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Cellulose from sources to nanocellulose and an overview of

synthesis and properties of nanocellulose/zinc oxide
nanocomposite materials

Amjad Farooq, Mohammed Kayes Patoary, Meiling Zhang,

Hassan Mussana, Mengmeng Li, Muhammad Awais Naeem,
Muhammad Mushtaq, Aamir Farooq, Lifang Liu

PII: S0141-8130(20)30358-5
DOI: https://doi.org/10.1016/j.ijbiomac.2020.03.163
Reference: BIOMAC 15114

To appear in: International Journal of Biological Macromolecules

Received date: 12 January 2020

Revised date: 16 March 2020
Accepted date: 16 March 2020

Please cite this article as: A. Farooq, M.K. Patoary, M. Zhang, et al., Cellulose from
sources to nanocellulose and an overview of synthesis and properties of nanocellulose/
zinc oxide nanocomposite materials, International Journal of Biological Macromolecules
(2018), https://doi.org/10.1016/j.ijbiomac.2020.03.163

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© 2018 Published by Elsevier.

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Cellulose from sources to nanocellulose and an overview of synthesis and

properties of nanocellulose/Zinc oxide nanocomposite materials

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

a
College of Textiles, Donghua University, Shanghai 201620, China.

b
Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, China.

c
Key Laboratory of Eco-Textile, Ministry of Education, Jiangnan University, Wuxi, China.

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School of Automation, Nanjing University of Science and Technology, Nanjing 210094, China.

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*
Corresponding author Professor in College of Textiles, Donghua University, Shanghai 201620, PR China

Abstract
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Recently, environmental and ecological concerns are increasing due to the usage of petroleum-based
products so the synthesis of ultra-fine chemicals and functional materials from natural resources is
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drawing a tremendous level of attention. Nanocellulose, a unique and promising natural material extracted
from native cellulose, may prove to be most ecofriendly materials that are technically and economically
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feasible in modern times, minimizing the pollution generation. Nanocellulose has gained tremendous
attention for its use in various applications, due to its excellent special surface chemistry, physical
properties, and remarkable biological properties (biodegradability, biocompatibility, and non-toxicity).
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Various types of nanocellulose, viz. cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), and
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bacterial nanocellulose (BNC), are deeply introduced and compared in this work in terms of sources,
production, structures and properties. The metal and metal oxides especially zinc oxide nanoparticles
(ZnO-NPs) are broadly used in various fields due to the diversity of functional properties such as
antimicrobial and ultraviolet (UV) properties. Thus, the advancement of nanocellulose and zinc oxide
nanoparticles (ZnO-NPs)-based composites materials are summarized in this article in terms of the
preparation methods and remarkable properties with the help of recent knowledge and significant findings
(especially from the past six years reports). The nanocellulose materials complement zinc oxide
nanoparticles, where they impart their functional properties to the nanoparticle composites. As a result
hybrid nanocomposite containing nanocellulose/zinc oxide composite has shown excellent mechanical,
UV barrier, and antibacterial properties. The nanocellulose based hybrid nanomaterials have huge
potential applications in the area of food packaging, biopharmaceuticals, biomedical, and cosmetics. Thus

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the functional composite materials containing nanocellulose and zinc oxide will determine the potential
biomedical application for nanocellulose.

Keywords: Cellulose; Natural sources; Zinc oxide.

Graphical abstract

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Contents
1. Introduction ............................................................................................................................................... 4
2. Structure and properties of cellulose and nanocellulose ........................................................................... 6
2.1. Sources of cellulose and nanocellulose .................................................................................................. 7
2.2. Isolation of nanocellulose from cellulose materials ............................................................................... 8
2.2.1 Cellulose pretreatments .................................................................................................................... 8
2.2.1.1. Alkaline-acid pretreatment ....................................................................................................... 9

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2.2.1.2. Enzymatic pretreatment ........................................................................................................... 9
2.2.1.3. Pretreatment by ionic liquids ................................................................................................. 10

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2.2.2. Nanocellulose isolation techniques ........................................................................................... 10

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2.3. Types of nanocellulose ........................................................................................................................ 13
2.3.1. Cellulose nanofibrils (CNFs) ........................................................................................................ 14
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2.3.2. Cellulose nanocrystals (CNCs) ..................................................................................................... 14
2.3.3. Bacterial nanocellulose (BNC) ..................................................................................................... 15
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2.4. Applications of nanocellulose .............................................................................................................. 16

3. Metal and metal oxide nanoparticles (NPs) ............................................................................................ 17
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3.1. Metal oxide: Zinc oxide nanoparticles (ZnO-NPs) .......................................................................... 17

3.2. Preparation and properties of Zinc oxide nanoparticles ................................................................... 18
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3.3. Preparation of Nanocellulose/ZnO-NPs composites materials ........................................................ 20

3.4. Properties and applications of nanocellulose/ZnO-NPs composite materials .................................. 21
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3.4.1. Application in Food Packaging ................................................................................................. 22

3.4.2. Biomedical applications ............................................................................................................ 23
3.4.3. Ultra-voilet (UV) sensing Properties ........................................................................................ 24
4. Future Perspectives ................................................................................................................................. 26
5. Conclusion .............................................................................................................................................. 26
References ................................................................................................................................................... 29

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1. Introduction
The rapid growth of nano-technology, eco-efficiency, sustainability, and green chemistry are guiding
the considerable interest and attention in the development of a variety of materials, products, and
applications. About 150 years cellulose has been known which is a renewable and biodegradable polymer
and for a long time, it has been used as a source of energy, building material, and clothing. During the
last few decades, scientists are trying to explore the bio-based materials so that the dependence on fossil
fuels can be prevented [1] [2, 3]. In this regard, cellulose and its derivatives have attracted considerable
attention as cellulose is one of the world’s most abundant, environmentally friendly, biocompatible
materials, natural and renewable macromolecules on the earth, is extensively present in numerous types of

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biomasses [4]. Cellulosic materials have excellent properties such as higher surface area, lower density,
higher aspect ratio, better mechanical properties, low cost, and adaptable surface characteristics. An

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annual production of one trillion tones of cellulose and its derivatives are reported to have global market
about USD 1.08 billion by 2020 because of its increasing demand in textile, food, pharmaceutical

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industries [5, 6]. As agricultural waste is an important source of cellulose biomass, so several attempts
have been made to extract cellulose from various agricultural wastes [7], such as forest residues [8],
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cotton stalk [9], fruits wastes [10], corn husk [11], marine biomass [12] and rice straw [13]. The excellent
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structural characteristics including physical and mechanical properties (higher surface area, lower density,
high aspect ratio, and tensile strength) of nano materials extracted from cellulose fibers [14] have
increased the demand of nanocellulose materials. It is reported that nanocellulose has been used as filler
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which improves the mechanical properties of the materials, for example, physical properties [15, 16],
thermo-physical and barrier properties of carboxymethyl cellulose (CMC) biopolymeric films[16],
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chitosan [17], agar [18, 19], starch derivatives [19], poly (lactic acid) [15] and alginate[19] films.
Nanocellulose materials are also reported to be used in enzyme immobilization [20], sensors technology
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[21], automotive [22], and electronic devices [23].

Except to be used in improving the mechanical properties of the polymer films nanocellulose
materials have also been reported in functionalizing the materials. Nanocellulose materials and its
derivatives have been used in various applications simply by mixing with antibacterial nanomaterials and
functionalizing the resulted composites [24]. Cellulose and its derivatives have been acknowledged from
the literature to be used with metal and metal oxides, for example, ZnO, TiO2, MgO, ZnO, CuO, Ag, and
Fe3O4 as mentioned in [25-28]. Recently, the industrial and medical reputation of these metal and metal
oxide nanoparticles (NPs) have obtained more consideration. Accordingly, anticancer, antimicrobial, anti-
diabetic and wound healing activities of ZnO-NPs were designated by plenty of studies, so the synthesis,
properties, and potential applications of nanomaterials containing nanocellulose/Zno-NPs with the recent
studies are the main objective of this review.

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The excellent properties of ZnO-NPs are caused by a relatively low cost of production, antibacterial
properties, chemical stability, reactive oxygen species (ROS), and photo-catalytic abilities [29, 30]. Since
relatively uniform absorption of ultraviolet light (UV) and visible light properties, zinc oxides were
reported to be widely used in papers, paints, and plastics industries [31]. The composite containing
nanocellulose and zinc oxide NPs compounds exhibited excellent catalytic performance, high
antibacterial activity, and better electrical conductivity, while they also have been reported to enhance the
UV-barrier properties, thermal stability values, and antibacterial activities of biopolymer films [32].
Similarly, the safety of ZnO particles was approved by the U.S. Food and Drug Administration (FDA)
(21CFR182.8991).
Nanocellulosic materials have been applied usually to be used as a substrate to fabricate nano-sized

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metallic particles [33]. In case of CNC suspension and metallic salts, the presence of electrostatic

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interaction between metallic particles and oxygen atoms of hydroxyl groups caused the metallic nano
particles to be adsorbed on the surface of CNC [34]. Surface modification of nanocellulose can be

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functionalized easily due to existence of plenty of hydroxyl groups through surface modification.
Renewable films of nanocellulose crystals and zinc oxide was prepared having blockage of ultraviolet
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light about 98.5% and thermal activation energy was also increased by adding 5 wt.% ZnO [35].
Nanocellulose having UV barrier, antibacterial, higher thermal, and antioxidant properties are generally
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functionalized by two ways: first technique is to modify nanocellulosic materials surface by oxidation or
cationization of the hydroxyl group of nanocellulose [36]. The approach used in a second technique is to
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form a hybrid with metal nanoparticles especially ZnO-NP, Ag-NP, CuO-NP and Fe3O4-NP imparting
functional properties, where nanocellulose materials are used as a template [37, 38]. In this method
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abundant hydroxyl groups on the nanocellulose act as a template itself and a capping agent for the
preparation of hybrid nanocellulose/metal oxide NP [39]. One-pot route synthesis of CNC/ZnO
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nanohybrid materials was done [40] as compared to earlier reported complex and time taking processes
[34, 41-43], exhibiting stronger antibacterial activity than the CNCs and excellent photo-catalytic activity.
Antibacterial effect of cellulose nanocrystals and zinc oxide nanohybride materials has been explored on
dental resin composites. Results exhibited that small amounts of CNC/ZnO nanohybrids have a great
influence on antibacterial and mechanical properties of dental resin composites [44]. Cellulose metal
oxide composite of ZnO was synthesized and results for photocatalytic degradation behavior of
methylene blue were studied using zinc oxide, cellulose, and ZnO-cellulose composites. The results
revealed that the composite was one of the best catalysts as maximum decolorizing effectiveness occurred
in less than 120 min with 50mg, 20 ml of ZnO catalyst dose for 20 ppm of the methylene blue solution
[45].

