly crystalline material, or single crystal, the location of every atom in the structure can be described
exactly measuring out from a single origin.
5
A crystalline structure is any structure of ions, molecules, or atoms that are held together in an ordered, three-dimensional
arrangement [123]. In perfectly crystalline material, or single crystal, the location of every atom in the structure can be described
exactly measuring out from a single origin.
10
Figure 2.0.5. Schematic diagram of microcrystalline cellulose separation during acid hydrolysis [17].

2.4. MCC production from sugarcane bagasse - sustainable process development:


One of the major challenges in chemistry and engineering focused by the demand for climate change
mitigation is to develop green and sustainable technologies for the translation of waste biomass to
biofuels, commodity chemicals and novel bio-based materials [42]. MCC production is generally
dependent on wood pulp for lignocellulosic source, which raises potential environmental concerns in
relation to deforestation. Agroindustrial wastes are abundantly available and inexpensive source of
lignocellulosic biomass. Sugarcane bagasse (SCB) is the solid waste generated in huge quantities every
year by the sugar processing and ethanol production industries, and mainly used to generate electricity in
the industry as it is having quite good calorific value. Production of eco-friendly and high-performance
materials has been in the spotlight in recent times, wherein microcrystalline cellulose (MCC) gained
prominence for its application in various industries due its rheological, extruding, physical and mechanical
properties [43]. Approximately 28 – 30 % of the processed sugarcane yields bagasse and only half of it is
used for co-generation (electricity) which is sufficient for the sugar processing unit, and the rest is remains
as waste [44]. Typically, SCB is highly heterogeneous material consisting 40 – 45% of cellulose (mainly
alpha cellulose) which have more crystalline domains, 30-35% of hemicellulose, 18 – 25% of lignin with
smaller amounts of minerals, wax and ash content [45].
MCC manufacturing process from SCB consists of 3 main steps:
SCB preparation
SCB was sorted and cleaned and dried in sunlight. The dried SCB cut into small pieces about 1-2 cm,
grinded and the fraction passing 40 meshes was selected as raw material for the process [46].
Cellulose Extraction
Cellulose is the major fraction in the SCB residues and it can be utilized as a sustainable feedstock for
MCC production. Cellulose was initially extracted from SCB followed by the production
(depolymerization of cellulose) of MCC from extracted cellulose. The variation in the yields resulted
might be due to the acids utilized for the pretreatment of SCB and the time of reactions. H 2SO4 was
considered to be best suitable for acid pretreatment than HNO 3 [46].

11
In acid pretreatment the hemicellulose content was removed effectively from SCB. As hemicellulose is a
not more complex material compared to cellulose and lignin, physical pretreatment may be sufficient
without using acid [46].
Lignin removal plays a key role. Due to its complex structure, strong alkali removes lignin content from
SCB. The alkali pretreatment was carried with NaOH in three designed methods for removing the lignin
content from the bagasse, which reacts with coniferyl, sinapyl and coumaryl groups of complex lignin
structure and breaks the cross linking between those groups results in dissolution of lignin [46].
Raw cellulose produced in all the processes, contains color due the presence of some of the pigments,
remove by a combination of bleaching agents such as CH 3COOH and NaClO resulted in the formation of
hypochlorous acid (HOCl) which is a highly reactive compound that acts as the best bleaching compound
[46].
Conversion of Cellulose to MCC
The important step was depolymerization of cellulose in presence of H 2O2 in presence of H2SO4 which
favors acid hydrolysis where the long polymeric chain of cellulose will break to result in small chains of
glucose molecules, which was merely microcrystalline cellulose. The advantage of using hydrogen
peroxide was it can act as bleaching agent as well as delignifying agent and that result in complete
removal of lignin and color of produced MCC [46].

Figure 2.0.6. Process of MCC production from sugarcane bagasse [46].

12
Figure 2.0.7. Process of the MCC extraction from sugarcane bagasse with specific steps [47].

3. Classification of microcrystalline cellulose


a) In pharmaceutical industry: MCC is classified based on the size of the particles. There are several
commercial types of the MCC, namely PH 6 101, 102, 103, 105, 112, 113, 200, 301 and 302, partical
size and utilization of which described in table 3.1 below.

Table 3.1. Types of the commercial microcrystalline cellulose [6].

b) In food and beverage industry: MCC can be separated into two quite different grades in terms of
function and application. These are powdered MCC and colloidal MCC [48].
Powdered MCC has the E number7 E460 and is derived from naturally occurring cellulose similar to that
found in fruits and vegetables. Drying the crystalline bundles results in aggregates of very porous particles
that absorb large amounts of water or oil onto the surface [48].

6
PH stands for the pharmaceutical grade of MCC.
7
E numbers ("E" stands for "Europe") are codes for substances used as food additives for use within the European
Union (EU) and European Free Trade Association (EFTA) [124]. Commonly found on food labels, their safety assessment and
approval are the responsibility of the European Food Safety Authority (EFSA) [125].
13
Colloidal MCC (commercial name Avicel® RC/CL), which is also known as cellulose gel, is a co-
processed combination of natural powdered microcrystalline cellulose E460 and Sodium
carboxymethylcellulose E4668. Properly dispersed, colloidal MCC sets up into a three-dimensional
network of these colloidal particles that imparts stability in the finished product; the system is held
together by weak hydrogen bonding [48].
4. Chemical structure and morphology of microcrystalline cellulose
Cellulose, the raw material of MCC, is a polysaccharide consisting of tens of thousands of glucose units
linked together by β-1,4-glycosidic linkages to form a linear polymer. As a product of purified cellulose,
MCC particles are also composed of glucose units linked together by β-1,4-glycosidic linkages to form a
linear polymer chain of shorter length. Each glucose monomer in the polymer chain has three free
hydroxyl groups on C2, C3 and C6 (Figure 4.1) which define the chemical reactivity of the crystalline
polymer. These reactive sites allow possible modification of the cellulose crystals into a number of
functionalized materials for specific applications.

