Journal Pre-proof

Recent Advancements in the Synthesis, Functionalization, and

Utilization of Cellulose Nanocrystals

Xiao Zhang , Hui Ni , Xiangming Xu , Long Li , Hailan Kang ,

Donghan Li

PII: S2772-4433(24)00018-7
DOI: https://doi.org/10.1016/j.recm.2024.05.003
Reference: RECM 73

To appear in: Resources Chemicals and Materials

Received date: 20 March 2024

Revised date: 11 May 2024
Accepted date: 28 May 2024

Please cite this article as: Xiao Zhang , Hui Ni , Xiangming Xu , Long Li , Hailan Kang ,
Donghan Li , Recent Advancements in the Synthesis, Functionalization, and Uti-
lization of Cellulose Nanocrystals, Resources Chemicals and Materials (2024), doi:
https://doi.org/10.1016/j.recm.2024.05.003

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition
of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of
record. This version will undergo additional copyediting, typesetting and review before it is published
in its final form, but we are providing this version to give early visibility of the article. Please note that,
during the production process, errors may be discovered which could affect the content, and all legal
disclaimers that apply to the journal pertain.

© 2024 The Author(s). Publishing services by Elsevier B.V. on behalf of KeAi Communications Co.,
Ltd.
This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
Highlights
 The main preparation methods of cellulose nanocrystals are introduced.

 The modification method of cellulose nanocrystals was described.

 The main applications of CNCs and their contributions in improving the

properties of polymer matrices are introduced.

1
Recent Advancements in the Synthesis, Functionalization, and
Utilization of Cellulose Nanocrystals
Xiao Zhang,a,b Hui Ni,a,b Xiangming Xu,a,b Long Li,a,b Hailan Kang, ⁎,a,b Donghan Li,⁎,a,b
aKey Laboratory for Rubber Elastomer of Liaoning Province, Shenyang University of
Chemical Technology, Shenyang, 110142, China
bCollege of Materials Science and Engineering, Shenyang University of Chemical
Technology, Shenyang, 110142, China
Correspondence to: Hailan Kang (E-mail: [email protected]) and Donghan Li (E-
mail: [email protected]).

Abstract
The utilization of cellulose nanocrystals (CNCs), a renewable and eco-friendly
nanomaterial, has emerged as the favored option for sustainable fillers. This paper
presents diverse methods for CNCs preparation, including acid hydrolysis, oxidation,
mechanical method, enzymatic hydrolysis, solvent method and hybrid approach. The
strategies for modifying CNCs can be summarized as encompassing physical
adsorption through non-covalent bond interactions and chemical modifications via
covalent bonding. Moreover, the applications of CNCs in sensing systems, electronic
skin devices, packaging materials, electronics industries, stabilizers and cosmetics are
discussed with a particular emphasis on their contribution to enhancing polymer
matrix properties. Lastly, future prospects for the advancement of CNCs are explored
with a focus on its potential impact on sustainability efforts.
Keywords

Cellulose Nanocrystals; Preparation; Modification; Application

Abbreviations

CNCs, cellulose nanocrystals; AGU, anhydro-glucopyranose units; CNFs, cellulose

nanofibers; BC, bacterial celluloses; NCC, nanocellulose; CNWs, nanowhiskers; NR,
natural rubber; SBR, styrene butadiene rubber; EUG, Eucommia ulmoides gum,
XNBR, carboxylated nitrile rubber; PLA, polylactic acid; PBS, poly (butylene
succinate); PU, polyethylene; CA, citric acid; FA, formic acid; MCC, microcrystalline
cellulose; TMEDA, tetramethylethylenediamine; HPH, high-pressure
homogenization; ILs, liquid ionic methods; DESs, deep eutectic solvents;
[EMIM][OAc], 1-ethyl-3-methylimidazolium acetate; DCP, diisopropylphenyl
peroxide; PHDA, poly (hexadecyl acrylate); PANI, polyaniline; ABS, acrylonitrile-
butadiene-styrene; Al2O3, aluminum oxide nanoparticles; PHBV,
2
polyhydroxybutyrate-co-valerate; WPU, waterborne polyurethane; WBPUU,
waterborne polyurethane-urea; PDMS, polydimethylsiloxane; PDA, polydopamine.

1. Introduction

In light of the urgent energy crisis and resource scarcity, there has been a
significant increase in interest regarding research on renewable and sustainable green
materials[1-4]. Cellulose, the most abundant and sustainable resources available on
earth, is mainly derived from the cell wall of various plants. The cellulose molecule
consists of β-(1-4) connected chains of anhydro-glucopyranose units (AGU), with
every AGU unit being twisted 180° in relation to its neighboring units. One end
contains a reducing hemiacetal unit, while the other is nonreducing (Fig.1) [5].
According to their preparation methods and sources, nanocellulose can be divided into
cellulose nanocrystals (CNCs, nanorod-like materials), cellulose nanofibers (CNFs,
with three-dimensional nanofiber networks and excellent mechanical properties) and
bacterial celluloses (BNCs, a biodegradable natural nanostructured polymer material
produced by bacteria) [6]. According to the ISO/TS 20477: 2017 (Nanotechnologies-
Standard terms and their definition for cellulose nanomaterial), CNCs are highly
crystalline with aspect ratio of usually greater than 5 but less than 50, and not inter-
particle entanglement or network-like structures (Fig.2). CNFs show low degrees of
crystallinity and exhibit dimensions of nanoscale in cross-section and typically up to
100 μm in length, with greater aspect ratio and entanglement between particles or
network-like structures. BNCs represent nanocellulose produced by bacteria. The
presence of abundant surface hydroxyl groups in all types of nanocellulose contain
presents a significant challenge to achieving uniform dispersion within conventional
hydrophobic polymer matrixes due to their inherent strong hydrophilicity.
CNCs, also referred to as nanocellulose (NCC) and cellulose nanowhiskers
(CNWs), are nanoparticles characterized by a rod-like morphology derived from
natural polymers such as microcrystalline cellulose, hemicellulose, lignin, wood pulp,
bagasse pulp or cotton fibers. As one of the most widely utilized types of
nanocellulose, CNCs not only possess the inherent characteristics of cellulose, such as
exceptional mechanical strength (due to strong intramolecular hydrogen bonds), well-
defined structural order (resulting from intermolecular interactions) and facile
modification (owing to abundant hydroxyl groups)[7, 8]. Simultaneously, they exhibit
distinctive features including a significantly large specific surface area, high
crystallinity, high Young's modulus, low thermal expansion coefficient, remarkable
transparency and excellent barrier properties. Due to the presence of abundant
hydroxyl groups, CNCs possess the capability to form intricate networks through both
intramolecular and intermolecular hydrogen interactions (Fig. 1), rendering them a
prominent choice for various industrial applications[9-14]. Recently, CNCs have been
incorporated into polymeric composites with natural rubber (NR), styrene butadiene
rubber (SBR), Eucommia ulmoides gum (EUG), carboxylated nitrile rubber (XNBR),
polylactic acid (PLA), poly (butylene succinate) (PBS) and polyethylene (PU). These
3
polymer/CNCs nanocomposites demonstrate significant potential in a wide range of
applications, including biomedicine, food, optoelectronics and packaging.

Fig.1. Intramolecular (---) and intermolecular (---) hydrogen bonding networks in cellulose structure[14]

Fig.2 TEM (a)[12], SEM (b)[15] and AFM (c)[16] images of CNCs

In the 1950s, Ranby first reported that colloidal suspensions of cellulose could be
obtained by controlling the sulfuric acid catalytic degradation of cellulose fibers[17].
Subsequently, numerous researchers have dedicated their efforts to the eco-friendly
and efficient preparation, modification and application of CNCs. The present review
will discuss the latest advancements in CNCs preparation methods, functional
modifications, and applications in subsequent sections. Ultimately, the challenges for
rapid progress in renewable fillers using CNCs are addressed along with future
prospects for CNCs across various fields.

2. Preparation of CNCs

The preparation of CNCs can be achieved through various methods, including

chemical routes (such as acid hydrolysis, oxidation and solvent), mechanical
techniques (like ball milling, ultrasonication, high-pressure homogenization) and
biological routes (such as enzymatic hydrolysis).

4
 2.1 Acid hydrolysis
The cellulose structure contains both amorphous and crystalline regions
(Fig.3)[18]. The objective of acid hydrolysis is to selectively separate the crystalline
component of cellulose fibers from the amorphous portion, which is primarily
attributed to the difference in hydrolysis kinetics between amorphous and crystalline
domains. During the hydrolysis process, the amorphous regions were preferentially
hydrolyzed, while the crystalline regions exhibited higher resistance to acid and were
ultimately retained, resulting in rod-shaped CNCs with enhanced crystallinity. The
most commonly used method for preparing CNCs is through acid hydrolysis, which
can be categorized into inorganic acid hydrolysis[19-21], organic acid hydrolysis[22-
25] and mixed acid hydrolysis[15, 26, 27].

Fig.3. The mechanism of cellulose nanocrystals prepared by acid hydrolysis[18]

The most commonly employed method for the production of CNCs involves
sulfuric acid hydrolysis, wherein a fraction of the surface hydroxy groups undergoes
esterification to generate anionic sulfate half-ester groups. The presence of these
groups contributes to the stabilization of aqueous suspensions of CNCs by promoting
electrostatic repulsion and facilitating their dispersion in water[28]. However, the
thermal stability of CNCs is reduced upon the introduction of sulfate half-ester
groups[25]. Thus, Hu et al. effectively introduced a substantial amount of carboxyl
groups onto the surface of sulfonated CNCs through the utilization of citric acid (CA),
thereby imparting higher chemical reactivity and thermal stability[19]. Subsequently,
researchers achieved the production of CNCs using oxalic acid at concentrations from
0.06 to 1.11mol∙L-1, exhibiting a maximum thermal degradation temperature of
350 °C[24]. Besides, CNCs prepared through FeCl3-catalyzed hydrolysis of formic
acid (FA) exhibited a remarkable yield surpassing 75 %. Intriguingly,
thermogravimetric analyses revealed that F-CNCs demonstrated significantly higher
thermal stability (314℃), surpassing CNCs prepared by conventional sulfuric acid
hydrolysis (215℃)[23]. Similarly, a small amount of inorganic acid was also utilized
as a catalyst to enhance the rate of organic acid hydrolysis for the preparation of
CNCs. Yu et al. successfully obtained carboxylated CNCs with a relatively stable
structure from microcrystalline cellulose (MCC) through the hydrolysis of using a

5
mixture of CA and hydrochloric acid (HCl) (Fig.4)[27]. Subsequently, the hydrolyzed
CNCs underwent mechanical treatment, typically sonication, which facilitated the
dispersion of nanocrystals into a uniform stable suspension.