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About the last decades, a lot of review articles, research papers, and several book chapters have been
published, concentrating on the application of nanocellulose as a reinforcing agent in a variety of areas.
Similarly, an article on the nanocellulosic material usage for metal NPs support and their catalytic
reactions application has also been reported [37]. But until now only a few articles on multi-functional
composite containing nanocellulose and zinc oxide nanocomposite materials have been published [46,
47]. The present review paper will focus on cellulose and nanocellulose types, structure, sources and
production as well as the synthesis and properties of multifunctional nanocellulose and zinc oxide
composite, and their excellent potential application in various fields. The study is compiled with the help
of plenty of recent research articles, review papers and book chapters [48-51].

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2. Structure and properties of cellulose and nanocellulose
Cellulose, an environmentally friendly substance is a linear series of glucose molecules forming a

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flat ribbon-like structure. The repeated unit contains of two anhydroglucose rings combined together
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through an oxygen, which is covalently bonded with one glucose ring C1 and C4 of the adjacent glucose
ring (1-4 linkage) [52]. The degree of polymerization (n) generally varies from 10,000 to 15,000, where n
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is dependent on the source of cellulose material. The presence of hydrogen bonding between hydroxyl
groups and oxygen atoms of the adjacent ring molecules stabilizes the linkage between them, causing in
the linear conformation of the cellulose chain.
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Cellulose is situated within the plant fiber walls. Fibers obtained from different plants have different
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shapes and dimensions. Fibers extracted from bast plants and cotton are long, having length in the range
of centimeters, while wood fibers are short (1–3 mm in length). Fibers obtained from cotton are twisted,
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whereas fibers from wood are generally untwisted and subjected to linear when delignified [53]. Bast
plant (ramie, flax, etc.) fibers are straight along longitudinal direction and polygonal along transverse
direction. Usually, the capillary covering most of the length of the fiber is called lumen. Cellulose fibers
comprise of various dislocations and defects such as cracks, compression failures, pores, thin places, and
other points of damage. That defects and disorders are the weak points for mechanical forces and
chemical attack. The width of various plant fibers vary in the range of 15–30 μm, including the lumen.

Generally, the cell wall of the various plant fiber has a thickness of 4–6 μm and comprises of
primary (P), secondary (S), and inside tertiary (T) walls. The primary and tertiary walls of the plant fibers
are thin (~100 nm). The nanofibrillar packs of the primary and tertiary walls procedure disordered nets.
The secondary (S) wall has a thickness of 3–5 μm , which is composed of three layers (S1, S2, and S3).

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The core layer in the cell wall is the S2 layer that is typically 2–4 μm. The S2 layer covers nanofibrillar
bundles and lamellas, locating parallel to each other and positioned under an acute angle towards the fiber
axis [54]. This typical orientation imparts the increase of mechanical properties of cellulose fibers. The
lamesllas of cell wall comprise of elementary nanofibrils having lateral size 3–15 nm and length of 1 μm,
that nanofibril contain well-ordered nanocrystallites and disorderly nanodomains particles. The
crystallites length range between 50 to 150 nm, while the lengths of disordered domains vary between 25
to 50 nm, depending on the different types and sources of cellulosic materials [53]. Fig. 1 shows the
network of microfibrils in plants.
Majorly there are four different polymorphs of cellulose: cellulose I, II, III, and IV which can be
transformed from one to another by chemical and thermal treatments. Cellulose I is a native cellulose,

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which is found into two allomorphs Iα and Iβ. Cellulose II is the most stable crystalline form also named

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as regenerated cellulose, which is obtained by the process of mercerization or re-crystallization [55]. The
major difference between two forms of cellulose is dues to the arrangement of their atoms, for examples,

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cellulose II is packed in antiparallel direction while cellulose I in parallel direction. Cellulose III is
normally obtained by treating Cellulose I and cellulose II with ammonia respectively, similarly cellulose
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IV is produced with the modification of cellulose III by heat treatment at 260 oC [56]. The cellulose fibers
can be evaluated using either controlled acid hydrolysis or mechanical shearing, resulting in yielding
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diff erent structural properties according to the approach mentioned in [57]. Cellulose fibers converted
into their nanoscale units but comparatively longer such as several micrometers, called CNF [58]. Due to
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acid hydrolysis, cellulose fibers disintegrate into their highly crystalline, rod-like and nanometer-long sub
structural units named as CNCs. The nanosized biomaterial can be biosynthesized via a bottom-up
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approach using microorganisms and is known as bacterial nanocellulose (BNC).

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Fig. 1.

2.1. Sources of cellulose and nanocellulose

Cellulose as one of the most abundant biopolymer is considered to be an increasing demand for
biodegradable and biocompatible products estimated that annually about 1010–5×1010 tons of lingo-
cellulosic materials have been produced [61, 62]. Out of this tremendous production, about 6×109 tons of
cellulose is processed by industries such as textile, paper, and chemical industries [52]. Internationally
researchers are trying to yield the valuable resources of nanocellulose, by efficiently managing bio-waste.
Biomass includes various natural organic materials especially refering to the plants and plant-based
materials which are the largest promising resources for the sustainable production of biochemical. Forest
production of crops and agriculture residues are also considered as biomass for cellulose and nano

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cellulosic materials production [63]. A large number of studies have been done to extract CNF and CNC
from a variety of bio-resources, including hardwood and softwood [64-66], bamboo [67, 68], sugar beet,
cotton [69], potato tubers [70], soybean stock [71, 72], banana rachis [73], and agricultural wastes [74].
Table 1 shows the various sources of nanocellulose. CNF were extracted from Australian native
“spinifex” grass (Triodia pungens) with small diameter (<8 nm) and high aspect ratio (>500) by applying
the powder form conditions and then passing through the process of ultra-high pressure homogenization
[75]. Cotton is also another major source of nano cellulosic material. Habibi et al [76] extracted
nanoparticles from cotton having dimensions as length reported from 70 to 300 nm and width 5 to11 nm.
Cellulose extraction for the CNF production by ball milling through waste corncobs was done by using
single step mechanochemical esterification reported by Kang et al. [77]. Pandey et al. [78] obtained CNF

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using newspaper waste as the cellulosic material sources due to significance of environmental and
economic reasons.

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Table 1.

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Due to excellent properties, several attempts have been made to extract BNC by using submerged
fermentation process. Bacterial nanocellulose can be extracted in various culture media using carbon
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sourcing from glucose, agricultural wastes, fructose, and saccharified food waste, and nitrogen from
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peptone yeast extracts. Generally, that process is performed using typical shaken or static flasks or jar
fermenters placing any bacterial strains such as Gluconacetobacter hansenii, Acetobacter xylinum,
Gluconacetobacter xylinus, Gluconacetobacter, and Acetobacter. Table 2 shows the various culture media
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used to produce bacterial cellulose. Usually, acid hydrolysis of bacterial cellulose is done to extract the
BNC. To get the desired yield and dimensions of the bacterial nanocellulose reaction conditions are
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maintained by optimizing acid concentration, temperature, sonication duration and reaction time, the
BNC production rate usually varies between 0.01 and 0.31 g L− 1 h− 1 [101, 102].
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Table 2.

2.2. Isolation of nanocellulose from cellulose materials

2.2.1 Cellulose pretreatments
Cellulose is occurred in nature as assemblies of individual cellulose long chain-forming fibers,
instead of an isolated molecule aligned in a hierarchical order. Several individual cellulose particles make
one large unit called as proto-fibrils (elementary fibrils) that are packed into larger sections, generally
named as microfibrils [118]. Plants, the natural major source of cellulose are consist of cell walls
cellulose molecules and other closely packed polysaccharide moieties, which results in a complex
morphology of the cellulose fibers. The presence of various hydroxyl radicals (which participated in

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hydrogen bonding) in the long chains of cellulose is evident from the glucose and cellobiose structures
presented in plants [119]. The individual entities of tightly packed material can be obtained only by
overcoming the interfibrillar hydrogen-bonding energy existing between them. Only one type of H-
bonding is evidenced in cellulose, so a limited amount of energy can be used to quantify the hydrogen
bonding strength, which is 19 and 21 MJ kg−1 mol−1 as reported in [120]. Chemical or enzymatic
pretreatments help to reduce energy consumption for cellulose fibers.