Figure 0.8. Chemical structure of microcrystalline cellulose [49].

Figure 4.1. Chemical structure of microcrystalline cellulose [49].

The morphology of MCC obtained from different sources such as cotton, wood, rice straw, bean hull,
alfalfa fiber, oil palm front, empty palm fruit bunch, rice hull, bean hull, and commercial MCC (Figure
4.2) are somewhat similar [38], [50]. However, surface morphology of the material may change in terms
of size and level of smoothness [51]. SEM and TEM analysis of MCC obtained from variety of sources
revealed the presence of rodlike or needle-like aggregates of particles, and further analysis of these
particles showed thatthey could be of varied particle size and shape [38], [24], [52]. Thus, MCC is
distinguished from native purified starting material by the measure of its DP (usually less than 400
glucose units) [2]. Apart from the raw material, the extent of processing significantly defines the chemical
composition and the morphological characteristics[11]. Although MCC is made up of water-soluble
glucose units, it is poorly soluble in aqueous media due to its crystalline structure. The crystallinity is due
to an ordered array of tightly packed linear glucose polymers connected with intra- and intermolecular
hydrogen bonds [53]. According to [11] Hamid et al.(2014), the degree of crystallinity achieved following
hydrolysis of the parent cellulose is a very important attribute of the polymer because it defines and
influences several characteristics of the material.

8
If a food grade sodium carboxymethylcellulose is added to the microcrystalline cellulose, with additional wet attrition before
drying, a colloidal microcrystalline cellulose is produced termed as Avicel® RC/CL which can function as a suspending agent,
emulsion stabilizer, etc.[6]. Due to the presence of Sodium Carboxymethylcellulose, colloidal MCC cannot be classified as
natural [48].
14
Figure 4.2. SEM of three different avicel PH MCC taken at the same magnification [49].

Avicel PH is an ideal wet granulation binder which rapidly produces robust granules that remain stable in
high shear environments, enabling broad processing windows and maximizing batch to batch
reproducibility.
PH: pharmaceutical
Avicel PH 101: ~50 μm particle size
Avicel PH 102: ~100 μm particle size
Avicel PH 200: ~200 μm particle size
5. Functional properties of microcrystalline cellulose
5.1. Physical properties
MCC is a porous, aggregate, white, odorless, impurity-free crystalline powder [11]. It is characterized by
lower degree of polymerization when compared with the starting material [41]. The crystallinity of MCC
depends largely on the degree of crystallinity of its starting material and processing technology.

Figure 5.1. MCC powder [54].

MCC is non-toxic, physiologically inert, renewable and biodegradable. Additionally, micro/nano-scale


particles of crystalline celluloses have unique physicochemical properties, offering the material excellent
functional properties such as rheological, thermal and mechanical characteristics [11].

MCC is hygroscopic in nature, and insoluble in water, but swells when in contact with water.
5.2. Techno-functional properties of MCC in processed food
An emulsion is a mixture of two or more liquids that are normally immiscible (unmixable or unblendable)
owing to liquid-liquid phase separation.

15
A suspension is a system consisting of a dispersion phase of solid particles suspended in a liquid-dispersed
medium (heterogeneous mixture); insoluble (difficult to dissolve) solid particles into the dispersing
medium. If left, the seeds will sink to form a layer of sediment, settling.
Foam stabilization is defined as the time that foam will maintain its initial properties as generated.
Emulsion, suspension and foam stabilization
In general, crystals of cellulose within micro/nano-scale dimension (MCC/NCC) by virtue of their
amphipathy are able to stabilize emulsions since the presence of the free hydroxyl groups on the material
surface acts as hydrophilic points, while the crystalline portion could function as the hydrophobic edge,
giving overall amphiphilic character [55]. These particle-stabilized emulsions are termed ‘Pickering’
emulsions.
The particles used to formulate Pickering emulsions should be wetted by both the dispersed and the
continuous phases. Thus, particle wettability is a crucial parameter [56], [57] . In Pickering emulsion
studies, particle wettability is characterized by the threephase contact angle (θ). The latter, measured in the
aqueous phase, corresponds to the angle between the aqueous phase, the oil phase and the particles
(Figure 5.2), and is commonly defined by the Young equation:

γ po−γ pw
cos θ=
γ ow
where γpo, γpw, γow are respectively the particle-oil, particle-water and oil-water interfacial tensions (Figure
5.2).
For particles stabilizing Pickering emulsions, θ is the equivalent of the HLB (hydrophilic-lipophilic
balance) for surfactants . They both denote the relative affinity of the particles or surfactants for oil and
water. The emulsion type mainly follows the empirical Finkle rule, which is the equivalent for Pickering
emulsions of the Bancroft rule used for emulsions stabilized by surfactants [56]. Indeed, it is commonly
admitted that θ is directly linked to the type of the stabilized emulsion (O/W, W/O or multiple). When θ <
90°, particles are mostly hydrophilic and can stabilize O/W emulsions as a larger part of the particles is
immersed in the aqueous phase. Conversely, when θ > 90°, particles are mostly hydrophilic and favor the
stabilization of W/O emulsion (Figure 5.2). To obtain a firm anchoring of the particles at the interface, θ
should be close to 90° (this point will be further discussed in Section 3.3.). However, this rule is not
always verified. By changing other parameters that will be later described, particles with initially θ < 90°
are able to stabilize O/W emulsions and, conversely, particles with θ > 90° are able to stabilize W/O
emulsions. It should also be noted that emulsion stabilization has been obtained with fully hydrophilic or
hydrophobic particles. In some recent studies, it was assumed that particles with θ = 90° (or very close)
would enable the formation of double emulsions, thanks to their capacity to adsorb at both interfaces: O/W
and W/O. The stabilization mechanism with “droplets bridging” also depends on θ, as it is usually
observed with particles whose θ is between 30° and 70°. To control the emulsion type (O/W or W/O,
simple or multiple) or the droplet size, the wettability of the particles can be tuned, as for example with
silica NP silanization .

16
Figure 5.2. Schematic representation of an O/W and a W/O Pickering emulsion at microscopic scales.
The three-phase contact angle (θ) as well as the particle-oil (γ po), particle-water (γpw) and oil-water (γow)
interfacial tensions are materialized on nanoscopic scale pictures (right) [58].

The mechanism of stabilization is based on particle shape, size, and partial dual wettability defined by
crystallinity [59]. Two major mechanisms have been putforward for the stabilization of particlestabilized
emulsions. Firstly, the solid particles can be irreversibly [60] adsorbed at the interface creating a layer
around the emulsion droplets to preventtheir coalescence [61]. For the second mechanism, stabilization of
particle-stabilized emulsion can be achieved by the formation of two or three dimensional networks [62],
[63]. MCCs are good candidates for interfacial stabilization, particularly for food use due to their
nontoxicity, sustainability, biodegradability and renewability in addition to excellent native
physiochemical properties including large elastic modulus and high aspect ratio [64], [55], [62].
Kalashnikova previously demonstrated that cellulose microcrystals in the absence of a dispersing agent
could effectively stabilize o/w emulsions for several months by the Pickering mechanism of stabilization
provided the particles are properly dispersed. Similarly, cellulose crystals in nano scale dimension
obtained from asparagus by sulphuric acid hydrolysis were used to successfully form stable Pickering
emulsions for several weeks in a palm oil/water (30/70, v/v) model solution [63]. Colloidal MCC (11%
MCC combined with 1% sodium carboxymethylcellulose) have also used to stabilize oil-in water (O/W)
emulsion and water-in-oil-in water (w/o/w) multiple emulsions via a formation of a network around the
emulsified oils [63]. MCC in such systems functions to orientate at the oil-water interface thereby offering
mechanical barrier to oil droplet coalescence [61], while the other material in the system mainly acts as a
dispersing and protective colloid for the MCC [63]. Colloidal MCC not only thickens the continuous
phase between the droplets, but also effectively builds a weak three-dimensional network anticipated to
stabilize the emulsions [60]. However, the strength of the networks formed by the cellulose depends on its
aspect ratio, which is invariably defined by the particles size and shape. Microfibrillated cellulose by
virtue of its high aspect ratio reportedly formed strong entangled disordered networks in contrast to low
aspectratio MCC, which created feebly bonded networks[65]. Suspensions of MCC are shear-thinning
and thixotropic but the extent differs according to the raw material source and the preparation technology.
17
For instance, suspension of MCC produced by HCl hydrolysis was more shear-thinning compared with
sulphuric acid hydrolysis MCC suspension. While the former is thixotropic at concentrations greater than
0.5% (w/v), the latter is not [63] due to the introduction of sulphate charges on the surface of the MCC
particles prepared with sulfuric acid [66]. In a recent study involving the use of MCC in active
pharmaceutical ingredient nanocrystal suspensions for spray drying, it was realized that the polymeric
dispersant was not only able to prevent the aggregation of the nanocrystals in the suspensions state but
also eliminated agglomeration throughout the spray drying process [67]. The authors explained that MCC
in water forms “charged network” structure, which adsorbs the active ingredients onto its surface and
prevents them (the active pharmaceutical ingredients) from particle–particle associations and
agglomerations. At pH below 3, MCC exhibits solid-like behavior due to the formation of the three-
dimensional network structures of the aggregates via non-electrostatic and electrostatic interactions [68].
Tang reported that micro or nanocrystalline cellulose produced using sulfuric acid hydrolysis led to the
formation of stable suspensions in water due to the formation of surface charges on the final crystalline
material. In using both sulfuric and hydrochloric acids to produce cellulose crystals from the same source,
it was observed that the products obtained by sulfuric acid treatment had negatively charged surfaces, due
to the introduction of O-SO3 during the acid treatment, while the sample treated with hydrochloric acid
did not have charges on the surfaces [69]. Moreover, the researchers noted that the zeta potential values
of the charged cellulose increased with both sulphuric acid concentration and treatment time. Accordingly,
stability of the cellulose suspension improved with increasing reaction time and acid concentration.
In foam based food products, materials with amphipathic characteristics are commonly employed to
stabilize the system dueto the ability of such ingredients to undergo flexible activation of their lyophilic
and lyophobic groups. MCC is a promising material for foam systems stabilization due to its
amphipathicity, and large elastic modulus.