Fig.4. HCl catalyzed hydrolysis mechanism of MCC by CA[27]

2.2 Oxidation
The hydroxyl group on the surface of cellulose exhibits high reactivity towards
oxidative degradation, rendering it susceptible to oxidation by potent oxidizing agents
and leading to the formation of carboxyl groups. This characteristic represents a
promising route for the synthesis of CNCs through oxidation. TEMPO system,
ammonium persulfate and periodate chlorite are commonly used oxidants in this
process. These oxidants displayed selectivity towards the oxidation of cellulose while
effectively inhibiting the oxidation of other hydroxyl groups.[29]
TEMPO has gained considerable attention as a water-soluble catalytic oxidation
system for its ability to selectively oxidize the primary hydroxyl groups (C6) of pulp
fibers. The systems are classified as alkaline TEMPO/NaClO/NaBr and acidic
TEMP/NaClO/NaClO2, which are typically mixed using mechanical or acid
hydrolysis methods. In Okita's investigation, TEMPO-mediated oxidation was utilized
to treat a diverse range of native celluloses, ensuring comprehensive oxidation of all
C6 primary hydroxyls accessible to the oxidation process. The resulting oxidized
cellulose microfibrils, when dispersed in water, exhibited a consistent potential of
approximately -75 mV across all native cellulose types. However, the oxidized
celluloses displayed varying carboxylate contents, ranging from 0.5 to 1.7 mmol/g,
depending on the cellulose source. Minimal quantities of aldehydes (0.0-0.1 mmol/g)

6
were detected in the oxidized products. These findings affirm the efficacy of TEMPO-
mediated oxidation in converting nearly all exposed C6 primary hydroxyls on the
entire surfaces of cellulose microfibrils into sodium carboxylate groups[30]. Fraschini
et al. successfully oxidized cellulose nanocrystals using catalytic amounts of sodium
bromide and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical at pH 10 in water
(Fig.5). The selective introduction of carboxylic acid groups can enhance the
functionality of CNCs, allowing them to be used in a broader range of applications,
such as in composites, hydrogels, or as carriers for drug delivery. Additionally, the
final acid content can be easily adjusted by changing the amount of oxidant
introduced [31]. The carboxylated CNCs were prepared by Fukui et al. through the
TEMPO oxidation method using wood cellulose, followed by hydrophobic
modification with tetrabutylamine. Subsequently, a composite film consisting of
HNBR and hydrophobic CNCs was fabricated, exhibiting a high Young 's modulus of
45.0 MPa and a low thermal expansion coefficient of 20 ppm/K [32].

Fig.5. Mechanism of carboxylated CNCs prepared by TEMPO oxidation[31]

Simultaneously, ammonium persulfate can selectively oxidize the hydroxyl groups
(C6) on the surface of cellulose to -COOH, as shown in Fig.6. The combined action of
SO42-, H2O2 and HSO4- leads to both destruction of the amorphous region in cellulose
and selective oxidation of hydroxyl groups (C6) on its surface to -COOH by H2O2
generated by S2O82- hydrolysis, ultimately resulting in carboxylated CNCs [33]. Liu et
al. prepared carboxylated CNCs through the redox reaction of
tetramethylethylenediamine (TMEDA) and ammonium persulfate. The addition of
TMEDA facilitated a more rapid conversion of S2O82- into free radicals and hydrogen
peroxide, resulting in an increased yield of CNCs up to 62.5%[34]. In order to further
enhance the preparation of CNCs with a smaller particle size, Wang et al. employed a
combined oxidation method involving sodium persulfate and ultraviolet combined
oxidation to produce oxidized CNCs. The CNCs obtained through this combined
oxidation approach exhibited a smaller (13-20μm) and more uniform particle size,
accompanied by improved Young 's modulus (124.9%) and mechanical strength
7
(180MPa) [35].

Fig.6. The process of cellulose oxidation by ammonium persulfate[33]

Periodate has the ability to selectively cleave carbon-carbon bonds in a variety of
1,2-difunctionalised alkanes, making it an intriguing option for a range of
fundamental and industrial applications. The oxidation of polysaccharides by
periodate under relatively mild conditions is widely utilized to introduce aldehyde
groups into the polysaccharide chains, such as transforming cellulose into polymeric
2,3-dialdehyde cellulose. The specific process is that the C2-C3 bonds of cellulose
can be cleaved by periodate oxidation, leading to the selective oxidation of C-2 and
C-3 vicinal hydroxyl groups to form 2,3-dialdehyde units along the cellulose chains.
Subsequently, under acidic conditions, further oxidation of 2,3-dialdehyde groups
resulted in the formation of 2,3-dicarboxylic groups and carboxylated CNCs
(Fig.7)[29, 36-38].

Fig.7. Periodate oxidation mechanism of cellulose[29, 38]

8
 2.3 Mechanical method
The mechanical method of CNCs stands out for its operational simplicity and
universal applicability when compared to other preparation methods. This technique
holds great potential for industrial applications as it facilitates the large-scale
production of nanofillers[39]. Mechanical methods can be categorized into high-
pressure homogenization (HPH), ball milling and high-intensity ultrasonication
(HIUS).
During high-pressure homogenization, the cellulose suspension is propelled
through extremely narrow gaps or nozzles, creating a rapid flow that generates
exceptionally high shear forces. These forces efficiently disrupt the hydrogen bonds
within cellulose fibers, facilitating depolymerization and leading to the formation of
smaller cellulose nanocrystals. Khawas et al. observed that an increased number of
passages in the homogenizer resulted in the shortening of CNCs, while also yielding
more stable aqueous suspensions with zeta potential values ranging from -16.1 to -
44.1 mV [40]. Liu et al. optimized the process parameters for the preparation of CNCs
through HPH, focusing on maximizing yield, controlling zeta potential, and achieving
desired morphology. The optimal process parameters were determined to be as
follows: ultrasound power of 125 W, ultrasound time of 15 min, homogenization
pressure of 40 MPa four times. The resulting CNCs exhibited a yield of 19.81%, a
zeta potential of 15.60 mV, and a diameter range between 20-60 nm [41].
Subsequently, CNCs with uniform widths ranging from 4-14 nm and lengths ranging
from 60-320 nm were successfully achieved by Park et al. via an efficient and
sustainable HPH method[42].
The ball milling method utilizes mechanical and frictional forces to disrupt
cellulose particles, reducing their size to the nanometer scale. Due to the friction
generated by mechanical motion and collision, the temperature of the local area
increases. This frictional heat serves to soften cellulose particles, enhancing their
deformability and rendering them more susceptible to fragmentation under the
influence of mechanical forces. Baheti et al. found that the CNCs prepared after 3h of
wet milling in deionized water (Fig.8) exhibited a narrower particle size distribution.
Furthermore, it was suggested that optimization of the ball milling duration,
incorporating of active agents, or utilization of smaller ball size may potentially
facilitate the effective reduction in the size of CNCs particles[43]. Yao et al.
demonstrated the production of aqueous dispersions of CNCs by stirring an aqueous
dispersion of MCC at room temperature for 10 min, followed by colloid milling for 6
h until achieving a minimum pitch between the rotor and stator[44].

9
 Fig.8. Ball milling process[43]

HIUS waves generate a powerful mechanical oscillating force through the

phenomenon of cavitation. This process includes the formation, growth, and collapse
of tiny gas bubbles as the liquid molecules absorb ultrasonic energy. Within these
cavitation bubbles and their surrounding areas, intense shock waves are produced.
These shock waves are leveraged for extracting fibrils from cellulose fibers,
effectively breaking them down into finer components. [45] Xu et al. prepared hollow
annular CNCs (HTA-CNCs) with diameters ranging from 10 to 30 nm, widths of 3 to
4 nm, and thicknesses of 2.0 to 5.0 nm by subjecting rod-shaped CNCs to HIUS at a
power of 1000 W and frequency of 20 kHz for 90 min. Importantly, HTA-CNCs
exhibited enhanced -OH content, thereby expanding the potential applications of
cellulose nanomaterials in diverse fields including drug delivery[46]. The molecular
dynamics simulation of the HTA-CNC formation is shown in Fig.9. Xie et al. utilized
a microwave liquefaction system in combination with bleaching and acid hydrolysis
to extract pure white cellulose fibers from bamboo with large particle size (20 - 80
mesh). These purified fibers were then subjected to high-intensity ultrasonic
treatment, which produced CNCs with diameters of 4-18 nm and lengths exceeding
550 nm [47]. Khawas et al. applied HIUS to extract CNCs from edible banana peels,
successfully eliminating non-cellulosic impurities. They explored ultrasonic power
levels ranging from 0 to 1000W and observed a significant influence on the CNCs'
dimensions and morphology. Higher ultrasonic powers led to the production of
smaller CNCs and more refined, needle-like structures. [48]

10
 Fig.9. Molecular dynamic simulation of HTA-CNC formation: (a) initial structure of CNCs with
hydrogen-bonding networks illustrated; (b) schematic diagram of external forces exerted on CNCs; (c)
process of HTA-CNC formation driven by external forces [47].

In conclusion, mechanical extraction of CNCs presents several advantages,

including straightforward operation, environmental friendliness, and energy
efficiency. Additionally, it offers high product purity and precise controllability. These
characteristics make it a promising method with great potential for widespread
application in both research and industry.
2.4 Enzymatic hydrolysis
The enzymatic hydrolysis process has a favorable effect on reducing the celluloses
primary fibrillation capacity compared to conventional hydrolysis, thereby positioning
itself as a promising approach for advancing environmentally sustainable industrial
processes[49]. Chen et al. showed that the enzymatic hydrolysis of hemicellulose
using a synergistic interaction between xylanase and cellulase (9:1) resulted in the
production of spherical CNCs with exceptional monodispersity and uniformity,
exhibiting an average particle size of approximately 30 nm. Fig.10 (a) and (b) are
SEM figures of the sample prepared from the enzymolysis of cellulose with single
cellulase, (c) and (d) were SEM figures of the sample prepared from the enzymolysis
of cellulose by the complex enzyme of cellulose and xylanase [50]. In a subsequent
study, Tong et al. reported the synthesis of rod-shaped CNCs with dimensions of 600
nm in length and 30 nm in width, possessing a thermal decomposition temperature of
345°C. Additionally, spherical CNCs were obtained with an average particle size of
40 nm and a thermal decomposition temperature of 343°C. These CNCs were
produced through the combined action of cellulases and xylanases (9:1) at total
enzyme concentrations of 10 and 500 U mL-1, respectively, for hydrolysis durations of
12 and 5 hours[51].