2.2.1.1. Alkaline-acid pretreatment

In this pretreatment process, the biomass is treated mostly with an alkali like sodium hydroxide or
potassium hydroxide. The chemical treatment process is famous for the surface modification of natural

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fibers which involves the removal of hemicellulose, lignin, extractives, and waxes. The procedure for this
treatment is explained in several reports; as also mentioned in our recent publication [121]. Alkali

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treatment causes fibrillation and swelling of cellulose fibers, giving an increase in surface area and
ductility [122]. Similarly, the chemical modification of natural fibers has also been widely reported by

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using silanes, the basic process involved in this treatment is the self-condensation followed by the
reactivity of the siloxane toward the OH-groups of natural cellulose fibers [123]. The alkaline-acid
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pretreatments were also engaged before mechanical isolation of nanocellulose to remove lignin,
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hemicellulose, and pectin [71, 80], which usually involves the following three steps [124]:
(1) Waterlogging of the biomass natural fibers in NaOH (12–17.5 wt%) solution for 2 h to make it
susceptible to hydrolysis by increasing the surface area of the cellulosic materials.
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(2) Hydrolyzing of the fibers is done with hydrochloric acid (HCL) solution at 60–80°C, which
causes to solubilize the hemicellulose material.
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(3) Fibers treatment with NaOH (2 wt% ) solution at about 50-75 °C to interrupt the lignin structure.
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2.2.1.2. Enzymatic pretreatment

Enzymatic pretreatment is a biological treatment that used for modification of biomass cellulose
fiber by degrading the non-cellulosic (lignin and hemicellulose) contents. Enzymes used for this
pretreatment process are cellobiohydrolase, endoglucanase, and cellulase. In this pretreatment process,
enzymes are used in the assistance of the restrictive hydrolysis of several particles or the selective
hydrolysis of specified elements in the cellulose fibers [125]. The enzymatic treatment mechanism is
complex, but the enzyme action is based on the catalysis of the H-bonding linkage between cellulose
microfibers [126]. As a single enzyme can’t degrade all the cellulosic fibers because it comprises several
organic compounds, so a set of selective cellulose enzymes which is reported in [127] can be summarized
as (1) Cellobiohydrolases: A- and B-type cellulases effectively attack especially on the crystalline
cellulose; and (2) endoglucanases: C-type and D-type cellulases required a disordered structure in

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cellulose fiber to attack. Under mild conditions, generally, the reaction time required for enzymatic
pretreatment is much higher as compared to the acid hydrolysis process [125]. Several reports [128, 129]
have been done for the CNF production by using enzymatic pretreatment processes. Enzymatic hydrolysis
combined with homogenization and refinement to obtained nanocellulose materials from softwood pulp
selective and mild hydrolysis using a mono-component endoglucanase enzyme allowed a greater aspect
ratio and was less aggressive compared to acid hydrolysis.

2.2.1.3. Pretreatment by ionic liquids

Ionic liquids have nonflammable, lower vapor pressure, and higher thermally stability properties, as
well as lower melting temperature (below 100°C). Except for alkali-acid and enzymatic pretreatments,

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ionic liquids have also been extensively reported to be used [130-132], to dissolve cellulosic materials by
using an ionic liquid 1-butyl-3-methylimidazolium chloride, after that high-pressure homogenization was

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used to isolate nanocellulose fibers from sugarcane bagasse. Generally, the power of the microwave,
reaction time, temperature, and the weight ratio of cellulose to ionic liquid have a great influence on the
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2.2.2. Nanocellulose isolation techniques
After the chemical purification of natural biomass materials, the second process is the conversion of
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purified cellulosic content to nanoscale particles (CNC or CNF) by using several techniques especially
acid hydrolysis and mechanical treatments separately or in a combination of the various methods to obtain
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the desired characteristics of the nanoparticles [134-136]. Mechanical methods are followed by chemical
treatments to decompose or remove the amorphous material or partially functionalize the particle surface.
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To break the hydrogen bonding of interfibrillar materials, major preprocessing steps applied are: the
partial removal of the matrix material, and the chemical treatments. The appropriate pretreatments of
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cellulosic material promoted the accessibility of hydroxyl groups, increased the crystallinity and inner
surface area, and broke the cellulose fibers hydrogen bonding and therefore, increased the reactivity of
obtained fibers [136]. Similarly, the interfibrillar repulsive forces of the never dried materials increase by
imparting a charge to the surface of the fibrils using either adsorption of charged polyelectrolytes (such as
carboxymethyl cellulose treatment) or through oxidation (2,2,6,6-tetramethyl-piperidinyl-1-oxyl radical
selective oxidation) [50, 76]. Several mechanical approaches to convert cellulose fibers into nanofibers
particles are high-pressure homogenizers [137], cryo crushing [138], microfluidization [139, 140], and
high-intensity ultrasonic treatments [141, 142].

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2.2.2.1 Mechanical treatments

During mechanical treatments, the grinding, shearing, and forces generated which causes the basic
techniques for nano cellulosic material production. Karande et al. examined the refining process of
cellulose nanofibrils extraction [143]. Nakagaito et al. evaluated the nanocellulose fibrils properties from
pulp fibers using a high-pressure homogenizer as the diameter of 20-100 nm and length of about tens of
micrometers. Similarly, by using the homogenization technique the dimension change (an increase of
length and reduction in diameter) of cellulose fibers is acknowledged [144]. As well as CNF extracted
from wood pulp having a diameter between 20 to 90 nm has been reported by using a super grinding
method [145]. Subsequently, high strength ultra-sonication is used to isolate CNF by oscillating power
(hydrodynamic forces of ultrasound ) [146]. Generally, ultra-sonication techniques are used after

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biochemical treatments such as TEMPO oxidation [147]. In cryocrushing technique cellulosic fibers are

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immersed in liquid nitrogen and subsequently crushed by using a grinder, CNF materials can easily be
extracted from frozen cellulosic fibers due to cell wall rupturing during high impact forces exerted

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pressure by ice crystals [148, 149]. Similarly steam explosion process is also reported to be used for the
extraction of cellulosic material by hydrolysis of hemicellulose and depolymerization lignin [150, 151].
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For CNF production there is another method recently used, named as ball mailing method, in which the
cellulose suspension is placed in the cylindrical container (partially filled with metal, ceramic, or zirconia
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balls). During container rotation, cellulose fibers are disintegrated into small particles by high energy
collisions between the balls. CNF structural properties depend on the ball sizes and ball-to-cellulose
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weight ratio, using softwood kraft pulp 100 nm nanocellulose fibrils were obtained [152].

2.2.2.2. Acid hydrolysis

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The first isolation of CNC using sulfuric acid was reported by Rånby and co-workers in 1949 [153].
Later on hydrochloric acid, phosphoric acid, maleic acid, and bromic acid were used [154, 155].
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Fabrication of CNC by chemical treatment methods using hydrochloric acid and sulfuric acid is the most
common method used for decades [50, 76, 156]. For this method extracted cellulose material is subjected
to de-ionized water and followed by prescribed addition of sulfuric acid. After the specific reaction time,
the final mixture is filtered, centrifuged, and washed against clean water for a neutral pH of the
suspension [157]. A series of publications have been done to figure out the optimal conditions of the acid
hydrolysis process like reaction time, temperature and concentration of the acid. Optimal conditions of
hydrochloric acid concentration was found as 64% (w/v) with a liquor ratio of 1:8.75 at a specified
reaction conditions (1 h reaction time, 45°C temperature, and 5 min ultra-sonication) [50]. Revol et al.
[158] reported the surface charged sulfate esters production by using sulfuric acid, which caused to avoid
CNC aggregation in the solution and promoted the CNC dispersion in H2O. Sulfuric and hydrochloric

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acids combination during hydrolysis of CNC is reported to produce sphere-shaped nanoparticles with
enhanced thermal stability values due to fewer sulfate groups on their surfaces.
Time, temperature, and acid concentration of hydrolysis reaction are the major influencing factors
regarding the structural and dimensional properties of the obtained fibers. The reaction condition was
experimentally determined on several types of cellulosic materials, optimal conditions are: 65% (wt)
sulfuric acid concentration, 20–70°C reaction temperature, and the hydrolysis time varies between
30 minutes to overnight (depending on the reaction temperature) [159]. Cellulose nanocrystals from
coconut husk fibers with diameters 5 nm and aspect ratio up to 60 obtained by sulfuric acid hydrolysis
process were acknowledged in the report [93].

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2.2.2.3. TEMPO oxidation method
TEMPO-mediated oxidation was initially applied with polysaccharides like amylodextrin, starch,

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and pullulan [160]. Subsequently, it became the most commonly used method for CNF extraction; the
process involved the carboxylate and aldehyde, functional groups, onto the cellulose structure by using an

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oxidizing agent like sodium hypochlorite (NaOCl) in the presence of 2,2,6,6-tetramethyl-1-piperidine-N-
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oxy (TEMPO) radical and iodine or a bromide as catalyst under adequate conditions [161-163]. During
this process oxidation only occurs in the hydroxymethyl groups (C6 primary hydroxyl) of the
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polysaccharides. Because of the topological structure of the cellulose fibers, the surface of the cellulose
chains only oxidized [164]. The nature of cellulose fibers is much dependent on the products obtained
after the TEMPO oxidation. When mercerized or regenerated celluloses are used for TEMPO oxidation,
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generally, the obtained oxidized products are water-soluble β-1, 4-linked polyglucuronic acid sodium salt.
But native cellulose maintained their fiber structural properties after TEMPO-mediated oxidation even
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under severe process conditions [165]. ). As in this case, the oxidation followed only at the surface of the
microfibrils, which gave a negative charge to them and resulted in repulsion of the nanofibers particles,
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thus fibrillation of cellulose occurred easily. The alteration in structural and physical properties (length,
morphology, thermal stability, crystallinity, etc.) of nano-cellulosic materials prepared by two distinct
methods TEMPO-oxidation and sulfuric acid hydrolysis comparison was acknowledged in [166-168].
Similar study involves in the effectiveness of the isolation methods using mechanical, enzymatic, acid
hydrolysis and TEMPO-mediated oxidation methods was also done by Sacui et al. [134]. Fig. 2 shows the
various isolation methods of nanocellulose materials.
In 2006 Oksman et al. and his co-workers used an N, N-DMAc solvent system with the addition of
LiCl to swell microcrystalline cellulose for the first time [169]. Later on, with the boom of
nanotechnology, a number of researchers have fou`nd ultrafine cellulose fibers by means of electro-
spinning of cellulose solutions, which was elaborated under a strong direct current-induced electric field

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by extrusion of the concentrated polymer solution from syringe-type needle [170-172]. Similarly,
cellulose nanoparticles were also obtained with the addition of non-solvent material in the solution
containing agitated cellulose [173].