5.3. Nutritional and health benefits of microcrystalline cellulose


The nutritional effect of MCC in humans could best be described as indirect, principally because human
carbohydrate digestive enzymes cannot degrade β-glycosidic linkages. The major constituent of MCC is
cellulose (Table 5.1), which is widely accepted as a dietary fiber. According to FMC health and nutrition
department, powdered and colloidal MCC are reported to contain 93 g and 98 g of dietary fibers,
respectively, per 100g. Many dietary fibers have been shown to offer potential health benefits to the
gastrointestinal tract. Mechanisms proposed for these dietary fibers beneficial effects include but not
limited to the control of gastric emptying and ileal brake (satiety effect), hypoglycemic response
(diabetes), plasma cholesterol levels (cardiovascular disease) [70].
T a b le 4
T y p ic a l N u tr itio n a l c o n te n t o f M C C ( p e r 1 0 0 g ) .

N u tr ie n t C o llo id a l A v ic e l P o w d e r e d A v ic e l

T o ta l C alo r ie 20 cal 0 cal


T o ta l fa t 0 0
T o ta l d ie ta r y fi b er 93 g 98 g
S o lu b le d ie ta r y fi b e r 5g 0g
Su gar ND ND
P r o t e in ND ND
V ita m in A ND ND
V ita m in C ND ND
S o d iu m 934 m g 4 mg
Ir o n 0 .5 m g 0 .2 4 m g
C a lc iu m 2g 0 .1 m g
A sh 2g 1g

A d o p te d fr o m F M C , N D = n o t d e te c te d .

Table 5.1. Typical nutritional content of MCC (per 100g); adopted from FMC . ND = not detected [49]

18
However, the mechanisms controlling the positive nutritional and health effects may vary according to
fiber type. This is because each dietary fiber has distinct physicochemical properties, which define its
functionality. Additionally, distinct fiber-based processes occur in the gastric, small intestinal and large
intestinal environments, with significant biological cross talk between the sites [70].

5.3.1. Safety of microcrystalline cellulose


According to the Select Committee on GRAS 9 Substances, microcrystalline cellulose is generally regarded
as safe when used in normal quantities: “There is no evidence in the available information on [substance]
that demonstrates, or suggests reasonable grounds to suspect, a hazard to the public when they are used at
levels that are now current or might reasonably be expected in the future.”[71]
MCC are reported to be chemically in chemically inert, not absorbed systemically 10 following oral
administration as well as nonhazardous and non-irritating (table 5.2).

Table 5.2 Material safety data sheet (MSDS) of the microcrystalline cellulose (MCC) [4]
9
GRAS (Generally Recognized As Safe) is an FDA (Food and Drug Administration) certification for products circulating with
stringent safety requirements. Only a few are FDA approved and recognized as safe under GRAS. For GRAS ingredient uses, the
extra added element is the general recognition required that the available safety evidence is both widely known (e.g., available in
the published literature or in commonly accessible knowledge sources such as text books) and that there is a consensus among
qualified experts about that evidence in support of the safe use of the material in food. In fact, the GRAS criteria are in some
ways more difficult to satisfy because of the additional requirement of public availability of the data and general recognition and
acceptance of a safety conclusion based on those data [126]. Currently, in the FDA's GRAS list, there are only nearly 500
approved food additives.
10
Systemic absorption: Systemic chemicals or drugs are absorbed into the whole of an organism such as a plant or person, rather
than being applied to one area (Collins Dictionary).
19
5.3.2. Hypoglycemic, hypolipidemic effects and plasma cholesterol levels control
In summary, the possible underlying mechanisms of health benefit, specifically the hypolipidemic
and hypoglycemic actions of MCC in the body relate to the following:
 Prebiotic effect, which modulates gut microbiota and increases host metabolism (This content will be
further discussed in 5.3.3).
 Dietary energy restriction due to dilution of nutrients by the fiber. For slow digestion, more of the
nutrient uptake will take place towards the end of the small intestine. This can result in a hormonal
response, known as the ileal brake [72], which sends signals to slow gastric emptying and thereby
limit nutrient losses to the large intestine.
 Improved viscosity of GIT content due to the fiber influences. The viscosity and viscoelasticity of the
small intestinal content are increased by the presence of the MCC. Viscosity could influence glucose
absorption by several mechanisms which can be cumulated: slowing of gastric emptying, decrease of
the accessibility of alpha amylase to its substrate (starch), slowing of glucose absorption produced
from starch hydrolysis (due to a slowing of glucose diffusion and an increase of the unstirred water
layer at the surface of the small intestine) [73].
 Increased fecal excretion and intestinal bile acid due to the increased hydrophobic interactions
between bile acids and MCC, together with induced MCC viscosity of the digesta. Moreover, MCC
viscosity causes a down regulation of enzymes involved in lipid synthesis, while those responsible for
ileal apical sodium dependent bile acid transporter and intestinal bile acid binding protein were up-
regulated [54]. Serum cholesterol is also used for bile acid synthesis. Therefore, the increased bile
acid excretion and subsequent hepatic synthesis from cholesterol can lead to the reduced serum
cholesterol concentration [73].
 Improved hydrophobicity due to its crystalline nature.
Apart from viscosity, it is possible that fat and bile acid binding abilities of MCC may be due to its
increased hydrophobicity as a result of its crystalline component. Modification of crystalline cellulose
to increase hydrophobic interactions with bile acids has been reported in literature. When
investigating the interactions between amphiphilic microfibrillated cellulose and bile salts, Zhu et al.
(2015) reported optimum chemical structure of hydrophobic modified microfibrillated cellulose for
bile binding. They noted that binding capacity of the modified polymer to bile acids due to the
hydrophobic interactions significantly increased to optimum as the chain length of the alkyl
substitutes (R2) increased to chain length of C16 [74].