Fig.10. SEM of cellulose samples enzymatically hydrolyzed by cellulase ((a) and (b)) and cellular-

11
 xylanase complex ((c) and (d)).[50]

2.5 Solvent method

Among the pretreatment methods, solvent method has gained recognition as an
effective approach for the separation of lignocellulosic components in accordance
with the principles of green chemistry, including liquid ionic methods (ILs) and deep
eutectic solvents (DESs). ILs possess the ability to facilitate the hydrolytic cleavage
of glycosidic bonds between adjacent anhydroglucose units in cellulose, leading to the
reconfiguration of interlinking chain ends and consequent release of internal
strain[52]. In previous investigations, it has been established that 1-ethyl-3-
methylimidazolium acetate ([EMIM][OAc]) exhibited a distinct affinity for dissolving
lignin[53, 54]. Consequently, Abushammala et al. have successfully demonstrated the
unprecedented capability of [EMIM][OAc] ILs to directly extract CNC (with
dimensions ranging from 2 to 5 nm in width and 75 to 125 nm in length) from wood,
showcasing a remarkable crystallinity index of about 75%[55]. In addition, Miao et al.

successfully extracted CNCs (Tonest=328.8℃) with enhanced thermal stability

compared to CNCs (Tonest=268.8℃) prepared through sulfuric acid hydrolysis,

utilizing an ILs solvent system comprising tetrabutylammonium acetate and
dimethylacetamide [56].
The DESs, as a new generation of green solvents, are composed of two- or three-
component mixtures comprising hydrogen bond acceptors and donors, predominantly
including oxalic acid, formic acid, alkaline glycerol, etc. The hydrogen bonds in the
DESs establish a robust interaction, thereby facilitating the applicability of this
approach to diverse materials, including hydroxyl-rich polymers [57]. The
distinguishing features of DESs lie in their biodegradability, environmental
friendliness, and efficient recyclability. Interestingly, the solvent can be successfully
recycled and reused for at least three additional pretreatment cycles while maintaining
its pretreatment capability; however, they exhibit drawbacks such as high viscosity
and production cost. Diluting DESs with water is an efficient way for reducing
viscosity, as demonstrated in Fig.11 [58-60]. Sirvio et al. investigated the impact of
four acidic DESs, including lactic acid/choline chloride, levulinic acid/choline
chloride, malic acid/choline chloride, glutaric acid/choline chloride, and one alkaline
DESs (glycerol/K2CO3) on the extraction of wood cellulose fibers. The results
revealed that the CNCs treated with lactic acid/choline chloride acid system and
glycerol/K2CO3 alkaline system exhibited higher viscosity (1360-555 Pa∙s) and
crystallinity (54-38%), while the alkaline system treated nanofibers displayed superior
tensile strength (170-132 MPa) and Young 's modulus (8.6-5.2 GPa) [61]. The CNCs
prepared by Liu et al. exhibited a width ranging from 9 to17 nm, length ranging from
310 to 410 nm and crystallinity of 66-71 %, through the utilization of DESs composed
of choline chloride/oxalic acid dihydrate at elevated temperature (50-100 ℃)[62].

12
 Fig.11. The mechanism of diluting DESs with water to reduce their viscosity[59]

2.6 Hybrid approach

In the preparation of CNCs, a single preparation method entails prolonged reaction
time or prolonged reaction conditions. Consequently, most researchers are dedicated
to achieving uniform and stable CNCs through diverse methodologies, thereby
significantly enhancing reaction efficiency and offering novel approaches for broader
industrial production. For an instance, the extraction of CNCs from MCC can be
achieved by integrating ethanol solvothermal pretreatment followed by ultrasonic
disintegration [63]. The combination of HCl gas hydrolysis and TEMPO oxidation
was employed by Paakkonen et al. to generate carboxylated BC from BC aerogel,
successfully reducing the polymerization degree of BC aerogel from 2160 to 220 with
a CNCs yield exceeding 80% [64]. Meanwhile, Azrina et al. found that the utilization
of ultrasonic during acid hydrolysis process can further enhance the quality of CNCs
[65]. In the study conducted by Li et al., it was found that carboxylated CNCs with a
higher surface charge could be synthesized through the utilization of formic acid to
remove hemicellulose and swell cellulose fibers followed by TEMPO oxidation.
Notably, the increased surface charge resulted in higher redispersibility and viscosity
of aqueous dispersions of the CNCs [66].
In summary, during the process of preparing CNCs, mechanical methods are
commonly employed in a large-scale industrial production, while chemical methods
are preferred for synthesizing CNCs with specific properties such as carboxylation.
However, mechanical methods exhibit relatively favorable environmental
characteristics, whereas chemical methods enable the attainment of uniform CNCs.

13
 Table.1. Introduction of various preparation methods of CNCs including major chemical reagents, and some other advantages disadvantages.
Method Major chemical reagents Advantages/ Disadvantages Ref.
inorganic acid
H2SO4, HCl, H3PO4, HBr It is difficult to treat waste acid like H2SO4 and [19-21]
hydrolysis
HCl presents challenges due to their corrosive
nature, potentially causing equipment damage.
organic acid hydrolysis Citric acid, Oxalic acid, Formic acid In contrast, CNCs synthesized via the H2SO4 [22-25]
Acid hydrolysis
method demonstrate remarkable suspension
stability. Furthermore, formic and oxalic acids can
mixed acid hydrolysis HCl/HNO3, HCl/Citric acid be efficiently recycled with minimal impact on [15, 26, 27]
equipment corrosion.

TEMPO/NaClO/NaBr,
TEMPO [30-32]
TEMP/NaClO/NaClO2
Carboxylated CNCs can indeed be synthesized.
Oxidation Ammonium persulfate Ammonium persulfate However, a notable quantity of oxidants is [33-35]
utilized during this process.
H5IO6/NaOH, sodium
Periodate (meta)periodate/sodium chlorite, [29, 36-38]
sodium periodate
high-pressure
-
homogenization The mechanical method indeed boasts
simplicity, environmental friendliness, and
ball milling - controllability; nevertheless. [43, 44]
Mechanical method
It has its drawbacks, including high energy
consumption, low crystallinity, and challenging
high-intensity process condition control.
- [45-48]
ultrasonication

14
 Table.1. Continued
Method Major chemical reagents Advantages/ Disadvantages Ref.

This method is environment-friendly, but the

Enzymatic hydrolysis - Xylanase and Cellulase [49-51]
cost is very high.

Ionic liquids can be recycled, providing an

[EMIM][OAc], [BMIM]HSO4, advantage in the preparation of functional CNCs.
Ionic liquid [52-56]
[BMIM]Cl, TBAA/DMAc Deep eutectic solvents are recoverable,
biodegradable, and environmentally friendly.
Solvent method
Lactic acid/Choline chloride, Levulinic However, Ionic liquids currently comes at a
acid/Choline chloride, Malic high cost. Additionally, the DES reaction degree is
Deep eutectic solvents [57-62]
acid/Choline chloride, Glutaric low, requiring subsequent mechanical treatment to
acid/Choline chloride, Glycerol/K2CO3 obtain the desired CNCs products.