2.2.2.4. Ammonium persulfate (APS) method

Most recently, instead of TEMPO-oxidation and acid hydrolysis methods a novel, one-step oxidation
technique named ammonium persulfate (APS) method was used to extract nano-cellulosic materials[174].
APS method has non-toxic, higher water solubility and low-cost properties which can generate CNC from
cellulose fibers by eliminating the amorphous region and providing the carboxyl group at the C6 position
[174, 175]. The single-step process of CNC extraction by the APS method is a less harmful sustainable

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process as compared to acid hydrolysis which can also be applied to remove hemicellulose, pectin, and
lignin of the biomass materials. Overall the main mechanism of the APS method relies on the oxidation

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and hydrolysis of cellulose fibers by disintegrating the amorphous regions of the cellulosic materials with
the formation of free radicals (SO4), hydrogen peroxide (H2O2), and HSO4 [176]. For the dissolution of

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cellulosic materials, several other solvents have been reported to be used such as ionic liquids, metal
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solutions, hydrates of molten inorganic salt, alkali/urea, NaOH aqueous solution, and NaOH/thiourea
aqueous solution [177-181]. The main mechanism of cellulosic material dissolution during these
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processes relies on the reduction of intermolecular hydrogen bonding between the cellulose particles to
obtain a cellulose polymer solution.
Fig. 2.
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In NaOH/urea system, OH-ions and amino groups provided by NaOH and urea respectively, interact
directly via hydrogen bonding but there is no interaction between urea and cellulosic material [182]. For
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instance when cellulose particles thawed in NaOH/urea system, NaOH hydrates develop new hydrogen
bonds (relatively stable) in cellulose molecules, and urea “hydrates” bounded the cellulose molecules
(NaOH hydrogen-bonded) to build an inclusion complex as sheath-like structure [183].

2.3. Types of nanocellulose

The lignocellulosic biomass usually has firmly packed nanocellulose consisting of some crystalline
region, which gives the strength to the cellulose fibers, meanwhile the amorphous regions contribute to
the flexibility of biomass cell wall [76]. Cellulose fibers are composed of outstanding physical and
mechanical properties due to various hydroxyl groups and strong hydrogen bonding networks. Actually,
nanocellulose is cellulose owing to the shape of crystals or fibers having several hundred nanometers in

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length and less than 100 nm in diameter [184], which can be extracted by various methods from natural
cellulose [51]. Generally, nanocellulose materials are categorized into three main types, named cellulose
nanocrystals (CNC), cellulose nanofibrils (CNF), and bacterial nanocellulose (BNC) [76, 185] extracted
by various techniques. CNF is generally obtained by distracting the cellulosic fibers using mechanical
treatments, for example, ultra-sonication, ultra-homogenization, grinding and wet grinding treatments
[178, 186]. It is worth noticing that there is considerable inconsistency in the denominations and
terminology of all those products obtained from cellulose dictated by sources of raw materials and
processing methodologies. Since there is not any single term universally applied to define “nanoscale
cellulose”, we will illuminate three types of produced nanocellulose and their exclusive properties.

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2.3.1. Cellulose nanofibrils (CNFs)
CNF can be expressed as a natural cellulosic material, consists of high-volume and large surface area

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cellulose fibers, having diameter 20-60 nm and several micrometer lengths [187, 188]. According to the
approach used in [187], CNF extraction process involved disrupting cellulosic fibers along an axis by

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using mechanical means such as ultrahigh friction grinding, high-pressure homogenization, wet grinding,
cryogenic cooling and ultrasonic treatments combined with chemical and enzymatic pretreatments [178,
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186]. Usually mechanical methods are involved with different pretreatments like phosphorylation [189],
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enzymatic hydrolysis [190, 191], carboxymethylation and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)

oxidation [66]. TEMPO oxidation is the most commonly used pretreatment method for CNF extraction.
The resulting product of CNF is aqueous suspension that demonstrates gel-type properties. The basic
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properties of obtained CNF depend on the natural source of the cellulose materials. Similarly, the methods
employed vary the degree of crystallinity, the intensity of fibrillation, morphological and structural
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properties of the resulting CNF [192]. Generally, CNF obtained from primary cell wall fibers are longer
and thinner as compared to those which are attained from the secondary cell wall of natural fibers. CNF
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has resulted from various sources of natural cellulose including corn husk [193], cotton stalk [9], and rice
straw [74], soft and hardwoods [194, 195], sugar beet pulp [196] and banana [197, 198]. Nanocellulose
materials evaluation by Transmission electron microscope (TEM) is shown in Fig. 3.
Fig. 3.

2.3.2. Cellulose nanocrystals (CNCs)

Cellulose nanocrystals are whisker-shaped material isolated by the biosynthesis process from
cellulose, also nominated as cellulose nano-whiskers with gorgeous domains of crystalline regions [198,
201]. During acid hydrolysis a larger proportion of the amorphous regions is removed and due to
excellent crystallinity, CNC is regarded as highly rigid as compared to CNF [202, 203]. They are also
known as nanorods [204], nanowhiskers [205], and rod-like cellulose crystals [206], which are generally

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resulted by acid hydrolysis from cellulose fibers. Usually, a method applied to extract the CNC particles
involves the pretreatment processes (alkali and bleaching treatments). Subsequently, after applying the
controlled conditions of reactions such as temperature, agitation, and acid hydrolysis washing of the
supernatant is performed with deionized water (centrifugation, and ultra-sonication). The resulted
suspension may further be subjected to freeze-drying or spray-drying techniques to obtained the pure
CNC materials. Sulfuric acid (64 wt%) is the most commonly used acid for the preparation of CNC
particles. Both the reaction conditions such as the nature of the acid and the source of cellulosic material
have a great impact on the obtained properties of CNC, for example, aspect ratio, degree of crystallinity,
structural and morphological properties, and size and dimensional dispersity [76]. They show relatively
width of 3-50 nm and length varies between 100 nm to several micrometers [207]. CNC particles are

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highly crystalline materials varying from 54-88% in crystallinity and are 100% cellulose with higher
thermal stability value (∼260°C), larger aspect ratio (10 to 70), and lower density value (1.5-1.6 g/cm3)

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[52, 208-210], as acknowledged in Fig. 4, adopted by various literatures.

2.3.3. Bacterial nanocellulose (BNC)

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Fig. 4.
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BNC is another type of nanocellulose differed from CNF and CNC particles, synthesized from several
bacterial species such as Gluconoacetobacter (e.g., Acetobacter xylinium) species within several days
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cultivation in aqueous culture media containing carbon and nitrogen sources [58]. Those bacteria are
capable of altering glucose into cellulose materials through a bio-fabrication assembly process [212].
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Glucose is used as a carbon source, peptone as nitrogen, yeast extract as vitamin, citric acid, and disodium
phosphate are used as a phosphate buffer for the medium. Even with similarities to CNF and CNC, BNC
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has native cellulose I crystal structure with high molar mass, a higher degree of polymerization, higher
crystallinity, similarly, have the ability to form an extremely ultrafine web structure that allows them to
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not to be dispersed in water [213-215]. BNC is regarded to have higher Young's modulus value (78 GPa),
higher molecular weight (8000 Da) and reported to have excellent water holding capacity [216, 217]. The
advantages of bacterially derived cellulose microfibrils are as lightweight, non-toxic as well as
controllable microfibril formation and crystallization by adjusting bacterial culture conditions, as
compared to nanoscale cellulose extracted from natural plants that required chemical treatments to
eliminate the lignin and hemicellulose material [218, 219]. Because of excellent characteristics such as
hydrophilic activity and outstanding interpenetrating nature with host tissue BNC is extensively used in
biomedical applications [220-222]. In addition, biomedical materials have claimed attention because of
the increased interest in tissue engineering materials for wound care and regenerative medicine [223].
Various terminologies used for different types of nanocellulose materials from open literature as
mentioned in

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Table 3

2.4. Applications of nanocellulose

There are plenty of application areas for nanocellulose-based materials derived from natural
resources (agricultural, biomass, and forestry residues) showing extensive and inclusive prospect in daily
life (Fig. 5). The envisaged applications comprise plastics, papers, food industry, automotive, and
building sectors used nanocellulose as strength additives in nanocomposites materials, food additives, and
barrier or coating applications. Similarly in cosmetics, medicine, pharmaceuticals sectors, organic LEDs,
photonic films, recyclable electronics, and 3D-printing nanocellulose are used as a novel and emerging

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material having excellent photonic and electrical properties. All applications of nanocellulose are
associated to their excellent properties, including nontoxicity, lightweight, dimensional stability, better

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thermal conductivity, higher thermal stability, environmentally friendly, recyclable, reusable, and
biodegradable [225].

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The optical, mechanical, and gas barrier activities of nanocellulosic materials have been well-
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studied, bringing them to a developed phase in terms of their applications. Outstanding CNC mechanical
properties such as excellent optical activities, higher strength (7450-7500 MPa) and better stiffness (135–
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155 GPa) have increased reinforcement applications (coating, nanocomposites, papermaking, additives,
etc.) with other polymers such as polypropylene, carboxymethyl cellulose (CMC), poly(lactic acid) [226-
228] as well as for extensive applications in food packaging [229]. On the other hand nanocellulose
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materials having better thermal conductive characteristics [230] are acknowledged to be used in various
applications especially in biomedical applications [231] and as a supporting agent in metal nanoparticles
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in catalysis [37] as well as for excellent ultraviolet properties [49, 232, 233].
Fig. 5.
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Nanocellulose materials are used in producing low-calorie foods for handling weight disorders [234,
235], as well as used in producing highly porous materials with higher tensile strength such as
nanocellulose papers, films, and aerogels for varied purposes [236, 237]. The capability of nanocellulose
to produce porous aerogels and strong transparent films is currently attracting the attention of the
researchers to utilize in new domains such as electronics and medicine. Isogai et al [238] prepared a
transparent nanocellulose (TEMPO-oxidized) film exhibiting extensive properties like modulus of
elasticity as 7 GPa and higher tensile strength of 200 - 300 MPa. Similarly nanocellulose fibers extracted
by TEMPO-oxidation method was also reported in composite films acting as reinforcing agent with
polyurethane, chitosan and poly (lactic acid) [239, 240]. TEMPO-oxidized cellulose nanofibrils have been
reported to be used in various forms such as: in sponge (alginate-based) as cross-linking partner [241],

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acting as a carrier for biological active molecules [242], producing in transparent nano papers [167], as
well as in gases (NH3, CO2) adsorption and exclusion (Cu II) applications [175, 243]. Recently,
nanocellulose particles in printing applications have become the subject of increasing study. Researchers
found that CNF material could improve the ink density and the quality of print when it was subjected to
be used as a coating agent to enhance the print quality of synthetic fiber sheet [244-246]. Because
nanocellulose fibers show outstanding heat-transfer properties and transparent due to the tightly-packed
structure as compare to glass [247]. In food packaging, oxygen barrier properties of the material used in
packaging film play an important role, and it was reported that CNF contributed to the impermeability of
oxygen molecules in packaging material [248-250].