MCC, with insoluble fiber (less fermentable cellulose) making up the majority of the composition, would
affect lipid metabolism mainly by lowering cholesterol 11 [73], [75]. Recent studies on hypolipidemic
effects of MCC demonstrated better cholesterol lowering ability of the crystalline cellulose.
Hypocholesterolemic and hypoglycemic effects of MCC have been studied, both in vivo 12 and ex-vivo13
models.
E.g:
MCC-potato starch composites exhibited better antilipidemic effects in rats compared to other fiber
composites, when the effects of five different fiber composites on obesity-induced rats were evaluated
[76].

11
By contrary, Inulin, a soluble DF selectively stimulating bifidobacteria growth, could increase SCFAs production, reduce food
intake, and modulate lipid and glucose metabolism in populations with metabolic disorders. The reduction in gut acetate-to-
propionate (A:P) induced by inulin supplementation would decrease liver lipogenesis [127], [128].
12
In vivo refers to a type of experiment that is carried out within a whole, living organism, such as a plant or animal.
13
Ex vivo means ‘outside of a living body’ in Latin and refers to methods wherein living tissues are taken directly from a living
organism rather than created artificially, and testing is carried out on them with very minimal changes to the tissue’s natural state.
20
Golden Syrian hamsters fed either freeze-dried ground pizza, pound cake, or hamburger and fries fortified
with MCC greatly increased fecal excretion of saturated and trans fatty acids [77].
In their study of the effects of different particle sized MCCs on lipid metabolism using ovariectomized
rats14, Lu et al. (2015) demonstrated that MCC extracted from sweet potato residues exhibited better
hypolipidemic effects, in contrast with the control groups with the effect being more pronounced in
smaller particle sized MCC fed rats [78].
Studies on hypoglycemic effects of MCC in vitro in human are very limited. However, in pigs [79] and
rats [80], MCC reduced blood glucose significantly. According to Takahashi et al. (2005), the viscosity
and viscoelasticity of the small intestinal content of rats were increased by the presence of the MCC [80].
The increase in viscosity and viscoelasticity of the gastric, small, and, cecal contents from rats were also
reported in vitro [81]. The authors concluded that MCC reduced the rate of absorption of glucose by
retarding diffusion within the lumen by increasing digesta viscosity.

5.3.3. Prebiotic effect


MCC is indigestible in the upper GIT (cannot be degraded by digestive enzymes secreted by human and
animals) but partially fermentable in the colon to produce short chain fatty acids (SCFAs) [82]. For
instance, when rats were fed with both high fat and low fat diets supplemented with MCC, appreciable
quantities of SCFAs were observed during the analysis of the cecal SCFAs [82]. Analysis of in vitro
fermentation of adult rabbits cecal content fed on MCC isolated from alfalfa hay, produced significant
levels of SCFAs [83].

The products of the cecal fermentation of MCC are mainly SCFAs [83], [84] as well as other metabolites,
such as lactate, pyruvate, hydrogen and succinate [85], similar to the products of highly fermentable
soluble prebiotics. Short chain fatty acids, produced by the fermentation process, is predominant acetic,
propionic and n-butyric and gases [73]. In vitro cecal content fermentation of adult rabbits fed on MCC
isolated from alfalfa hay yielded CH 4, H2 and CO2 gases, similar to the gases produced by inulin, fructo-
oligosaccharide, and guar gum during other in vivo studies [86], [85], [87], [82].

Human nutrition studies have shown that SCFAs produced by gut microorganisms have health effect not
limited in gut epithelium but also lipogenesis and carcinogenesis in other tissues [88].

 SCFAs can be utilized by intestinal epithelial cells as energy resources [89], [90] and also serve as
signal molecules to interact with G protein-coupled receptors (GPRs)15 to regulate appetite,
endocrine function, metabolism and immunity. Less fermentable cellulose would affect lipid
metabolism mainly by lowering cholesterol.
 SCFAs may activate the enteroendocrine cells of the gut to secrete a host of metabolically active
peptides that regulate satiety [91].
 Moreover, butyric acid producing bacteria are of interest because of their health-promoting effects
butyric acid is considered to be a major energy source for colonocytes (colonic mucosa), has been
implicated in protection against colitis and colorectal cancer [82], [92].
 The SCFAs produced by MCC are believed to modulate the motility by exerting a trophic effect
on the epithelial cells, thereby elevating the blood flow in the region [93].

14
An ovariectomized rat (OVX) is a female rat whose ovaries have been removed.
15
G protein-coupled receptor (GPCR), also called seven-transmembrane receptor or heptahelical receptor, protein located in
the cell membrane that binds extracellular substances and transmits signals from these substances to an intracellular molecule
called a G protein (guanine nucleotide-binding protein) [129].
21
The ability of crystalline cellulose to undergo fermentation in the cecum, however, depends on its
physicochemical properties. Recent findings revealed that the reduction of sweet potato cellulose particle
size to MCC and NCC fiber powders effectively enhanced the physicochemical properties and
consequently improved its physiological and biological effects [58].
In vitro fermentation of MCC and NCC demonstrated that the smaller particle size cellulose elevated
SCFAs production better than that ofthe larger particle size ones (MCC) [78], primarily due to the better
physicochemical properties of the smaller particles size samples [94].