15
 3. Functional modification of CNCs

The intermolecular and intramolecular hydrogen bondings in CNCs not only confer
significant advantages to their exceptional properties, but also contribute to their
propensity for agglomeration in aqueous dispersion system. Interestingly, the presence
of abundant hydroxyl groups on the surface provides an excellent modification
platform, leading to improved hydrophobicity and enhanced dispersibility and
comprehensive properties of CNCs in the composite system[67]. The functional
modification of CNCs can be categorized into physical adsorption via noncovalent
interactions and chemical modification through covalent bonding. Covalent
modifications include the characteristic reactivity of the hydroxyl group, such as
esterification, siloxane, epoxy ring-opening, amidation, Schiff base, and so forth.
3.1 Physical adsorption
Physical adsorption entails the binding of small surfactants or macromolecules onto
the surface of CNCs through non-covalent interactions, encompassing electrostatic
attraction, van der Waals forces, and hydrogen bonding [68]. For example, CTAB was
non-covalently attached to the surface of modified CNCs, and materials fabricated
using latex compounding method composed of NR latex and CNCs exhibited
significantly improved mechanical strength and anti-aging properties [69].
Furthermore, Ali et al. utilized CTAB as a template to facilitate the electrostatic
adsorption of SiO2 onto the surface of CNCs, which significantly enhanced the
thermal stability of the CNCs [70]. Michel et al. have developed innovative cryogels
using CNCs and β-cyclodextrins (β-CDs), incorporating various β-CDs derivatives
through physical adsorption. This versatile material is poised for a broad spectrum of
applications, from biomedical drug delivery systems to filtration for decontaminants
and scavenging devices [71].
3.2 Chemical modification
Chemical modification is achieved by forming conjugated covalent bonds, which
exhibits stronger adsorption on the CNCs surface compared to physical adsorption.
Furthermore, the functional groups introduced onto the surface of CNCs can react
with those in the matrix, forming covalent bonds.
3.2.1 Esterification
The esterification modification is accomplished by forming a covalent bond
between the hydroxyl group of CNCs and the carboxyl group of the modifier through
an esterification reaction. Hsu et al. prepared modified CNCs through an esterification
reaction between CA carboxyl group and CNCs hydroxyl group. These modified
CNCs served as both fillers to reinforce epoxy resin and partial substitutes for toxic
anhydride curing agent [72]. Lu et al. prepared the modified CNCs through
esterification reaction between carboxyl group of long-chain fatty acids (lauric acid,
16
palmitic acid, stearic acid) and hydroxyl group of CNCs in a FeSO4/H2O2 redox
system, demonstrating an improvement in water contact angle. This modification
played a crucial role in facilitating emulsification and dispersion [73]. Leszczynska et
al. employed succinic anhydride for targeted esterification of CNCs to improve their
thermal stability. Their research demonstrated that the degree of surface substitution
on the CNCs correlated with the molar ratio of hydroxyl groups from succinic
anhydride to CNCs and the duration of the reaction. Additionally, they found that the
reaction temperature had a minimal effect on the degree of esterification within the
temperature range of 70-110℃ [74].
3.2.2 Silanization
The silage coupling agent is commonly employed as a surface treatment agent due
to the reactivity of its siloxy group with inorganic substances, while its organic
functional groups exhibit compatibility or reactivity towards with organic substances.
The silane alcohol group, epoxy group and amino group synthesized through
hydrolysis of a silage coupling agent can undergo covalent bonding with hydroxyl
group [75]. Wang et al. utilized (3-mercaptopropyl) trimethoxysilane (MPTS)-
modified CNCs as reinforcement for EUG, resulting in a significant enhancement of
both of tensile strength and elongation at break to 16.2 MPa and 498 %, respectively
[76]. Furthermore, when CNCs modified by 3-isocyanatopropyl trimethoxysilane
were used as cross-linking agents and nano-fillers, the silicone elastomer
demonstrated significant improvements in both tensile strength (54% increase) and
shear strength of (68.6% increase) [77]. Aziz et al. applied 3-
Glycidoxypropyltrimethoxy (KH-560) for the silyl modification of CNCs,
significantly enhancing the crystallinity of the modified CNCs. This modification
resulted in notable improvements in tensile strength and modulus, and enhanced
interface adhesion [78]. Dhali et al. employed triethoxyvinylsilane (TEVS) to modify
CNCs through silanization, leading to the partial substitution of hydroxyl groups with
attached polysiloxane chains. This modification, featuring the grafting of the silane
agent with protruding vinyl groups, effectively enhanced the surface hydrophobicity
of the CNCs [79].
3.2.3 Grafting reaction
Common grafting techniques include surface-initiated ring-opening polymerization,
radical polymerization, and end-group grafting via reduction. For example, the
introduction of -COOH groups onto the CNCs through TEMPO oxidation, 1-methyl-
3-phenylpropylamine was grafted onto the CNCs in the presence of a catalyst to
enhance the dispersion and stability of modified CNCs in organic solvent, thus
facilitating the preparation of composites [80]. Zhou et al. employed an esterification
reaction of maleic anhydride with CNCs to modify them, followed by in situ cross-
linking of the composites with PLA using diisopropylphenyl peroxide (DCP) as a
cross-linking agent. When the mass fraction of modified CNCs is 5%, the tensile
strength and elastic modulus of the composites are increased by 73.2% and 122.7%
17
respectively [81]. An et al. synthesized a renewable copolymer by combining the high
tensile strength of CNCs with the antioxidant properties of lignin. This was achieved
by grafting lignin onto the surface of CNCs through a Diels-Alder “click” reaction.
The results showed that the addition of phenolic hydroxyl groups provided the CNCs
with outstanding antioxidant activity, as evidenced by an IC50 value of 1.49 mg/mL
[82]. Yin et al. enhanced the thermal stability and reduced the hydrophilicity of CNCs
by grafting synthesized hydrophobic triazine derivatives onto their surface. The
introduction of a protective layer of triazine hydrophobic aliphatic amine significantly
improved the thermal stability of the modified CNCs. This modification resulted in an
increase of approximately 100℃ in the initial thermal decomposition temperature
compared to the CNCs[83].

18
 Table.2. The chemical modification reaction formula of CNCs
Modifying agent Chemical modification reaction formula

Citric acid

Esterification Lauric acid

Succinic
anhydride

19
 Table.2. Continued
Modifying agent Reaction mechanism

(3-mercaptopropyl)
trimethoxysilane

3-isocyanatopropyl
Silanization trimethoxysilane

3-
Glycidoxypropyltrimethoxy

20
 Table.2. Continued
Modifying agent Reaction mechanism

Silanization Triethoxyvinylsilane

1-methyl-3-
phenylpropylamine

Grafting
reaction

Maleic anhydride

21
 Table.2. Continued
Modifying
Reaction mechanism
agent

Lignin

Grafting
reaction

Triazine
derivatives

22
 4. CNCs nanocomposites

The current utilization of petroleum-based fillers, which are nonrenewable, non-

degradable and environmental pollution, has prompted researchers to explore new
“green” nanofillers that show potential for replacing or partially replacing these “non-
green” reinforcing nanofillers. Due to the high aspect ratio and attractive mechanical
properties, CNCs have garnered significant attention as a potential candidate for
enhancing the mechanical and other properties of polymer systems. The properties of
these composites are influenced by the strength and extent of the interfacial
interaction between “matrix-filler” and “filler-filler”, while processing techniques are
also play a role in determining composite performance. The present section provides a
comprehensive overview of the preparation and properties of CNCs nanocomposites,
with particular emphasis on their applications in composite materials.
4.1 Preparation of CNCs nanocomposites

4.1.1 In-situ polymerization

The in-situ polymerization involves introducing the reaction monomer into the
CNCs, followed by subsequent polymerization within the CNCs. To tackle the issue
of reduced enthalpy in phase change materials (PCMs), Mu et al. synthesized solid-
solid phase change materials (SSPCM) by immobilizing poly (hexadecyl acrylate)
(PHDA) onto CNCs via in-situ free radical polymerization. The results indicated that
CNCs at the nanoscale exhibited nucleating properties, facilitating PHDA
crystallization and suggesting the potential SSPCM as a promising solution for energy
storage applications [84]. To enhance the flexibility and mechanical strength of
polyaniline (PANI), Nepomuceno et al. synthesized PANI/CNCs composites through
an in-situ polymerization of PANI within CNCs suspensions, resulting in the
formation of a nanostructured material. The findings indicated that the incorporation
of CNCs significantly enhanced the thermal stability of PANI by up to 50 ℃,
suggesting that cellulose nanostructure acted as a supportive framework for
facilitating PANI deposition [85]. Fraser S A et al. reported the preparation of
polypyrrole/cellulose nanocomposites in a reaction media based on
[Cu(NH3)4(H2O)2](OH)2 (known as Schweizer's reagent/cuoxam) via an in situ
polymerization. The results demonstrated that Schweizer's reagent effectively
controlled the wettability of conductive cellulose composites, as evidenced by contact
angle being less than 90°. Importantly, their study showcased the feasibility of
employing cellulose solvents as a straightforward approach to regulate the structure
and characteristics of in situ functionalized cellulose nanocomposites [86].
4.1.2 Solvent compounding
The solvent compounding method entails the dissolution of polymer and CNCs in
an organic solvent, resulting in a homogeneous system and subsequently removing the
23
solvent to prepare the composite. Ma et al. employed the solution casting method to
prepare nanocomposites, incorporating acrylonitrile-butadiene-styrene (ABS) and
CNCs. The FTIR tests revealed a significant reduction in free hydroxyl groups and
hydrogen bonds between the CNCs upon their combination with ABS. Intriguingly,
compared to pure ABS (32.80 MPa), a notable enhancement in tensile strength was
achieved, reaching a maximum value of 36.56 MPa [87]. Subsequently, a solvent
casting procedure was utilized to prepare PVA/ECNCs-Qn nanocomposite films by
blending ECNCs-Qn with a PVA matrix. The findings demonstrated that the
PVA/ECNCs-Qn nanocomposite films exhibited significantly enhanced maximum
tensile strength of 45.4 MPa and elongation at break of 318.4%, respectively,
representing improvements of 37.2% and 94.3% compared to pure PVA films [88].
Ashori et al. utilized CNCs and aluminum oxide nanoparticles (Al2O3) as reinforcing
fillers to fabricate polyhydroxybutyrate-co-valerate (PHBV) nanocomposite films
through the solvent casting method. The binary nanocomposite, comprising of 1wt%
CNCs and Al2O3 nanoparticles, exhibited remarkable mechanical properties with
respective values reaching 124 MPa and 100 MPa, surpassing the pure PHBV's
strength of 60 MPa [89].
4.1.3 Latex compounding
Due to the electrostatic repulsion between neighboring CNCs, CNCs can be utilized
as aqueous suspensions, while latex is the predominant form for most rubber
materials. Therefore, latex compounding represents the prevailing approach for
fabricating rubber/CNCs nanocomposites [90-93]. Li et al. prepared NR/end-modified
CNCs nanocomposites using the latex mixing technique to ensure a uniform
dispersion of end-modified CNCs (Fig.12 (a)). With the addition of 10wt% end-
modified CNCs, the tensile strength of nanocomposites increased by 160%, Young's
modulus by 468%, and storage modulus by 1041% [94]. Gao et al. utilized latex
compounding and open two-roll milling techniques to create XNBR/CNCs/ZnO
composites, with the aim of enhancing the properties of XNBR. The findings
demonstrated that the incorporating of 10% CNCs and 5% ZnO resulted in a
significant increase in tensile strength compared to pure XNBR. The presence of ZnO
facilitated the cross-linking reaction between XNBR and carboxylate groups, forming
Zn2+-carboxylate cross-linked networks (Fig.13 (b)). The observed enhancement was
attributed to the exceptional interfacial compatibility achieved between abundant
carboxyl groups of CNCs and XNBR [95].
Undoubtedly, the preparation of water-based polymer composites requires the
utilization of the latex composite method. Zhang et al. utilized chloroacetic anhydride,
butyric anhydride, and caproic anhydride as modifiers for CNCs in combination with
waterborne polyurethane (WPU) to form a composite film. The results revealed that
composite with 1.00% of CNCs modified by butyric anhydride resulted in a fracture
stress of 52.15 MPa, which was 1262% higher than that of WPU (3.81 MPa) [96].
Vadillo et al. incorporated CNCs into the synthesis process of waterborne
polyurethane-urea (WBPUU) and fabricated the WBPUU scaffold via the
24
combination of direct ink writing 3D-printing and freeze-drying techniques (Fig.13).
It was found that CNCs exhibited a reinforcing effect in the printing system,
enhancing thermal stability as evidenced by an increase in compression modulus with
increasing CNCs content [97].