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3. Metal and metal oxide nanoparticles (NPs)

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Metallic nanoparticles have involved the research community since more than a century. Their
unique excellent characteristics including electronic, catalytic, optical, and antibacterial properties are the

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major reasons for wide applications of metal NPs in various fields [251]. Due to the synthesis process,
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NPs vary in different shapes like a triangular, spherical, rod, polyhedral and cubic. For inorganic NPs,
MNPs/MONPs such as Ag, CuO, TiO2, ZnO, MgO, and Fe3O4 are more essential because of their various
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applications in medical and nonmedical technologies [252, 253]. Among all of them CuO, ZnO, and Ag
NPs are more attractive as they have plenty of potential applications in various fields (medical, polymers,
biosensors, ceramics, biomedical and healthcare products). Similarly, excellent antibacterial and UV
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barrier properties of CuO, ZnO, and Ag-NPs have directed it to be used in biomedical and food packaging
applications [254-256]. Ions release from metal and metal oxides are the main antibacterial mechanism
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that leads to stop the bacterial growth. In addition, ZnO-NPs and TiO2 can generate reactive oxygen
species which leads to radicals stress in bacteria [257].
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3.1. Metal oxide: Zinc oxide nanoparticles (ZnO-NPs)

Among metal oxide, Zinc oxide (ZnO) is increasingly accepted as environmentally friendly, non-
toxic, low cost, and abundant in nature material which is reported to exhibit photocatalytic activity and
higher quantum efficiency than TiO2 in certain circumstances [258]. The high surface reactivity of ZnO
leads to a plenty of native defect sites rising from oxygen non-stoichiometry, which gives it excellent
photocatalytic property as compared to other metal oxides [259]. ZnO shows comparatively higher
mineralization rates and reaction activities [260] and can create hydroxyl ions more efficiently than
titaniam (TiO2) [256, 261]. Zinc oxide nanoparticles are not toxic to human cells and also have been
reported in various research studies to exhibit UV blocking properties, antibacterial activities and high
photocatalytic properties [262]. The higher photocatalytic properties of zinc oxide nanoparticles lead to a

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photo persuaded oxidation process that can extinguish and inhibit organisms by creating oxidation
process species such as H2O2 and superoxide ions O2 [261, 263]. As zinc oxide particles involve the
disruption of membrane activity, destruction of DNA, and oxidizing the bacterial proteins, resulting in an
excellent antimicrobial activity. ZnO-NPs antibacterial activity depends on various factors such as
particle size, surface area, shape, surface charge, electronic states, roughness and surface energy [264,
265]. The practice of ZnO-NPs is toxic to some specific species of algae and plants [266, 267]. A lot of
studies on the toxicity of ZnO-NPs on Staphylococcus aureus and Escherichia coli have found that the
growth of E. coli was completely inhibited when the concentration of ZnO NPs ≥3.4 mM, and S. aureus
was inhibited at ZnO NPs ≥1 mM [268]. The comet evaluation of ZnO-NPs on Allium cepa root meristem
cells demonstrated that the smaller ZnO-NPs were more toxic as compared to the larger ones (Demir et

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al., 2014). Moreover, toxicity increased with the increase of ZnO-NPs concentrations. The survival rate

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of Dunaliella salina cells reduced to below 50% when ZnO-NPs ≥25 mg/L, but no major effects were
detected at 0-5 mg/L [269]. Similarly, when the concentration of ZnO-NPs in the cells of

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Pseudokirchneriella subcapitata increased upto 0.1 mg/L, the inhibition rate growth increased more than
90% after 72 hours exposure [270] In the same way, the genotoxic effects of 35 nm ZnO-NPs on Allium
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cepa reported that the DNA tail rate and the tail moment improved from 43% and 31.46 μm to 71% and
79.26 μm after exposing to 100 μg/L and 1000 μg/L, respectively [271]. When Chlorella sp. exposed to
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ZnO-NPs solution were the survival rate was 75%, 70% and 60% at the end of 2nd, 4th and 6th day [272].
The nanoparticles with small size show large interfacial area and can certainly penetrate into the
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bacterial membranes, increasing their antibacterial effectiveness. Several ZnO-NPs having similar surface
area but various types of shapes may have different active facets, which can lead to improving the
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antimicrobial activity, such as it has been stated that one-dimensional zinc oxide particles (i.e., rods and
wires) enter into the bacterial cell walls better than spherical shaped ZnO-NPs [265]. The outstanding
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antibacterial and UV properties of ZnO-NPs have encouraged the researchers to prepare antimicrobial
fabric preparation and poly(vinyl chloride) coatings for antibacterial packaging preparation [273, 274].

3.2. Preparation and properties of Zinc oxide nanoparticles

Zinc oxide nanoparticles have been a subject of huge research owing to their multifunctional
properties in multiple applications. ZnO-NPs have appeared as a potential candidate for applications in
energy harvesting, sensors, and several electronic devices, in which biomedical and antiviral areas are
prominent applications. This is because of their potential biocompatibility as compared to other metal
oxides, excellent solubility in alkaline solutions, and the Zn–O terminated polar surfaces [275]. During
synthesis, through various methods, ZnO nanoparticles properties can be changed by dimensions such as
size and shape, resulted in renewable potential applications relevant to their structural properties. Mostly,

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the synthesis methods are adopted according to the desired applications, as different techniques produce
different sizes and structural morphologies of ZnO particles. Similarly, physical and chemical parameters
(pH, temperature, precursors, solvent type, etc.) were highly considered. A variety of zinc oxide
nanoparticles have been reported to synthesis with different morphologies (Table 4) such as nanoneedles,
nanorods, nanotubes, nanosphere, and nanorings as acknowledged in [27]. Similarly, snowflakes, rod-
like, prism, and flower-shaped morphologies of zinc oxide nanoparticles were synthesized at a higher
temperature (~180℃) for 13h [33]. The spherical surface ZnO-NPs were prepared by a non-hydrolytic
(solution) process using zinc acetate dehydrate [276]. Accordingly, in another investigation spherical
shaped ZnO-NPs [277] were prepared using soft chemical solution method, and synthesized ZnO-NPs
were examined against bacteria such as P. aeruginosa, B. subtilis, and S. aureus as well as cancer cells

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(MCF-7, HepG2 cell lines). ZnO-NPs of various sizes and shapes such as quasi-spherical, hexagonal,

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rod-shaped and spherical were synthesized by a green synthesis method using plants like Anisochilus
carnosus [278], Plectranthus amboinicus [279], and Vitex negundo [280]. Results compared the size

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ranges using various techniques like field emission scanning electron microscopes (FE-SEM),
transmission electron microscopy (TEM), and X-ray Diffraction (XRD) which clearly indicated that by
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increasing the concentration of a plant extract, the dimensions especially size of synthesized nanoparticles
decreases [280-282]. Zinc oxide nanoparticles synthesized from leaves and flowers of Vitex negundo
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displayed the similar size of 38.17 nm as confirmed by XRD analysis obtained through Debye-Scherrer
equation [278]. For the green synthesis of zinc oxide nanoparticles leaves of plant Azadirachta indica of
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Meliaceae family have been most generally reported to be used [282].

While Stankovic´ et al. [283] reported hydrothermally ZnO powder production by using alternating
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stabilizing agents leading to different nanostructures. ZnO particles obtained through this method have
displayed hexagonal pyramidlike, hexagonal prismatic, ellipsoid, and spherical structures. In another
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effort [284] ZnO nanowires were extracted in heterojunction of silver-loaded ZnO using through UV light
decomposition techniques. Zinc oxide particles thus obtained show excellent antibacterial activity against
E. coli through disrupting the bacterial membrane.
Table 4.

ZnO-NPs exhibit good polarity, that possess difficulty in uniform dispersibility in nanocellulosic
materials, thus for excellent properties of the nanocomposite materials proper synthesis methods must be
adopted and structural properties of the ZnO-NPs should be cleared. Fourier-transform Infrared
Spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), as well as
scanning electron microscope (SEM) and transmission electron microscopy (TEM) have much
importance to understand the structural and morphological properties of nanoparticles [290]. Fig. 6
shows various forms of ZnO nanoparticles and its XRD and XPS analysis results.

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Fig. 6.