A common feature associated with highly fermentable soluble fibers is the production large of large
volumes of gases. Depending on the doses ofthese gases, they might create unwanted symptoms such as
flatulence bloating, and cramps [87], [93]. The low solubility and tight packing of the glucose polymers in
MCC reduces its fermentability by the colonic microflora, leading to less gas production compared to the
highly soluble fibers such as inulin and guar gum [86]. This suggests that MCC could be prebiotic with
less associated unwanted symptoms.
5.3.4. Bowel movement and constipation
MCC may also have a role in the possible prevention of colon carcinoma as well as to their regulatory
effect on dimensions, consistence and speed of intestinal transit [95].

Reduction of particle size of crystalline cellulose from micro to nano level increased the specific area,
water-holding capacity, swelling capacity, and oil-holding capacity of the cellulose crystals [94]. In the
colon, the relatively low fermentable crystalline cellulose absorbs water and improves fecal bulking. Its
swellability is due to the absorption of only a small fraction of water that is able to penetrate the individual
MCC particles, causing them to swell, with the remaining bulk of the water existing in free state between
the particles [28].

In order to move the more viscous and viscoelastic intestinal content containing dietary MCC, more
pressure is needed in the intestinal lumen [96]. Increased viscosity and viscoelasticity by MCC in the
small intestine increased the pressure during segmental contractions and peristalsis in rats and increased
the water potential and stimulated water absorption [80]. Greater proportion of propulsive duodenal
contractions and antral motility index are associated with the consumption of meals fortified with MCC,
due to the higher pressure and water potential created by the fiber [96].

Intestinal dysbiosis, characterized by an imbalance between undesirable and beneficial bacteria with the
undesirables dominating, relates positively to chronic constipation [97]. The imbalance may affect the
movements of the large intestine via alteration of the metabolic environment of the colon. The pH of the
colon with higher levels of undesirable bacteria is higher due to the reductioninthe production of
physiologically beneficial compounds such as SCFAs [98]. The imbalance may be corrected by probiotics
or symbiotics and dietary fibers with prebiotic effects such as MCC, that stimulate the growth of the
desirable colonic bacteria (e.g lactobacilli and bifidobacteria). SCFAs, is proven to be effective on the
modulation of intestinal motility by exerting a trophic effect on the epithelial cells, thereby elevating the
blood flow in the region. Among the SCFAs, Soret et al. (2010) observed that butyrate is the preferred
energy source for the colonic mucosa cells and has positive effects on mesenteric neurons and motility in
rats [99].

22
5.3.5. Obesity management
Hypoglycemic and hypolipidemic effects of food are important in the management of obesity and diabetes
mellitus. The important functions of dietary fibers in body weight maintenance and overall health is
increasingly recognized so daily dietary recommendation of >25 g for healthy persons has been given by
WHO. However, it is generally recognized that various dietary fiber types vary greatly in their
physicochemical characteristics and hence may differ greatly in their physiological effects [100].
Adel and El-shinnawy stated that novel composite of natural plant origin as MCC–potato starch is fully
inactive in the stomach and will not dissolve in any water volume so it will give fullness feeling in the
stomach (control of satiety) and prevent eating. In addition, it has a physical not chemical action as its
bulk forming where it has no caloric contribution because it is indigestible by digestive enzymes with no
chemical interaction with drugs[76]. Moreover, as a dietary fiber MCC can delay gastric emptying,
modify intestinal absorption of biliary salts, influence lipidemic and glucose metabolism [56].
Using obesity induced mice, Li, Guo, Ji, and Zhang (2014) qualitatively demonstrated differences in the
capabilities of dietary fiber types to suppress high-fat diet induced obesity, and reported that insoluble
fibers were more effective in suppressing high-fat induced obesity than soluble fibers [101]. Similarly,
Adel and Elshinnawy (2012) observed that rats fed on MCC-potato composites had the lowestfood
consumption as well as the most decrease body weight when they evaluated the effects of five different
fiber composites on previously induced hyperlipidemic rats [76]. The addition of MCC in the diet of
experimental ovariectomized rats significantly decreased body weight gain compared with the control
group [78]. The smaller particle-sized MCC reportedly produced the highest weight loss when four groups
of rats were fed with high fat diet supplemented with MCC of unequal particles size [78].
6. Application of microcrystalline cellulose in processed food
Microcrystalline cellulose (MCC) has been widely used in food and beverage industry for its special
techno-functional properties and health benefits (figure 6.1).
MCC possesses the merits of cellulose. It has a high potential to be used in several areas such as
pharmaceutical, cosmetic, food and polymer composites industries.
In the powder form, it is employed, for instance as a binder and filler in food, medical tablets, and
particularly as reinforcement agent in the development of polymer composites.
In the colloidal form, MCC is utilized as a suspension stabilizer, a water retainer, a viscosity regulator, and
emulsifier in different pastes and creams.
Features like lightness, stiffness, strength, fibrous nature, non-toxicity, water insolubility, crystallinity,
biodegradability and renewability make MCC more attractive to be used in miscellaneous industrial fields.