Fig.12. (a) The thiol-ene click reaction between end modification of CNCs and NR [94], (b) diagram of
double cross-linked network of XNBR/OCNCs/ZnO composites [95]

Fig.13. (a) Preparation process of WBPUU scaffold, (b) WBPUU/CNCs pieces immersed in CaCl2 [97]

25
 4.2 Application of CNCs nanocomposites

4.2.1 Sensing systems

The liquid crystal orderability of CNCs can be harnessed to fabricate a diverse
range of functional materials and even tailor their properties for specific sensing
applications. CNCs in water exhibit homogeneous suspensions at concentrations
below 4wt%, while significant aggregation becomes evident at concentrations
exceeding 15wt%. Interestingly, within the concentration range of 4 to 15wt%, CNCs
undergo self-assembled into chiral nematic liquid crystals. In these intricate systems,
CNCs exhibit remarkable capability in maintaining their inherent helical chiral
nematic order as one-dimensional photonic structures, thereby enabling their
utilization in sensing, laser technology, and optoelectronic devices [98]. Shao et al.
developed a facile and programmable method for the assembly of carboxylated CNCs
using capillary flow and the Marangoni effect. By combining this technique with 3D
inkjet printing technology, they successfully fabricated an encrypted QR code of
"SHTU" that could be decrypted under polarized light while remaining invisible
under natural light, making it readable by smartphone scanning under natural light
(Fig.14). This innovative approach exhibits significant potential for applications in
information encryption [99]. Zhang et al. discovered that the utilization of NMMO
solution as an "ink" for patterning CNCs films resulted in NMMO-treated CNCs films
exhibiting reversible responsive colors to humidity changes within a few minutes,
thereby enabling their potential applications in sensing, anti-counterfeiting, and
decoration fields [100]. Meanwhile, Zhao et al. successfully fabricated chiral nematic
papers (CNPs) with a mesoporous structure using CNCs through a swelling and
freeze-drying technique. Fig.15 demonstrated that CNPs/water suspension ink could
be formed after ultrasound treatment. When immersed in different solvents, patterns
written in suspension ink using different letters "Q," "L," and "U" displayed diverse
colors on paper. Undoubtedly, this varying color response of CNPs to different
polarities proved to be highly advantageous for numerous applications such as anti-
counterfeiting measures, decorative materials, and liquid sensors [101].

26
 Fig.14. Encryption and decryption of security QR label created by M-CNCs patterns in a 105×105
“pixelated” array fabricated through 3D inkjet printing [99]

Fig.15. Different ink was written on paper and display different colors when soaked with different
solvents [101]

4.2.2 Electronics industries

In recent years, there has been a growing emphasis on electronic devices, resulting
in the emergence of environmental contamination associated with electronic waste.
Consequently, the development of environmentally sustainable bio-based electronic
equipment has become a prominent area of research interest [102]. Martin-Sampedro
et al. fabricated NC-S nanopapers utilizing non-chemically pretreated lignocellulose
and bleached cellulose nanofibers, TEMPO-oxidized cellulose nanofibers (TOCNFs),
and CNCs in conjunction with sepiolite suspension as the raw materials. Fig.16
illustrates the optical transparency and transmission fog of the NC-S nanopapers. The
transmission haze can be tailored by selecting the appropriate type of nanocellulose
and adjusting the sepiolite content according to specific requirements, thereby
exhibiting potential applications in optoelectronic devices [103]. Peng et al. fabricated
a triboelectric nanogenerator (CTG) by incorporating CNCs as an effective dielectric
material into polydimethylsiloxane (PDMS). The results demonstrate that the
utilization of CNCs an efficient dielectric significantly enhanced the performance and
27
energy conversion efficiency of the generator. Notably, the improved power output of
these CTGs is capable of instantaneously illuminating up to 100 multicolor
commercial LEDs [104].

Fig.16. (a) Optical transparency and (b) transmission fog of NC-S nanopapers [103]
One key area in which electronic skin holds great potential is healthcare. By
integrating sensors into a flexible and stretchable material, it has the capability to
continuously monitor vital signs such as heart rate, blood pressure, and body
temperature in real-time. This technological advancement could facilitate early
detection of health issues and provide personalized medical care for individuals.
Additionally, electronic skin can be utilized in prosthetics to restore sensory feedback
for amputees, thereby enabling them to regain tactile sensation and enhance control
over their artificial limbs [105]. Chen et al. developed a self-assembled
PVA/nanocellulose-polyaniline (PVA/CP) E-skin using an innovative alternating
spraying technique driven by the Marangoni effect. The resulting PVA/CP40
composites film exhibited exceptional mechanical properties, high strain sensitivity,
and self-healing capabilities, thereby enabling effective detection and differentiation
of human motions and physiological signals (Fig.17). With its potential for multi-
signal capture and adaptability, this technology holds promise for various applications
in wearable electronics, E-skin development, personal health monitoring, and soft-
sensing systems in robotics [106]. Pi et al. successfully synthesized a physical-
chemical double crosslinked and double-network hydrogel by combining CNCs with
MXene through in situ polymerization and the cycle freeze-thaw method. This
innovative approach leveraged the excellent dispersibility of CNCs in water and their
electrostatic repulsion to effectively prevent MXene aggregation, thereby significantly
enhancing the mechanical properties of the hydrogel. It illustrates that even after
multiple cycles of action, the resistance signal's peak value remained essentially
unchanged, indicating elevated sensitivity, accuracy, and stability of the gel sensor.
Consequently, the CNCs/MXene hydrogel exhibits remarkable competitiveness for
human motion monitoring applications [107].

28
 Fig.17. PVA/CP40 detect human motions and physiological signals [106]

4.2.3 Packaging materials

The biodegradability and non-toxicity of CNCs have led to their been expanded
utilization in packaging materials and it easily incorporates or encapsulates various
natural antimicrobial and antioxidant agents, thereby enhancing their applicability
[108]. Lee et al. modified CNCs by acetic anhydride and 1-bromo-dodecane, and
prepared PLA/modified-CNCs composite membrane using a solution casting
technique. The investigation revealed that the incorporation of alkyl-CNCs resulted in
a significant enhancement in the mechanical and gas barrier properties (Fig.18) of the
PLA nanocomposites because of uniform dispersion and strong interfacial adhesion.
The PLA/modified-CNCs composites demonstrate significant potential for practical
applications in food packaging materials [109]. Wang et al. employed a sequential
deposition technique involving oxalic acid-modified cellulose and nano-alkali lignin
infiltration to effectively enhance the synergistic effect on barrier and mechanical
properties through self-bonding and crosslinking between cellulose and lignin. This
approach successfully restored the porosity and hydrophilicity of the paper packaging
material, resulting in a remarkable increase of over four times in tensile strength as
well as improved resistance against lipids and water [110].

29
 Fig.18. Permeability characterization of PLA composite [109]

4.2.4 Stabilizers
The application of Pickering emulsion in the industry necessitates improvement due
to the environmental, health, and cost issues associated with traditional emulsion
stabilizers. Consequently, there is a growing focus on employing non-toxic stabilizers
as an imperative topic within this field [111]. Tang et al. successfully grafted
hydrophobic polystyrene onto CNCs, subsequently employing them as stabilizers in
Pickering emulsion systems containing toluene or hexadecane dispersed in water.
Remarkably, both emulsions exhibited exceptional stability against coalescence for a
remarkable duration exceeding 4 months [112]. Sun et al. demonstrated that the
incorporation of sulfated CNCs (SCNCs) led to enhanced colloidal stability of
gelatin-encapsulated tea polyphenols (G-TPP). The presence of sulfate groups on the
surface of SCNCs improves capsule stability, while the layered structure of SCNCS
provides protective barriers for TPP, thereby enhancing its stability [113]. Gong et al.
successfully synthesized oxidized CNCs (O-CNCs) through periodate oxidation,
followed by the production of hydrophobic m-O-CNCs using
phenyltrimethylammonium chloride. The findings demonstrated that a lower quantity
of m-O-CNCs was sufficient to function as a Pickering emulsion agent in comparison
to conventional surfactants [114].
4.2.5 Drug delivery
CNCs serve as versatile carriers for both hydrophobic and hydrophilic drugs due to
their ability to form stable dispersions and accommodate a wide range of drug
molecules. The large surface area of CNCs facilitates efficient drug loading, leading
to increased drug loading capacity and encapsulation efficiency. Moreover, surface
modification of CNCs enables the integration of targeting ligands or stimuli-
responsive moieties, allowing for precise site-specific drug delivery. Yusefi et al.
demonstrated the anticancer activity of CNCs loaded with 5-fluorouracil (CNCs/5FU)
30
against colorectal cancer cells. They observed an improvement in the thermal stability
of the anticancer drug 5FU after loading onto CNCs and achieved a high drug
encapsulation efficiency of 83.50±1.52% for CNCs/5FU. Furthermore, they found
that CNCs did not impact the viability of CCD112 colon normal cells, while
CNCs/5FU exhibited anti-tumor effects on HCT116 and HT-29 colorectal cancer cells
(Fig.20) [115]. Emam et al. utilized succinic acid-modified CNCs along with N-
isopropyl acrylamide (NIPAm) to create a novel pH and temperature-responsive
system for drug release, referred to as Su-CNCs/PNIPAm (Fig.20). They observed a
notable acceleration in the rate of drug release as the pH shifted from 10 to 2 over a
period exceeding 6 hours at 25 °C [116].

Fig.20. Effect of pH and thermo-responsive on the active Su-CNCs/PNIPAm loaded drug release [116]

4.2.6 Cosmetics
Nanocelluloses, including nanoparticles, nanocrystals, nanofibers, nanoyarns, and
bacterial cellulose, have recently been incorporated into skincare products, cosmetics,
and health monitoring devices as environmentally friendly alternatives to synthetic
polymers like polyethylene, polyacrylamides, and nylon [117]. Xia et al. have
successfully developed chiral nanorods with a core-shell structure mimicking
melanin, wherein the core is composed of CNCs and the shell consists of
polydopamine (PDA). These novel nanorods exhibited distinct liquid crystal phases
characterized by well-defined chirality, showcasing their potential applications in
cosmetics industry, particularly as eyeshadows featuring an exquisite metallic color
design [118]. Xiong et al. have successfully developed a novel approach to enhance
the safety of bio-based sunscreens by employing bionic design, which involves
encapsulating cellulose with anthocyanin (AN). The application of this innovative
technology in lipstick formulation has resulted in a product that demonstrates
exceptional capabilities in ultraviolet shielding (high sun protection value), water
31
resistance, and effortless application through rubbing [119].