Various forms of ZnO particles were obtained as nanoparticles, nanorods and nanoflowers by
controlling the experimental conditions using microwave assisted aqueous solution techniques. Fig. 6
shows various forms of ZnO particles exhibiting similar peak positions, but nanorods own high intensity
because of comparatively higher values of crystallinity due to the controlled experimental conditions.
SEM shows that nanoparticles of ZnO have approximately irregular size, spherical shapes, and smooth
surfaces. But, nanoflowers ZnO samples have six petals developed in the medial part of the respectable.
Nanorods ZnO has biggest crystallite size as compared to nanoparticles and nanoflowers coming from the
experimental conditions. Crystallite size of ZnO particles, nanoflowers and nanorods was calculated as

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18.6 nm, 23.9 nm and 46.2 nm respectively by using Scherrer's formula [291]. Several reports show the
importance of the controlled morphology of ZnO-NPs for various applications [292-294]. Advantage and

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disadvantages of various synthesis procedures of Zinc oxide nanoparticles are as follows in Table 5.
Table 5

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3.3. Preparation of Nanocellulose/ZnO-NPs composites materials
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Several methods have been established to prepare nanoparticles hybrid composite material using
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metal or metal oxides nanoparticles and nano-cellulosic materials especially:

1. Cellulose and metal oxide nanoparticles mixing without using any external reducing elements,
2. By using an external reducing agent with metal/metal oxide-NPs and CNF particles,
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3. Nanoparticles composite materials synthesis without any reducing agent,

4. Nanoparticles preparation by chemical surface modification of nano-cellulosic materials as
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shown in Fig. 7.
Simple mixing of two nanomaterials i.e, CNF or CNC in already prepared zinc oxide nanoparticles
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suspension is reported in [301]. This technique is quite simple but uneven nanoparticles of zinc oxides in
cellulosic materials may aggregate during the drying process [41]. Generally, various methods of
nanocellulose/ZnO composite preparations are reported including: electro-spinning, sol-gel, ultrasonic,
precipitation, pulsed laser deposition, spray pyrolysis, which allows the particle size of ZnO-NPs between
20 to 40 nm, while other methods such as hydrothermal and microwave methods provides larger sizes of
ZnO-NPs particles [46]. Different cellulose and cellulose derivatives such as cellulose nanocrystals,
spherical cellulose, nanocrystals regenerated cellulose, cellulose fibers and cellulose acetate have been
used for the preparation of multifunctional cellulose/ZnO-NPs [302-304]. For nanocellulose/ZnO
composite preparation usually, chemical methods are preferred to physical ones because of simple
equipment used, milder reaction conditions, and facile scale-up. Generally, zinc ions are formed either
from ZnO, or in situ, from zinc precursors, such as zinc chloride (ZnCl 2), zinc nitrate hexahydrate

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(Zn(NO3)∙6H2O), and zinc acetate dihydrate (Zn(CH3CO2)2_2H2O). The size of zinc oxide particles has
great impact on the nanocellulose/ZnO composite materials, for example, ZnO-NPs prepared by zinc
nitrate water solution by precipitation technique exhibited rods-shape alignment having size of 25 ± 5 nm,
with an inter-planar d-spacing of 0.246 nm confirming the (1 0 1) planes of the hexagonal wurtzite
arrangement, impregnated efficient properties over nanocellulose fibers [305]. The differences concerning
the sizes of the ZnO-NPs are ascribed to the distinct surface coordination mechanisms when various types
of amines are engaged. It’s still a matter of deep discussion since many of the kinetic and thermodynamic
variables are considered to evaluate the effect of the solute precursors on the dimensions and structural
morphology of the obtained zinc oxide nanoparticles. One of the major reasons regarding the size of ZnO-
NPs preparation is the purity of the prepared NPs. It is obvious that pharmaceutical and biomedical

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applications require high purity nanoparticles.

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Fig. 1.

3.4. Properties and applications of nanocellulose/ZnO-NPs composite materials

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Since nanocellulose materials have unique mechanical and barrier properties, and metal and metal
oxide nanoparticles have photocatalytic properties, antimicrobial activities and ultraviolet barrier
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properties, so the nanohybrid materials with multifunctional properties containing
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nanocellulose/nanometal particles has attracted much attention in many areas such as catalysis
applications, electronics and sensors, nano-composite films, pesticides detection and biomedical applications
as shown in Fig. 8 [306-308].
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Fig. 8.

Zinc oxide is documented as an impressive inhibitor and bactericide agent toward a broad spectrum
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of Gram-negative and Gram-positive bacteria. ZnO-NPs incorporated with cellulosic fibers show
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excellent antibacterial activity against Escherichia coli, on lighting with 543 nm, 1000 lx (~0.1464
mWcm-2) light. ZnO-NPs can be detected antibacterial activity even in the absence of light, showing that
antimicrobial activity is caused by hydrogen peroxide (H2O2) generated from ZnO [305]. Recently,
researchers have evaluated the effect of CNC concentration, reaction conditions, and manufacturing
settings during preparation of CNC/ZnO nanocomposites on the various properties such as dispersibility,
morphology, and antimicrobial activities of ZnO-NPs [309]. Azizi et al. [310] acknowledged the ability of
CNC as a new stabilizer when effectiveness of CNC ratio on ZnO-NPs size was examined. They observed
that CNC/ZnO-NPs showed higher antimicrobial activity against Gram-positive and Gram-negative
bacteria as compared to Zn-NPs alone. During the preparation of nanocellulose/ZnO-NPs composite,
concentration of sodium hydroxide NaOH and reaction conditions especially temperature played an
important role in the morphology and properties of ZnO-NPs [311, 312]. ZnO-Ag hetero-structure

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nanoparticles were also reported to increase the antibacterial activity of cellulose nanocrystals (CNC)
[313]. Similarly, composite materials containing cellulose nanocrystals/ZnO as a multifunctional
nanofillers for poly(vinyl alcohol)/chitosan blend films were prepared to improve the antibacterial
properties, higher mechanical properties, crystallinity, and UV-barrier properties [309]. Composite films
composed of TEMPO-oxidized CNF (100 μm, 200 μm) particles and polyethylene glycine (PEG) using
different ratios (5% PEG for 100 μm, 10% PEG for 200 μm) was used to load ZnO NPs (size less than
100 nm). Shefa et al. evaluated that the film containing 5% PEG had less bleeding time as compared to
the one 10% PEG [24]. Similarly, heparinized carboxymethyl cellulose (CMC), ZnO-NPs and Polyvinyl
alcohol (PVA) nanocomposite hydrogels result in cell viability value up to 83% for the human dermal
fibroblast (HDF) and mouse fibroblast cells (L-929) [314]. Fig. 9 shows possible antibacterial activity

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caused by nanomaterials.

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Fig. 9.

The suitable oxygen permeability of the composite material is another major factor that is considered

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in wound dressing production. A combination of ZnO-NPs in Mesoporous silica NPs such as MCM-
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41/carboxymethyl cellulose hydrogels have excellent results showing swelling as 100%, gas permeability
as 500%, and excellent antimicrobial activities against E. coli and S. aureus [316]. Table 6 shows the
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synthesis techniques, and properties of nanocellulose/ZnO-NPs.

Table 6.
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3.4.1. Application in Food Packaging

There is highly increase of studies to use the novel and efficient polymeric materials for food
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packaging materials[335]. The reports in a study revealed that the food packaging materials established
with nanotechnology are the largest group of current nanotechnology applications for food sector [336].
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Food packaging is incredibly desirable to protect food materials from various exposures. Recently, new
progress aims to enhance the barrier properties to avoid microbiological infections of food [337].
Moreover, renewable and recyclable materials are highly considered to improve the sustainability of
packaging using metal or polymer coatings. Current developments in food packaging materials have
focused on high performance barriesr using minimum amount of material [338]. So, there is a need of
functional coatings of biodegradable cellulosic materials for special or enhanced properties in the field of
food packaging applications. Currently, Zinc oxide is listed as safe material by the Food and Drug
Administration and is also used as a food additive. ZnO is an inorganic compound extensively used in
daily life applications. The production of ZnO-NPs commercially is currently achieved by two ways: (1)
Physical vapor synthesis and (2) Mechano-chemical processing (Casey, 2006). However, there are also
some other works involving some steps like chemical reactions with several precursors and synthesis

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methods; precipitation, thermal decomposition and hydro-thermal synthesis have also been used widely.
Generally, the food industry practices ZnO as a source of zinc, which is considered as an essential micro-
nutrient and assists an important and critical role in development, growth, and well-being in human and
animals as reported [339]. ZnO-NPs have been incorporated with different polymers to improve the
properties of the nano-composites resulted in the improvement of barrier and mechanical properties as
well as heat resistance properties when compared with the original polymers itself or conventional
composites [340]. Cellulose (extracted from renewable sources) and its nano-composites, and modified
materials such as films (modified by metal oxides, food pigments, and chemical pigments) are highly
considerable materials that have recently been used [341-343]. Since composites formed by inorganic
particles and organic polymer materials with nanoscale sizes have improved a lot of their functional

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performance in comparison with noncomposite forms [344]. A composite containing bacterial cellulose

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(an interesting ecofriendly biomaterial), zinc oxide (an excellent semiconductor metal oxide with a 3.47
eV band gap), and polypyrrole (a famous conducting polymer) has been prepared and considered as a

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suitable candidate for applications in smart packaging in the food industry [345]. Also, the addition of
ZnO and cellulose nanocrystal hybrid nanofillers with poly(3-hydroxybutyrate-co-3- hydroxy valerate)
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(PHBV) has been examined and reported to efficiently improve the light-response and thermal properties
of PHBV films [346].
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3.4.2. Biomedical applications

The usage of non-conductive polymers such as cellulose, polythiophene and polypyrole are getting
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more attention. Cellulose is quite important as it has been used in various fields such as wood and paper,
clothes and fibres, pharmaceutical and cosmetics sectors [347]. Metal nanoparticles associated with the
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vegetable cellulose as semi-conductors have been severely increased in recent years [348]. That type of
composites are highly useful due to having high galvanostatic cycling stability, sensitivity, better thermal
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strength, ion absorption capability because of their respective application such as flexible energy devices,
nano-fibrous membrane, bio or gas sensors [349]. Those types of composite are biocompatible, fully
nontoxic, and biodegradable, mostly used in the healthcare products and formulation [350]. The polymer
composites are very advantageous over pure polymer due to insufficiency related to their applications
[222]. The citrus peels are reported as rich in source of cellulose, hemicelluloses, proteins and pectin in a
study, so the effective utilization of cellulose was done from citrus waste and synthesis of
pharmacologically important nano-composites containing zinc oxide is suggested to be exploited in
wound dressing; due to strong antimicrobial properties and healing effectiveness because of anti-oxidative
properties. Similarly, the nano-composite showed time dependent increase in photocatalytic behavior by
efficiently degrading methylene blue dye up-to 69% under sunlight irradiation within time of 90 minutes

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[351]. Similarly, impregnation of ZnO nanoparticles into bacterial cellulose sheets was tested and
confirmed for biomedical applications through various characterization techniques. The antimicrobial
properties of bacterial cellulose-zinc oxide nano-composites were tested against common burn pathogens
[352]. Hybrid nano-composites exhibited 90.9%, 94.3%, 90.0%, and 87.4% activity against Citrobacter
freundii, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa, respectively. Similarly,
nano-composites treated with animals showed significant (66%) healing activity. Through regenerated
bacterial cellulose and zinc oxide nanoparticles, biocompatible and nontoxic nano-composite films were
developed through a new technique which shows that animal cells effectively encouraged the
applicability of the synthesized composites in biomedical fields, as well as impressive enhancements in
the thermal, mechanical and bactericidal properties were also noticed [41]. Similarly, ZnO-NPs were

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shaped into a composite form by using biodegradable and biocompatible hydroxyethyl cellulose as a

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stabilizing agent through facile technique. The results of environmental friendly synthesis of
nanoparticles lead to a new generation of nanomaterial for treatment of diabetic complications [353].