23
Figure 6.1. MCC with fundamental roles as functional foods and dietary fiber [49].

6.1. Stabilizes the ice cream system


Ice creams are complex food systems and often require low levels of stabilizers (usually 0.1–0.5%) to
achieve good stability and other relevant functions [102]. Polysaccharides including MCC been
recognized as good stabilizers of ice creams and its roles in ice creams have been discussed in detailed by
some authors [102]. MCC may be used alone or in combination with other polysaccharides in ice cream to
achieve specific functions including stability and ice rheology. MCC gel has successful applications in ice
cream stabilization and overrun control. In order to maintain the original structure of ice creams during
storage and distribution, the incorporation of 0.4% of MCC to ice cream caused a gelto form and also
improved the ice cream resistance to heat shock via the maintenance of the three-phase system of air–fat–
water in the product (Glicksman, 1986). In corporation of MCC in ice creams also allows the increase of
solid content of the product as well as a source of dietary fiber for consumers.
6.2. Fat substitutes or replacers and bulking agent
MCC has been successfully used as fat substitute or replacer in some selected food systems. Prior to use,
the material is often dispersed into aqueous medium and used to simulate fat in food system. A significant
amount of work has been conducted to reduce the amount fats in ground meat, frozen desserts, dairy and
baked products (Table 6.1). By virtue of its insoluble nature in water,the use of MCC as fat replacement
or substitution in food systems reportedly produced excellent results. Gibis, Schuh, and Weiss observed
that MCC could effectively replace up to 50% fat compared to standard product when they studied the
effect of MCC as a fat replacer on microstructure and sensory properties of fried beef patties. The authors
also noted that sensory evaluations of the MCC-based beef patties exhibited fat-like mouthfeel and were
generally acceptable to the panelists. In the fried beef patties, it was observed heated samples with MCC
had more juiciness than control and so had better fat-like mouthfeel [103]. Low-fat beef patty is prepared
by adding MCCs with different concentrations dispersed in water and then adding beef patty to reduce fat
(MCC is insoluble fiber and does not contribute calories to food. weight loss). According to a study when
adding MCC to food can increase moisture, reduce fat for beef patties makes beef pies softer and
significantly tastier. Low-fat pies with MCC content of up to 3% by weight reduce 30% of fat.

24
Table 6.1. Application and functonality of MCC in different processed food systems [49].

Weight lossa Forcea (N/g)


(g/100g)
Control 19.2 ± 1.60a 6.3 ± 0.58a
Control 90% beef 24.3 ± 1.64b 6.4 ± 0.14a
0.5 wt% Fiber 24.2 ± 3.04 b
6.5 ± 0.45a
1.0 wt% Fiber 22.4 ± 3.47 ab
11.3 ± 0.79b
2.0 wt% Fiber 21.3 ± 3.00a 10.7 ± 2.74b
3.0 wt% Fiber 19.1 ± 2.25 a
10.1 ± 0.28b
Table 6.2. Weight loss and texture analysis (firmness measured as penetration force) of fried beef patties
(mean ± standard deviation) containing 0-3 wt% MCC or CMC after heating and cooling down. a Means
with different letters are significantly different (p < 0.05) [103].

The authors explained that since MCC is largely crystalline with no net charge, it formed particle gel
network as an inert molecule and filled the gaps of the tight meat fiber network and MCC particles may
not cause any disturbance of the protein network during heating. In emulsified sausage, the cellulose
microcrystals positively impacted on the mechanical properties of the product by enhancing the firmness
of the final product due to its high compactibility in the meat matrix [104]. Apart from meat, MCC has
also been used to replace fats in emulsions, baked products, frozen desserts, mayonnaise, gravies and
sauce. For instance, a 60% of soybean oil emulsion had similar stability characteristics and rheological
properties as a 20% soybean oil emulsion containing 1–1.5% colloidal MCC [105]. Replacement of fat
with MCC gives a rich creamy texture in low fat sauces and dressings because the material is insoluble
and can mimic fat.
6.3. Wall material for encapsulation
Nedovic, Kalusevic, Manojlovic, Levic, and Bugarski have reported the use of carbohydrate polymers as
wall materials for encapsulation, because they are edible, biodegradable and able to form a barrier
between the core and surroundings [106]. de Barros, Lechner, Charalampopoulos, Khutoryanskiy, and
Edwards (2015) reported improved survival of probiotic cells during extrusion/spheronization as well as
excellent protection from gastric acid, when they fabricated MCC calcium cross-linked alginate as the
wall material [107]. The researchers also observed that efficient sphere disintegration and rapid release of
the probiotics in intestinal conditions could be achieved with the combination of MCC and sodium
alginate. Apart from protection of probiotics, other food bioactive components such as essential oils and
volatile compounds could be encapsulated to protect them from degradation and evaporation. MCC could
produce coats to provide protection for the sensitive bioactive food components against moisture, oxygen,
light and temperature due to their barrier effects [108]. Koupantsis, Pavlidou, and Paraskevopoulou (2014)
reported good shell formation with good protective ability of essential oils when they investigated the
25
complex coacervation of milk proteins using carboxymethylcellulose (CMC) and MCC as the wall
materials [109]. Sometimes a native material/hydrocolloid may be modified for use as a wall material for
encapsulation. For instance, during comparative study of different carriers on properties of spraydried
rosemary essential oil, Fernandes, Borges, and Botrel (2014) reported that modified starch and inulin
could be a good substitute for gum arabic. It is therefore important to note that since MCC is a
hydrocolloid with multiple hydroxyl groups, it could be modified for use as a wallmaterial. The surface
charges of MCC produced with sulfuric acid could be ideal for encapsulation of flavors by coacervation.
Additionally, the good thermal and barrier effects of MCC positions it as an ideal shell wall material for
encapsulates which are usually subjected to high thermal treatment [110].