5. Conclusion and prospect

In this review, we offer a comprehensive overview of the preparation methods and

modifications of CNCs, along with their diverse applications across various fields.
Through meticulous analysis of current research, several key conclusions emerge.
Firstly, CNCs display significant potential for preparation and modification, owing to
their derivation from natural renewable resources. The continuous evolution of
diverse methods and techniques has provided abundant options for their
functionalization and surface modification, thereby facilitating precise regulation of
their properties. Secondly, CNCs show great promise in a wide array of applications
sensing systems, electronics industries, packaging materials, stabilizers, drug delivery,
and cosmetics. As carriers, CNCs not only ensure stable drug delivery but also enable
controlled and targeted release of drugs-opening up novel avenues and possibilities
for the design of drug delivery systems. In conclusion, CNCs emerge as a versatile
material with significant potential for applications and promising prospects for further
development. Their environmentally friendly nature and sustainable advantages are
poised to gain broader recognition and application in future research efforts. Through
ongoing innovation and collaborative efforts, we anticipate continued exploration of
their synthesis, modification, and application mechanisms in future research
endeavors, aiming to develop more sustainable and efficient preparation methods and
accelerate their commercial utilization across diverse fields such as medicine, food
production, cosmetics, and beyond.

Acknowledgments

This research was funded by National Natural Science Foundation of China (grant
number 52341301), the Basic Scientific Research Project of Liaoning Provincial
Department of Education, China (grant number LJKMZ20220767), and Outstanding
Young Talent Projects of Shenyang University of Chemical Technology, China (grant
number 2019YQ003).

Reference

[1] Zhao D, Li R, Shi L, Zeng X, Zhang W, Wu R, et al. Tendencies of research and