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Recently, the nanocomposite films of CNF and ZnO nanoparticles showed greater antimicrobial ability
against Gram-positive Staphylococcus aureus, recommending the CNF/ZnO films can be used in a
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targeted biomedical application. Thermo-gravimetric results of CNF/ZnO films indicated that the
presence of ZnO had almost no effect on the thermal degradation properties of the composite [223]. The
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scaffolds of ZnO-NPs and CNF are also synthesized and proven to be degradable (in vitro) in nature due
to swelling and degradation nature of TEMPO oxidized CNF resulting in high blood absorption in
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significant bleeding inhibition [24]. TEMPO oxidized CNF and ZnO nanoparticles showed excellent
swelling capacity and the lower bleeding time which makes it outstanding candidate for being hemostatic
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agent preventing the spreading of bacterial infections due to presence of ZnO particles. Hashem et al,
have synthesized nanocomposite of carboxymethyl cellulolse-ZnO hydrogels by in situ formation of ZnO
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nanoparticles. The prepared nanocomposite hydrogels exhibited outstanding antibacterial activity to

gram-positive and gram-negative bacteria [354].

3.4.3. Ultra-voilet (UV) sensing Properties

Recently, polymers based metal oxides have been reflected as important materials duo to their
extensive range of applications like solar photo-catalysis, cells, waste water treatment, photo-detector and
sensors [355-361]. ZnO nanoparticles have strong UV response that generally depends on the morphology
and nature of the surface in case of ZnO films, and surface area and crystalline-size in case of powder
form. The ZnO nanostructure composite with suitable polymers can significantly enhance its activity in
sensors [362, 363]. It is well known that ZnO is an excellent UV photosensitive material [364-366]. The
strong photo sensitivity of ZnO is illuminated as an adsorption effect relating the ZnO surface and
atmospheric O2. During the process, when O2 is adsorbed by ZnO nanoparticles, the doping electrons

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contributing to electrical conductivity of ZnO are stuck and the reduction of charge carriers makes ZnO
less conductive [367]. ZnO is found to be highly photo-catalytic efficiency among all inorganic photo-
catalytic materials, and is much more biocompatible than TiO2 [368]. ZnO-NPs can highly absorb and has
greater response to UV light [263]. Recent reports have revealed that nano-composites of ZnO with
cellulose nano-fibers can improve the UV sensing properties of ZnO [49, 366, 369-371]. Similarly,
cellulosic materials possess some level of permeability to gases [372, 373]. Therefore, it is expected that
nano-composite materials containing cellulose fibers will have outstanding gas permeability. Meanwhile,
the use of cellulosic materials is strongly justified as it’s a kind of renewable, inexpensive, and abundant
material [133, 374]. Several studies have successfully reported the synthesis and utilization of nano-
composite materials used for sensors. Reports [375, 376] involved an important sensitivity improvement

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when active sensing nano-materials are inside of a supporting matrix. In the nanocellulose/ZnO-NPs

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nanocomposite, micro templates (i.e. nanocellulose fibers) play an important role for a controlled
development of narrow size ZnO nanostructures. Moreover, cellulose fibers are good binder that

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effectively binds the ZnO nanoparticles during pellet making. Several reports have mentioned about the
UV sensing activity of ZnO-paper based hybrid film composites [366, 370, 377, 378]. Similarly, there are
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many reports on the applications of CNF/ZnO-NPs nano-composites as UV sensors [49, 379]. A
technique was applied to fabricate a composite material prepared by compressing Zinc Oxide (ZnO)
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nanoparticles and cellulose fibers, the structural, electrical, and photosensitivity testing were done,
synthesized composite material showed excellent electrical photoconductivity changes when exposed to
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UV light [379]. The synthesis of UV sensing of a cellulose and ZnO hybrid nano-composite was done by
vertically aligning and growing well the ZnO nanorods on a flexible cellulose film using ZnO seeding and
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hydrothermal growing processes. Composite involves the advantages of cellulose in terms of

sustainability, flexibility, transparency, and low price as well as exploitation of synergetic effects of ZnO
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functionality; characteristic results proved that it can be used for wearable sensors that can detect the UV
component of sunlight with great sensitivity and stability [369]. The cost effective abundant polymer
cellulose fibers present in environment were utilized to synthesize nanocomposite of ZnO-cellulose
nanocrystals in a study for UV and humidity sensing, about ~20nm of ZnO-NPs were developed on the
surfaces of the cellulose fibers by a technique called one pot aqueous chemical bath deposition process.
Samples were porous in nature. The porosity of the materials was suitable for sensing of various
applications [317]. Zinc oxide-cellulose nanocomposite powder is reported to be synthesized by a low
cost, simple, and two step chemical methods by growing ZnO nanorods on the cellulose fibers (powder)
surfaces at different temperatures using aqueous chemical method for the fabrication of UV sensor. The
study revealed that cellulose was crucial for development of the porosity of the ZnO surface and a higher
porosity leaded to an improved absorption of UV radiation. Hence, the ZnO-cellulose nanocomposites

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were extensively anticipated for ultra-high sensitive UV sensors [49]. Through aqueous chemical
method 20-50 nm size of ZnO-NPs were grown on cellulose surfaces; low-cost synthesized nano-
composite materials had a higher UV sensitivity with faster response [319].

4. Future Perspectives
The utilization of ZnO-NPs is toxic to some species of algae and plants. Plenty of studies on the
toxicity of ZnO-NPs have found that the growth of Staphylococcus aureus and Escherichia coli was
completely inhibited. The noble property of significant toxicity of ZnO-NPs to organisms have made
ZnO-NPs successful applicant among various other metal oxides. The composite of ZnO-NPS could also

of
be used in various fields such as biomedical, healthcare, and electronic devices. Special focus on the
mechanism of toxicity like ZnO particle size, concentration, morphology, and surface modification can be

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given and powerful antibacterial results would be obtained for the various applications. The brief
presentation of this review conducted by the authors will be helpful in fruitful utilization of

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nanocellulose/ZnO-NPs nanocomposites in many fields. The composite of nanocellulose/ZnO-NPs also
has advantage compared to ZnO-NPs which can be used in antimicrobial, bioactive, and photo-
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luminescent papers as well as in functional devices and food packaging materials. As powder ZnO-NPs
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are easy to mix with other materials but it is extremely hard to made into a device or moulding by itself.
However, cellulose particles have the advantage to make into the shape of devices due to its suppleness.
The combining of ZnO-NPs and cellulosic materials would enable the composite of suppleness,
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fluorescence, and excellent antibacterial properties. Thus it will expand the application of both cellulose
and ZnO.
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5. Conclusion
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In addition to the fundamental aspect of plant fibers structure, types, sources and trends, its
utilization with zinc oxide nanoparticle were focused on in this article. It demonstrates the current state of
significant research findings and future development of nanocellulose in various applications. Further
comparison and deep investigation on three types of nanocellulose (CNC, CNF and BNC) will regulate
their respective potential applications in multiple areas. Overall, by creating controllable properties, ultra-
fine and reproducible production methods for bio-compatible nanocellulose will be favorable to pave the
way for better acceptance of nanocellulose as a commercially available and substantial material for
multiple applications. Thus, the cellulose nanocomposites using CNF, CNC, and BNC will attract great
attention especially in food packaging and antibacterial coatings. The modification of cellulosic materials
with zinc oxide can significantly improve the physical, morphological and catalytical properties of the
matrix even at lower wt%. The incorporation of zinc oxide nanoparticles with cellulose or nanocellulose

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particles would significantly increase the modulus and strength as well as antibacterial and photocatalytic
properties. Nanocellulose/zinc oxide nanoparticles are regarded as multifunctional composite materials
that can improve the dielectric, thermal, mechanical, sensing, and energy storage (supercapacitor)
characteristics even at extremely low ZnO proportions. That excellent antibacterial, UV barrier and
photocatalytic properties using biodegradable, renewable and sustainable component nanocellulose and
zinc oxide nanoparticles will revolutionize the entire nanotechnology, by covering the overall potential
applications in mechanical, electronic, and chemical sectors. On the basis of recent and updated literature
the following conclusions can be drawn:
1. In spite of being known since ancient times, but from the last century advanced processing and
instrumentation has allowed researchers to discover new sources of natural cellulose such as various

of
plants (rich in cellulose content), agricultural residue, textile processing leftovers, waste cotton etc.

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Similarly, researches are concerning the new green extraction methods of nanocellulosic materials that
exhibit extraordinary properties.

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2. The interfacial interaction between zinc oxide nanocellulose particles plays a major role in improving
the final properties. Nanocellulose particles with functional groups and ZnO-NPs with existing physical
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interaction is the basic reason for the surprisingly improved mechanical properties and morphological
properties.
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3. The synthesis methods regulate the level of dispersion of zinc oxide-based fillers and which shows the
significant effect on reinforcement and, thus, in nanocellulose/zinc oxide composite properties. So the
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proper techniques should be used with an appropriate medium of reaction, molecular weight of
nanocellulose, dissolution medium, and ZnO architecture and the required output.
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4. Even the small proportion of ZnO particles in nanocellulose materials can have the UV sensing and
photocatlytic properties, so in future flexible and wearable electronics in biomedical field will need the
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nanocellulose/ZnO-NPs based material, with excellent lightweight and nontoxic properties. Thus many
more investigations should be done towards industrialization of nanocellulose/ZnO-NPs nanocomposites
to make them useful for human needs.