6.4. Reinforcement of edible films


Generally, the application of edible films in food, particularly fresh farm produce is fundamentally
constrained by the need to address diverse properties and needs; cost, availability, functionality,
mechanical properties, attributes, optical behavior, barrier effects against moisture and gases and
resistance to microbes [66]. MCC isolated from variety of cellulosic sources have been used to form
composite films with clear improvements in the optical and mechanical properties and thermal stability
[111]–[113]. In their study of composite edible films fabricated with HPMC reinforced with three
different MCC nanoparticles. Bilbao-Sainz et al. (2010) investigated the mechanical and barrier properties
of the composite nanocrystals [114]. The incorporation of unmodified MCC led to appreciable
reinforcement of the HPMC matrix, regardless of the particle size. Additionally, the presence of MCC in
nano scale dimension(nanocrystals) obtained frombacteria cellulosenot only improved the mechanical
properties of gelatin nanocomposites film but also reduced the moisture affinity of gelatin [115].
Crystallinity was generally identified and accepted as the key property responsible for the mechanical and
thermal stabilities of micro/nano crystalline celluloses. Under such conditions, hydrogen bonds conform
the cellulose polymers in closed packed crystals, thereby enhancing the mechanical and chemical stability
of the material [53]. Cao, Chen, Chang, and Huneault (2007) reported that nano/micro scale dimension
particles of crystalline cellulose are favored as reinforcing fillers in polymeric matrices due to their good
mechanical properties with very high bending strength and stiffness (e.g. Young’s modulus of about 150
GPa)[116]. In the micro/nano-scale range, materials may present different chemical properties, which in
turn affects their optical, catalytic and other reactive properties [112]. Most grades of MCC have good
moisture sorption properties [52], [117] and therefore negatively influence films produced with only
MCC; less desirable water and gas barrier functions. The challenges of moisture and gas barrier function
inefficiencies are minimized when materials with excellent moisture and gas barrier properties but poor
mechanical integrity are combined with MCC particles to fabricate a composite film. The use of MCC in
edible coating has been rarely investigated and so very limited information is available. Suppakul et al.
(2010) indicated that cellulose-based coatings could prolong the shelf life and maintain the quality of fresh
eggs by three weeks compared to control, when stored at room temperature [113]. This suggests that fresh
horticultural products such as fruits and vegetables could also be protected using colloidal MCC to
prolong shelf life and slow down their deterioration rate.
7. Gaps and implications for future research
The application and trading of the cellulose have become a global business. Its applications are well
established across diverse areas creating continual demands for it globally. The over reliance and general
dependence of wood pulp as the major raw materials by many MCC manufacturers raises potential
environmental concerns in relation to deforestation. Though the literature reviewed clearly showered that
extensive works have been done in identifying new sources of MCC including agricultural residues, which
are relatively cheaper than wood, most of these research works have mainly concentrated on the extraction
methods and physicochemical properties of the crystalline celluloses with negligible emphasis on

26
industrial application (particularly, food). Hence, it will be an interesting area to consider in the efforts to
make these new sources more acceptable, particularly to the food and pharmaceutical industries, which are
the major users of MCC [49].
In the pharmaceutical industry, MCC is the most widely used excipient for production of tablets, due to its
unique characteristics of plasticity and cohesiveness when wet [1]. Also the fact that MCC forms
sufficiently hard tablets, which rapidly disintegrate making it more relevant in the pharmaceutical
industry. However, the material still has certain limitations, such as the slow release rate of bioactives with
low water solubility. To overcome these disadvantages, coprocessing of the MCC with other excipients
has been identified to produce mixed excipient with better functionality. Development of new colloidal
cellulose by coprocessing MCC with cheap and lesser-known dispersible materials for food applications
can potentially overcome the poor solubility of the material and improve its functionality in food product
development. According to the literature reviewed in this paper, it is obvious that MCC obtained from
wood and other plant sources is not purely (100%) cellulose. Traces of lignin, and other contaminating
polysaccharides may be present. However, the contribution of these traces of polysaccharides in the MCC
on functionality, particularly surface activity has not been reported. It would be interesting for future
research on the material to consider it [49].
Increasingly knowledgeable consumers expecting high food product quality have challenged food
scientists to innovate in product development. Primarily, the efforts are geared towards providing products
with enhanced organoleptic and sensory properties with a healthier image or extended shelflife, at reduced
production cost by incorporating less costly ingredient that give better manufacturing efficiency through
new processing technology. An area at the forefront of MCC research is the development of new
functional foods or nutraceuticals. Advances in the functional food industry have released potential
design-directed functional foods formulations using the cellulose based on its indigestibility as a dietary
fiber. Though MCC has no direct nutritional contribution, its presence in food has physiological effects
on gastrointestinal health. Notwithstanding, studies on nutritional and health effects of MCC remain
equivocal and less understood compared to soluble fibers. Therefore, with advancement modern
technology in food and nutritional sciences, the area presents opportunity for more scientific exploration
[49].
8. Conclusions
MCC has many applications in the food industry and has improved the quality of new products and their
properties. The ingredient is used as a fat substitute or replacer in meat products (sausages, beef patties),
baked (bread, cakes, etc.,) and emulsion based products, suspending agent for beverages and thickening
agent for emulsions and suspensions. The presence of MCC in these products not only impact mechanical,
and rheological properties of the final product for better textural, sensory and organoleptic attributes, but
also improve human health. While there are countless applications of MCC in food and beverages, its
places second to pharmaceutical uses as far its industrial consumption is concerned. As a dietary fiber, its
roles are recognized in the physiological functions of the gastrointestinal tract and its nutrient dilution
effect. Though widely accepted as a good source of dietary fiber, the literature reviewed seems to suggest
that the mechanistic understanding of MCC nutraceutical functions is not as fully understood as soluble
dietary fibers. It is also established that unlike most prebiotics especially soluble fibers, MCC has minimal
colonic fermentation in contrast with soluble dietary fibers such as inulin.

27
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