development in resources chemicals and materials-Summarization of a Youth's topic
forum. Resources Chemicals and Materials. 2023; 2(3): 215-222.
[2] Xie Y, Gao S, Zhang D, Wang C, Chu F. Bio-based polymeric materials
synthesized from renewable resources: A Mini-Review. Resources Chemicals and
Materials. 2023; 2(3): 223-230.
[3] Zhu X, Jiang G, Wang G, Zhu Y, Cheng W, Zeng S, et al. Cellulose-based
functional gels and applications in flexible supercapacitors. Resources Chemicals and
Materials. 2023; 2(2): 177-188.
32
[4] Han Z, Yue J, Zeng X, Yu J, Wang F, Guan Y, et al. Major challenges and recent
advances in characterizing biomass thermochemical reactions. Resources Chemicals
and Materials. 2024; 3(2): 146-158.
[5] Liu BR, Cheng L, Yuan Y, Hu J, Zhou LJ, Zong L, et al. Liquid-crystalline
assembly of spherical cellulose nanocrystals. International Journal of Biological
Macromolecules, 2023, 242: 124738.
[6] Leong MY, Kong YL, Harun MY, Looi CY, Wong WF. Current advances of
nanocellulose application in biomedical field. Carbohydrate Research. 2023; 532:
108899.
[7] Poletto M, Zattera AJ, Forte MMC, Santana RMC. Thermal decomposition of
wood: Influence of wood components and cellulose crystallite size. Bioresource
Technology. 2012; 109: 148-153.
[8] Spagnol C, Rodrigues FHA, Neto A, Pereira AGB, Fajardo AR, Radovanovic E, et
al. Nanocomposites based on poly(acrylamide-co-acrylate) and cellulose
nanowhiskers. European Polymer Journal. 2012; 48: 454-463.
[9] Doan TKQ, Chiang KY. Characteristics and kinetics study of spherical cellulose
nanocrystal extracted from cotton cloth waste by acid hydrolysis. Sustainable
Environment Research. 2022; 32(1): 26.
[10] Dias IKR, Siqueira GA, Arantes V. Xylanase increases the selectivity of the
enzymatic hydrolysis with endoglucanase to produce cellulose nanocrystals with
improved properties. International Journal of Biological Macromolecules. 2022; 220:
589-600.
[11] Manrich A, Martins MA, Mattoso LHC. Manufacture and performance of peanut
skin cellulose nanocrystals. Scientia Agricola. 2022; 79(6): +20210010.
[12] Ramakrishnan A, Ravishankar K, Dhamodharan R. Preparation of nanofibrillated
cellulose and nanocrystalline cellulose from surgical cotton and cellulose pulp in hot-
glycerol medium. Cellulose. 2019; 26: 3127-3141.
[13] Padhi S, Singh A, Routray W. Nanocellulose from agro-waste: a comprehensive
review of extraction methods and applications. Reviews in Environmental Science
and Bio-Technology. 2023; 22: 1-27.
[14] Tang L, Wang B, Bai SR, Fan B, Zhang L, Wang FZ. Preparation and
characterization of cellulose nanocrystals with high stability from okara by green
solvent pretreatment assisted TEMPO oxidation. Carbohydrate Polymers. 2024; 324.
[15] Cheng M, Qin ZY, Chen YY, Liu JM, Ren ZC. Facile one-step extraction and
oxidative carboxylation of cellulose nanocrystals through hydrothermal reaction by
using mixed inorganic acids. Cellulose. 2017; 24: 3243-3254.
[16] Vanderfleet OM, Cranston ED. Production routes to tailor the performance of
cellulose nanocrystals. Nature Reviews Materials. 2021; 6: 124-144.
[17] Gond RK, Gupta MK, Jawaid M. Extraction of nanocellulose from sugarcane
bagasse and its characterization for potential applications. Polymer Composites. 2021;
42: 5400-5412.
[18] Bian HY, Chen LH, Dai HQ, Zhu JY. Integrated production of lignin containing
cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using an easily recyclable di-
33
carboxylic acid. Carbohydrate Polymers. 2017; 167: 167-176.
[19] Hu J, Kong ZQ, Liu K, Qin JL, Tao YH, Zhou LJ, et al. Carboxylation of
cellulose nanocrystals for reinforcing and toughing rubber through dual cross-linking
networks. ACS Applied Polymer Materials. 2021; 3: 6120-6129.
[20] Tuerxun D, Pulingam T, Nordin NI, Chen YW, Bin Kamaldin J, Julkapli NBM, et
al. Synthesis, characterization and cytotoxicity studies of nanocrystalline cellulose
from the production waste of rubber-wood and kenaf-bast fibers. European Polymer
Journal. 2019; 116: 352-360.
[21] Salari M, Khiabani MS, Mokarram RR, Ghanbarzadeh B, Kafil HS. Preparation
and characterization of cellulose nanocrystals from bacterial cellulose produced in
sugar beet molasses and cheese whey media. International Journal of Biological
Macromolecules. 2019; 122: 280-288.
[22] Lv D, Du HS, Che XP, Wu MY, Zhang YD, Liu C, et al. Tailored and integrated
production of functional cellulose nanocrystals and cellulose nanofibrils via
sustainable formic acid hydrolysis: Kinetic Study and Characterization. ACS
Sustainable Chemistry & Engineering, 2019, 7(10): 9449-9463.
[23] Du HS, Liu C, Mu XD, Gong WB, Lv D, Hong YM, et al. Preparation and
characterization of thermally stable cellulose nanocrystals via a sustainable approach
of FeCl3-catalyzed formic acid hydrolysis. Cellulose. 2016; 23: 2389-2407.
[24] Xu WY, Grénman H, Liu J, Kronlund D, Li B, Backman P, et al. Mild oxalic-
acid-catalyzed hydrolysis as a novel approach to prepare cellulose nanocrystals.
ChemNanoMat, 2017, 3(2): 109-119.
[25] Chen LH, Zhu JY, Baez C, Kitin P, Elder T. Highly thermal-stable and functional
cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids.
Green Chemistry. 2016; 18: 3835-3843.
[26] Liu C, Li B, Du HS, Lv D, Zhang YD, Yu G, et al. Properties of nanocellulose
isolated from corncob residue using sulfuric acid, formic acid, oxidative and
mechanical methods. Carbohydrate Polymers. 2016; 151: 716-724.
[27] Yu HY, Zhang DZ, Lu FF, Yao JM. New Approach for Single-step extraction of
carboxylated cellulose nanocrystals for their use as adsorbents and flocculants. ACS
Sustainable Chemistry & Engineering. 2016; 4: 2632-2643.
[28] Trache D, Hussin MH, Haafiz MKM, Thakur VK. Recent progress in cellulose
nanocrystals: sources and production. Nanoscale. 2017;9:1763-1786.
[29] Liu PW, Pang B, Dechert S, Zhang XC, Andreas LB, Fischer S, et al. Structure
selectivity of alkaline periodate oxidation on lignocellulose for facile isolation of
cellulose nanocrystals. Angewandte Chemie-International Edition. 2020; 59: 3218-
3225.
[30] Okita Y, Saito T, Isogai A. Entire surface oxidation of various cellulose
microfibrils by TEMPO-mediated oxidation. Biomacromolecules. 2010; 11: 1696-
1700.
[31] Fraschini C, Chauve G, Bouchard J. TEMPO-mediated surface oxidation of
cellulose nanocrystals (CNCs). Cellulose. 2017; 24: 2775-2790.
[32] Fukui S, Ito T, Saito T, Noguchi T, Isogai A. Surface-hydrophobized TEMPO-
34
nanocellulose/rubber composite films prepared in heterogeneous and homogeneous
systems. Cellulose. 2019; 26: 463-473.
[33] Wang H, Pudukudy M, Ni YH, Zhi YF, Zhang H, Wang ZQ, et al. Synthesis of
nanocrystalline cellulose via ammonium persulfate-assisted swelling followed by
oxidation and their chiral self-assembly. Cellulose. 2020; 27: 657-676.
[34] Liu YX, Liu LH, Wang KT, Zhang H, Yuan Y, Wei HX, et al. Modified
ammonium persulfate oxidations for efficient preparation of carboxylated cellulose
nanocrystals. Carbohydrate Polymers. 2020; 229: 115572.
[35] Wang CP, Yuan ZY, Wang A, Qu JL, Fang Z, Wen YB. Ultraviolet light enhanced
sodium persulfate oxidation of cellulose to facilitate the preparation of cellulose
nanofibers. Cellulose. 2020; 27: 2041-2051.
[36] Yang H, Alam MN, van de Ven TGM. Highly charged nanocrystalline cellulose
and dicarboxylated cellulose from periodate and chlorite oxidized cellulose fibers.
Cellulose. 2013; 20: 1865-1875.
[37] Sultana N, Edlund U, Guria C, Westman G. Kinetics of periodate-mediated
oxidation of cellulose. Polymers. 2024; 16(3): 381.
[38] Pandeirada CO, Achterweust M, Janssen HG, Westphal Y, Schols HA. Periodate
oxidation of plant polysaccharides provides polysaccharide-specific oligosaccharides.
Carbohydrate Polymers. 2022; 291: 119540.
[39] Lin XB, Guo XY, Xu CF, Wu M. Carboxymethyl cellulose assisted mechanical
preparation of cellulose nanocrystals with high yield. Cellulose. 2019; 26: 5227-5236.
[40] Pelissari FM, Sobral PJdA, Menegalli FC. Isolation and characterization of
cellulose nanofibers from banana peels. Cellulose. 2014; 21: 417-432.
[41] Liu XW, Sun HN, Mu TH, Fauconnier ML, Li M. Preparation of cellulose
nanofibers from potato residues by ultrasonication combined with high-pressure
homogenization. Food Chemistry. 2023; 413: 135675.
[42] Park NM, Choi S, Oh JE, Hwang DY. Facile extraction of cellulose nanocrystals.
Carbohydrate Polymers. 2019; 223: 115114.
[43] Baheti V, Abbasi R, Militky J. Ball milling of jute fibre wastes to prepare
nanocellulose. World Journal of Engineering. 2012; 9: 45-50.
[44] Yao AN, Tan L, Guo RH, Zhou M, Zhang Y, Zhu PX. Preparation of cellulose
nanocrystals and their application in reinforcing viscose filaments. Cellulose. 2020;
27: 10553-65.
[45] Cheng QZ, Wang SQ, Han QY. Novel process for isolating fibrils from cellulose
fibers by high-intensity ultrasonication. II. Fibril Characterization. Journal of Applied
Polymer Science, 2010, 115(5): 2756-2762.
[46] Xu YJ, Gao ML, Zhang YQ, Ning LL, Zhao DQ, Ni YH. Cellulose hollow
annular nanoparticles prepared from high-intensity ultrasonic treatment. ACS Nano.
2022; 16: 8928-38.
[47] Xie JL, Hse CY, Li CJ, Shupe TF, Hu TX, Qi JQ, et al. Characterization of
microwave liquefied bamboo potential use in the generation of nanofibrillated residue
and its cellulosic fiber. ACS Sustainable Chemistry & Engineering. 2016; 4: 3477-
3485.
35
[48] Khawas P, Deka SC. Isolation and characterization of cellulose nanofibers from
culinary banana peel using high-intensity ultrasonication combined with chemical
treatment. Carbohydrate Polymers. 2016; 137: 608-616.
[49] Berto GL, Mattos BD, Velasco J, Zhao B, Segato F, Rojas OJ, et al.
Endoglucanase effects on energy consumption in the mechanical fibrillation of
cellulose fibers into nanocelluloses. International Journal of Biological
Macromolecules. 2023; 243: 125002.
[50] Chen X-Q, Deng X-Y, Shen W-H, Jia M-Y. Preparation and characterization of
the spherical nanosized cellulose by the enzymatic hydrolysis of pulp fibers.
Carbohydrate Polymers. 2018; 181: 879-884.
[51] Tong X, Shen W, Chen X, Jia M, Roux JC. Preparation and mechanism analysis
of morphology℃controlled cellulose nanocrystals via compound enzymatic hydrolysis
of eucalyptus pulp. Journal of Applied Polymer Science. 2020; 137: 48407.
[52] Xiang Q, Lee Y Y, Pettersson P O, et al. Heterogeneous aspects of acid
hydrolysis of α-cellulose. Biotechnology for Fuels and Chemicals: The Twenty-Fourth
Symposium. Humana Press, 2003: 505-514.
[53] Brandt A, Hallett JP, Leak DJ, Murphy RJ, Welton T. The effect of the ionic
liquid anion in the pretreatment of pine wood chips. Green Chemistry. 2010; 12: 672-
679.
[54] Hou XD, Smith TJ, Li N, Zong MH. Novel renewable ionic liquids as highly
effective solvents for pretreatment of rice straw biomass by selective removal of
lignin. Biotechnology and Bio-Engineering. 2012; 109: 2484-2493.
[55] Abushammala H, Krossing I, Laborie M-P. Ionic liquid-mediated technology to
produce cellulose nanocrystals directly from wood. Carbohydrate Polymers. 2015;
134: 609-616.
[56] Miao J, Yu Y, Jiang Z, Zhang L. One-pot preparation of hydrophobic cellulose
nanocrystals in an ionic liquid. Cellulose. 2016; 23: 1209-1219.
[57] Wang H, Li J, Zeng X, Tang X, Sun Y, Lei T, et al. Extraction of cellulose
nanocrystals using a recyclable deep eutectic solvent. Cellulose. 2020; 27: 1301-1314.
[58] Ma Y, Xia Q, Liu Y, Chen W, Liu S, Wang Q, et al. Production of nanocellulose
using hydrated deep eutectic solvent combined with ultrasonic treatment. ACS
Omega. 2019; 4(5): 8539-8547.
[59] Lynam JG, Kumar N, Wong MJ. Deep eutectic solvents’ ability to solubilize
lignin, cellulose, and hemicellulose; thermal stability; and density. Bioresource
Technology. 2017; 238: 684-689.
[60] Yiin CL, Quitain AT, Yusup S, Sasaki M, Uemura Y, Kida T. Characterization of
natural low transition temperature mixtures (LTTMs): Green solvents for biomass
delignification. Bioresource Technology. 2016; 199: 258-264.
[61] Sirvio JA, Visanko M, Liimatainen H. Acidic deep eutectic solvents as hydrolytic
media for cellulose nanocrystal production. Biomacromolecules. 2016; 17: 3025-
3032.
[62] Liu S, Zhang Q, Gou S, Zhang L, Wang Z. Esterification of cellulose using
carboxylic acid-based deep eutectic solvents to produce high-yield cellulose
36
nanofibers. Carbohydrate Polymers. 2021; 251: 117018.
[63] Gao A, Chen H, Hou A, Xie K. Preparation of high-aspect-ratio cellulose