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Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or
publication of this article: The work was supported by “National Key R&D
Program of China (2018YFC2000900)” and “Fundamental Research Funds for the Central Universities”
(2232018A3-04)”.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Graphical abstract

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 2. a) SEM image of the network of microfibrils covering the outer wall layer of the fiber, b) SEM
image of the cross-section of neat fiber to show the micro-fibrils, c) schematic illusion to show the
hierarchical structure of natural fibers, reproduced and modified from [59, 60].

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 3. The schematic diagram for the isolation of nanocellulose materials.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 4. (a) Transmission electron micrographs of cellulose nanofibrils [199], (b) cellulose nanocrystals
[200], and (c), (d) fleeces of bacterial nanocellulose produced by two different Gluconacetobacter strains
[58].

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 5. (a) lyotropic liquid crystalline (LCP) behavior [211], (b) higher thermal stability [96], and (c) the
SEM photograph of CNC materials [5].

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 6. Various applications of nanocellulose materials.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 7. (a) XRD and (b) XPS spectra of different forms of ZnO particles (a) NPs; (b) nanoflowers and (c)
nanorods synthesized through microwave aqueous solution techniques [291].
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 8. Schematic presentation for the synthesis of metal NPs/nanocellulose hybrid composite. (a) Simple
blinding of prepared inorganic NPs and cellulose source (b) Synthesis of NPs using nanocelluloses
without using external reducing agents, (c) Preparation of NPs composite using an external reducing
agents, and (d) Synthesis of NPs composite through nanocellulose surface modification.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 9. Nanocellulose/ZnO-NPs nanocomposite material production and properties in a schematic illusion.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES

Amjad Farooq a, Mohammed Kayes Patoary a, Meiling Zhang a, Hassan Mussanaa, Mengmeng Li a
Muhammad Awais Naeemc, Muhammad Mushtaqc, Aamir Farooq d, Lifang Liu a,b *

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Fig. 10. Mechanism of antimicrobial activities of nanoparticles [315].

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Table 1. Various sources of nanocellulose materials extraction.

Cellulose Source Biomass sources References
Water hyacinth (Eichhornia crassipes) [79]
Hemp [80]
Cotton [81]
Flax [82]
Potato tuber cells [83]
Sugar beet [84]
Non-woody sources Soybean [72]

of
Ficus Barkcloth [66]
Jute [82]

ro
Branch-barks of mulberry [85]
Sisal [86]
Pea hull -p [87]
re
Tomato peel [88]
Hardwood: birch, poplar, eucalyptus [89, 90]
Wood
lP

Softwood: Douglas fir, pine [70, 91]

maize straw [92]
na

Wheat straw [71]

Coconut husk [93]
Rice (straw, husk, etc.)
ur

Agricultural residues Lemon peel and maize [94]

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sunflower stalks [95]

Agave tequilana bagasse, barley husks [96]
Pineapple leaf [97]
waste pulp residues [98]
Tunicates [99]
Animals
Exoskeleton (prawns, crabs) [100]

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Table 2. Culture media used to produce bacterial cellulose.

Sources Bacterial Strain Culture Media References

K. xylinus BPR 2001 Molasses [103]
K. hansenii MCM B-967 Fruit peels [104]
K. sacchari Dry olive mill residue [105]

K. xylinus NRRL B-42 Glycerol from biodiesel production [106]

Industrial by-

of
products K. medellinensis ID13488 Apple residues from cider production [107]

ro
Blackstrap molasses solution and
K. xylinus ATCC 10245 [108]
CSL

K. hansenii PJK
-p Waste from the beer fermentation
broth
[109]
re
Thin stillage, from rice wine
K. xylinus BCRC 12334 [110]
distillery
lP

Industrial
[111]
wastewater K. xylinus ATCC 23770 Low-solids potato effluents
na

K. xylinus ATCC 23770 Waste fiber sludges [112]

K. xylinus CH001 Bagasse acid hydrolysate [113]

ur

Lignocellulosic
K. xylinus ATCC 23770 Cotton cloth hydrolysate [114]
biomass
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K. xylinus ATCC 23770 Konjac powder hydrolyzate [115]

K. xylinus BPR 2001 Maple sirup [116]
Sugar
K. xylinus NBRC 13693 Fruit juices [117]

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Table 3. Terminologies used for three types of nanocellulose, adapted from [208].

Type Acronyms Name Production Dimensions

NCC Nanocrystalline From plant cellulose
cellulose Diameter:
Microcrystalline 5–70 nm
MCC Length:
cellulose
Cellulose 100-250 nm
CMC
microcrystal
Wh Whiskers
Cellulose Cellulose Acid From celluloses of
CNW

of
nanocrystals nanowhiskers hydrolysis bacteria, tunicates, algae
Rod-like cellulose Diameter:

ro
crystals 5–70 nm
Microcrystals, Length:

CNC
nanocrystals
Nanorods -p 100 nm-several μm
re
Cellulose
nanocrystals
lP

Cellulose
CNF
nanofibrils/cellulos
Chemical or
e nanofibers Diameter:
enzymatic
na

Nanofibrillar 5–60 nm
Cellulose Pretreatment
NFC cellulose,
nanofibers and
nanofibrillated Length:
Mechanical
ur

cellulose, several μm
treatments
Micro-fibrillated
MFC
cellulose
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Bacterial cellulose
Bacterial Biocellulose Bacterial
BNC
nanocellulose Microbial culture Diameter: 20–100 nm
cellulose

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Table 4. ZnO synthesis process and resultant morphology.

ZnO morphology Process Type References

Nano-flowers, nanorods,
Solvothermal method [262]
nano-spheres

Hexagonal prismatic rods Hydrothermal synthesis [283]

Microwave hydrothermal
Mulberry-like [285]
method

Nanorods Hydrothermal technique [286]

of
Sphere Microwave decomposition [287]

ro
Nano and micro-flowers,
dumbbell-shaped, rice flakes,
and rings
-p
Simple wet chemical route [288]
re
Nano-flakes Simple precipitation method [289]
lP
na
ur
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Table 5 Advantage and disadvantages of various synthesis procedures of Zinc oxide nanoparticles.

Synthesis method Advantages Disadvantages

Simple, can be used on large
scale, low production cost, Higher amount of impurities
Mechano-chemical process
lower particle size, higher [295]
crystallinity
Simple, cheap, controllable
Co-precipitation method reaction by controlling Agglomerated particles [296]
reaction parameters

of
Agglomerated particles, large
Simple, cheap, reliable,
Sol-gel method scale production are difficult
repeatable

ro
[297]

Biological method
-p
Cost effective, ecofriendly
Lack of uniform size
distribution [298]
re
Require surfactants for
Easy, reversible, stability, limited solubilizing
lP

Microemulsion method
thermodynamically stable capacity for substance having
higher melting point [299]
na

High pressure and high

Solvothermal and High degree of crystallinity,
temperature are Required
hydrothermal method high purity
ur

[300]
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Table 6. Types of nano-cellulosic particles, metal, and method of synthesis for multifunctional composite
nano-materials.

Nanocellulose Metal Obtained Reference

Method Properties
source oxide material s
TEMPO- Freeze-drying
ZnO Spongy Topical bleeding [24]
oxidized CNF method
Chemical bath UV and humidity
CNF Zno Pellet [317]
deposition sensor
Solution casting Antibacterial and
CNC ZnO Paper coating [318]
method antifungal activity

of
chemical bath
Cellulose ZnO Pellet Ultraviolet sensing [319]
deposition

ro
Chemical bath Photocatalytic
Cellulose ZnO Nano-sheet [320]
deposition activity
Photocatalytic and
bacterial
cellulose
ZnO Film
-p
Facile method antibacterial
properties
[321]
re
Hydrothermal Absorption of
CNC ZnO Sheet [322]
method cationic dyes
lP

Aqueous
Cellulose UV sensing
ZnO Powder chemical growth [49]
powder properties
technique
na

Nano-
Filter paper Antimicrobial
ZnO composite Precipitation [34]
CNC applications
material
ur

Nano- Low Photocatalytic

Bamboo pulp ZnO composite temperature activity for dye [323]
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material precipitation degradation

Reduction and Removal efficiency
CMC ZnO Aerogel [324]
precipitation of Methylene blue
Nano-
Hydroxy-propyl Bottom-up UV–Visible
ZnO composite [325]
methylcellulose synthesis absorption properties
material
Nano-
Hydrothermal Antibacterial
cellulose ZnO composite [326]
method activities
material
Nano- Ultrasonic-
Bacterial
ZnO composite assisted in Antibacterial activity [327]
cellulose
material situ synthesis
In situ
CMC ZnO Hydrogels Antibacterial effects [328]
formation

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Single-step
Seaweed
ZnO Sheet hydrothermal Antimicrobial activity [329]
cellulose
method
Ultrahigh UV-
Sheet like
Hydrothermal Shielding and
Bamboo powder ZnO nano- [330]
method Antibacterial
composite
Performances
Nano-fibrous Electro-spun Antibacterial and
Cellulose acetate ZnO [331]
membrane method water repellent
Ultrasonic-
Hetero-
Bacterial assisted Antibacterial and
ZnO structure nano- [313]
cellulose synthesis Thermal properties
composite
method

of
Water Sorption
Hydrothermal
Cellulose acetate ZnO Films Properties and [332]

ro
method
Antimicrobial Action
Nano-fibrous Electro-spun antibacterial activity
CMC ZnO [333]
membranes
-p
method in wound dressing
Antifungal activity,
re
UV-Shielding, and
CMC ZnO Films Casting method [334]
Antibacterial
Performances
lP
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ur
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Highlights
The main contributions of this review paper are as follows:

 Consolidated study on cellulose and nanocellulose structure, sources and applications.

 Reviewing various extraction techniques of nanocellulose, their types, properties, and
characteristics.
 All recognized excellent properties and recent advancement of nanocellulose/ZnO-NPs
composite materials are presented.
 Challenges and future viewpoints of ZnO nanoparticles with nanocellulose materials are

of
discussed.

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