nanocrystals by solvothermal synthesis followed by mechanical exfoliation. Cellulose.
2019; 26: 5937-5945.
[64] Pääkkönen T, Spiliopoulos P, Nonappa D, Kontturi KS, Penttilä P, Viljanen M, et
al. Sustainable high yield route to cellulose nanocrystals from bacterial cellulose. ACS
Sustainable Chemistry & Engineering. 2019, 7(17): 14384-14388.
[65] Azrina ZZ, Beg MDH, Rosli M, Ramli R, Junadi N, Alam AM. Spherical
nanocrystalline cellulose (NCC) from oil palm empty fruit bunch pulp via ultrasound
assisted hydrolysis. Carbohydrate Polymers. 2017; 162: 115-120.
[66] Li B, Xu W, Kronlund D, Määttänen A, Liu J, Smått J-H, et al. Cellulose
nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated
oxidation. Carbohydrate Polymers. 2015; 133: 605-612.
[67] Eyley S, Thielemans W. Surface modification of cellulose nanocrystals.
Nanoscale. 2014; 6: 7764-7779.
[68] Cheng D, Wen Y, Wang L, An X, Zhu X, Ni Y. Adsorption of polyethylene glycol
(PEG) onto cellulose nano-crystals to improve its dispersity. Carbohydrate Polymers.
2015; 123: 157-163.
[69] Jiang W, Shen P, Yi J, Li L, Wu C, Gu J. Surface modification of nanocrystalline
cellulose and its application in natural rubber composites. Journal of Applied Polymer
Science. 2020; 137: 49163.
[70] Ali SD, Imiete IE, Orlandi ME, Castellani L, Hanel T, Zoia L. Novel CNC/silica
hybrid as potential reinforcing filler for natural rubber compounds. Journal of Applied
Polymer Science. 2020; 137: 48332.
[71] Michel B, Imberty A, Heggset EB, Syverud K, Bras J, Dufresne A. Adsorption
characterization of various modified β-cyclodextrins onto TEMPO-oxidized cellulose
nanofibril membranes and cryogels. Sustainable Chemistry and Pharmacy, 2021, 24:
100523.
[72] Hsu Y-I, Huang L, Asoh T-A, Uyama H. Anhydride-cured epoxy resin
reinforcing with citric acid-modified cellulose. Polymer Degradation and Stability.
2020; 178: 109213.
[73] Lu J, Lang J, Lan P, Yang H, Yang J, Wu X, et al. Evalution of surface activity of
hydrophobic modified nanocrystalline cellulose. Cellulose. 2020; 27: 9299-9309.
[74] Leszczynska A, Radzik P, Szefer E, Micusík M, Omastová M, Pielichowski K.
Surface modification of cellulose nanocrystals with succinic anhydride. Polymers.
2019, 11(5): 866.
[75] Brochier Salon M-C, Belgacem MN. Hydrolysis-condensation kinetics of
different silane coupling agents. Phosphorus, Sulfur, and Silicon and the Related
Elements, 2011, 186(2): 240-254.
[76] Wang Y, Xie R, Li D, Shen Y, Xie W, Wang H, et al. A cross-linking/percolating-
integrated strategy to enhance crystallizable rubber using rod-like reactive biobased
nanocrystals. ACS Applied Bio Materials. 2019; 3(1): 441-449.
[77] Fan X, Yang X, Wang S, Wang S, Xu X, Jiang J, et al. Modified cellulose
37
nanocrystals are used to enhance the performance of self-healing siloxane elastomers.
Carbohydrate Polymers. 2021; 273: 118529.
[78] Aziz T, Iqbal M, Ullah R, Jamil MI, Raheel M, Ali A, et al. Improving Adhesive
Properties of Cellulose Nanocrystals Modifying By 3-Glycidoxypropyltrimethoxy
Silane (KH-560) Coupling Agents. Biomedical Journal of Scientific Technical
Research. 2021; 34(1): 005492.
[79] Dhali K, Daver F, Cass P, Adhikari B. Surface modification of the cellulose
nanocrystals through vinyl silane grafting. International Journal of Biological
Macromolecules. 2022; 200: 397-408.
[80] Le Gars M, Delvart A, Roger P, Belgacem MN, Bras J. Amidation of TEMPO-
oxidized cellulose nanocrystals using aromatic aminated molecules. Colloid and
Polymer Science. 2020; 298: 603-617.
[81] Zhou L, He H, Li MC, Huang SW, Mei CT, Wu QL. Enhancing mechanical
properties of poly(lactic acid) through its in-situ crosslinking with maleic anhydride-
modified cellulose nanocrystals from cottonseed hulls. Industrial Crops and Products,
2018, 112: 449-459.
[82] An LL, Chen J, Heo JW, Bae JH, Jeong H, Kim YS. Synthesis of lignin-modified
cellulose nanocrystals with antioxidant activity via Diels-Alder reaction and its
application in carboxymethyl cellulose film. Carbohydrate Polymers. 2021; 274:
118651.
[83] Yin Y, Zhao L, Jiang X, Wang H, Gao W. Poly (lactic acid)-based biocomposites
reinforced with modified cellulose nanocrystals. Cellulose. 2017; 24: 4773-4784.
[84] Mu M, Huang J, Chen Y, Li Y, Yu H-Y, Yao J. Simultaneously enhance the heat
storage capacity and shape stability of poly (hexadecyl acrylate) by immobilizing it to
cellulose nanocrystal via in situ free radical polymerization. ACS Applied Polymer
Materials, 2022, 4(2): 899-907.
[85] Nepomuceno N, Seixas A, Medeiros E, Mélo T. Evaluation of conductivity of
nanostructured polyaniline/cellulose nanocrystals (PANI/CNC) obtained via in situ
polymerization. Journal of Solid State Chemistry. 2021; 302: 122372.
[86] Fraser SA, van Zyl WE. In situ polymerization and electrical conductivity of
polypyrrole/cellulose nanocomposites using Schweizer's reagent. RSC advances,
2022, 12(34): 22031-22043.
[87] Ma L, Zhang Y, Wang S. Preparation and characterization of acrylonitrile℃
butadiene℃styrene nanocomposites reinforced with cellulose nanocrystal via solution
casting method. Polymer Composites. 2017; 38: 167-173.
[88] Meng L, Li J, Fan X, Wang Y, Xiao Z, Wang H, et al. Improved mechanical and
antibacterial properties of polyvinyl alcohol composite films using quaternized
cellulose nanocrystals as nanofillers. Composites Science and Technology. 2023; 232:
109885.
[89] Ashori A, Jonoobi M, Ayrilmis N, Shahreki A, Fashapoyeh MA. Preparation and
characterization of polyhydroxybutyrate-co-valerate (PHBV) as green composites
using nano reinforcements. International Journal of Biological Macromolecules.
2019;136:1119-1124.
38
[90] Varghese S, Karger-Kocsis J. Natural rubber-based nanocomposites by latex
compounding with layered silicates. Polymer. 2003; 44: 4921-4927.
[91] Potts JR, Shankar O, Du L, Ruoff RS. Processing-morphology-property
relationships and composite theory analysis of reduced graphene oxide/natural rubber
nanocomposites. Macromolecules. 2012; 45: 6045-6055.
[92] Wu Y-P, Wang Y-Q, Zhang H-F, Wang Y-Z, Yu D-S, Zhang L-Q, et al. Rubber-
pristine clay nanocomposites prepared by co-coagulating rubber latex and clay
aqueous suspension. Composites Science and Technology. 2005; 65: 1195-202.
[93] Cao L, Liu C, Zou D, Zhang S, Chen Y. Using cellulose nanocrystals as
sustainable additive to enhance mechanical and shape memory properties of
PLA/ENR thermoplastic vulcanizates. Carbohydrate Polymers. 2020; 230: 115618.
[94] Li L, Tao H, Wu B, Zhu G, Li K, Lin N. Triazole end-grafting on cellulose
nanocrystals for water-redispersion improvement and reactive enhancement to
nanocomposites. ACS Sustainable Chemistry & Engineering. 2018; 6: 14888-14900.
[95] Gao B, Yang J, Chen Y, Zhang S. Oxidized cellulose nanocrystal as sustainable
crosslinker to fabricate carboxylated nitrile rubber composites with antibiosis,
wearing and irradiation aging resistance. Composites Part B: Engineering, 2021, 225:
109253.
[96] Zhang Y, Wang X, Luo L, Huang Y, Li K, Li J. Enhancement effect of acylated
cellulose nanocrystals on waterborne polyurethane. Journal of Polymer Research.
2022; 29: 347.
[97] Vadillo J, Larraza I, Calvo-Correas T, Martin L, Derail C, Eceiza A. Enhancing
the mechanical properties of 3D-printed waterborne polyurethane-urea and cellulose
nanocrystal scaffolds through crosslinking. Polymers. 2022; 14(22): 4999.
[98] Risteen BE, Blake A, McBride MA, Rosu C, Park JO, Srinivasarao M, et al.
Enhanced alignment of water-soluble polythiophene using cellulose nanocrystals as a
liquid crystal template. Biomacromolecules. 2017; 18: 1556-1562.
[99] Shao R, Meng X, Shi Z, Zhong J, Cai Z, Hu J, et al. Marangoni flow manipulated
concentric assembly of cellulose nanocrystals. Small Methods. 2021; 5: 2100690.
[100] Zhang Y, Tian Z, Fu Y, Wang Z, Qin M, Yuan Z. Responsive and patterned
cellulose nanocrystal films modified by N-methylmorpholine-N-oxide. Carbohydrate
Polymers. 2020; 228: 115387.
[101] Zhao H, Dai X, Yuan Z, Li G, Fu Y, Qin M. Iridescent chiral nematic papers
based on cellulose nanocrystals with multiple optical responses for patterned coatings.
Carbohydrate Polymers. 2022; 289: 119461.
[102] Kim JW, Park H, Lee G, Jeong YR, Hong SY, Keum K, et al. Paper℃like, thin,
foldable, and self℃healable electronics based on PVA/CNC nanocomposite film.
Advanced Functional Materials. 2019; 29: 1905968.
[103] Martín-Sampedro R, Eugenio ME, Ibarra D, Ruiz-Hitzky E, Aranda P, Darder
M. Tailoring the properties of nanocellulose-sepiolite hybrid nanopapers by varying
the nanocellulose type and clay content. Cellulose. 2022; 29: 5265-5287.
[104] Peng J, Zhang H, Zheng Q, Clemons CM, Sabo RC, Gong S, et al. A composite
generator film impregnated with cellulose nanocrystals for enhanced triboelectric
39
performance. Nanoscale. 2017; 9: 1428-1433.
[105] Dong Y, Yu H-Y, Tian Y, Yao X, Xue B, Xu D, et al. Highly sensitive, self-
healable, and robust polyvinyl alcohol/nanocellulose composite electronic skin by
single-step Marangoni self-assembly for multipoint sensing. ACS Sustainable
Chemistry & Engineering. 2023;11:13149-13163.
[106] Chen H, Dejace L, Lacour SP. Electronic skins for healthcare monitoring and
smart prostheses. Annual Review of Control, Robotics, and Autonomous Systems.
2021; 4: 629-650.
[107] Pi M, Jiang L, Wang Z, Cui W, Shi L, Ran R. Robust and ultrasensitive
hydrogel sensors enhanced by MXene/cellulose nanocrystals. Journal of Materials
Science. 2021; 56: 8871-8886.
[108] Xiang H, Wang B, Zhong M, Liu W, Yu D, Wang Y, et al. Sustainable and
versatile superhydrophobic cellulose nanocrystals. ACS Sustainable Chemistry &
Engineering. 2022;10: 5939-5948.
[109] Lee JH, Park SH, Kim SH. Surface alkylation of cellulose nanocrystals to
enhance their compatibility with polylactide. Polymers. 2020; 12(1): 178.
[110] Wang W, Gu F, Deng Z, Zhu Y, Zhu J, Guo T, et al. Multilayer surface
construction for enhancing barrier properties of cellulose-based packaging.
Carbohydrate Polymers. 2021; 255: 117431.
[111] Rayner M, Marku D, Eriksson M, Sjöö M, Dejmek P, Wahlgren M. Biomass-
based particles for the formulation of Pickering type emulsions in food and topical
applications. Colloids and Surfaces A: Physicochemical and Engineering Aspects.
2014; 458: 48-62.
[112] Tang C, Spinney S, Shi Z, Tang J, Peng B, Luo J, et al. Amphiphilic cellulose
nanocrystals for enhanced Pickering emulsion stabilization. Langmuir. 2018; 34:
12897-12905.
[113] Sun B, Zhang M, Ni Y. Use of sulfated cellulose nanocrystals towards stability
enhancement of gelatin-encapsulated tea polyphenols. Cellulose. 2018; 25: 5157-
5173.
[114] Gong X, Wang Y, Chen L. Enhanced emulsifying properties of wood-based
cellulose nanocrystals as Pickering emulsion stabilizer. Carbohydrate Polymers. 2017;
169: 295-303.
[115] Yusefi M, Soon ML-K, Teow S-Y, Monchouguy EI, Neerooa BNHM, Izadiyan
Z, et al. Fabrication of cellulose nanocrystals as potential anticancer drug delivery
systems for colorectal cancer treatment. International Journal of Biological
Macromolecules. 2022; 199: 372-385.
[116] Emam HE, Shaheen TI. Design of a dual pH and temperature responsive
hydrogel based on esterified cellulose nanocrystals for potential drug release.
Carbohydrate Polymers. 2022;278.
[117] Kim SM, Gwak EJ, Jeong SH, Lee SM, Sim WJ, Kim JS. Toxicity evaluation of
cellulose nanofibers (CNFs) for cosmetic industry application. Journal of Toxicology
Risk Assessment. 2019; 5: 1-6.
[118] Xia K, Zheng X, Wang Y, Zhong W, Dong Z, Ye Z, et al. Biomimetic chiral
40
photonic materials with tunable metallic colorations prepared from chiral melanin-like
nanorods for UV shielding, humidity sensing, and cosmetics. Langmuir. 2022; 38:
8114-8124.
[119] Xiong L, He H, Tang J, Yang Q, Li L. Self-assembly of cellulose nanocrystals
and organic colored pigments as reinforcement matrix of lipstick for enhancing SPF.
Oxidative Medicine and Cellular Longevity. 2022;2022.
Declaration of interests

☒ The authors declare that they have no known competing financial interests or

personal relationships that could have appeared to influence the work reported in this

paper.

☒ The author is an Editorial Board Member/Editor-in-Chief/Associate Editor/Guest

Editor for [Journal name] and was not involved in the editorial review or the decision

to publish this article.

☐ The authors declare the following financial interests/personal relationships which

may be considered as potential competing interests:

41
42