Current Opinion in Colloid & Interface Science 29 (2017) 32–45

Contents lists available at ScienceDirect

Current Opinion in Colloid & Interface Science

journal homepage: www.elsevier.com/locate/cocis

Recent advances in the application of cellulose nanocrystals

Nathan Grishkewich, Nishil Mohammed, Juntao Tang, Kam Chiu Tam ⁎
Department of Chemical Engineering, Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue, Waterloo, ON N2L 3G1, Canada

a r t i c l e i n f o a b s t r a c t

Article history: This review describes recent advances on the application of cellulose nanocrystals (CNCs) in selected
Received 19 October 2016 applications. CNCs are produced via acid hydrolysis of cellulosic materials, such as wood, cotton, tunicate, or
Received in revised form 31 January 2017 other biomass. It possesses many desirable properties, such as large surface area, high tensile strength and
Accepted 31 January 2017
stiffness, excellent colloidal stability, and potential for modification due to the abundance of surface hydroxyl
Available online 17 February 2017
groups. By modifying its surface with small molecules, polymers, and nanoparticles, they can be utilized as a
Keywords:
zero-dimension nanostructure for drug delivery, spun into 1-dimension fibers for enhanced strength, cast into
Cellulose nanocrystals 2-dimension films for flexibility, or molded into 3-dimension hydrogels and aerogels for compressibility or
Nanocomposites porous materials. The use and impact of CNCs in three industrial sectors: biomedical, wastewater treatment,
Films energy and electronics are described and discussed, and we will offer our perspective on the future and new
Nanoparticles applications of this sustainable nanomaterial.
Modification © 2017 Elsevier Ltd. All rights reserved.
Biomedical
Wastewater treatment
Sensors
Energy storage

1. Introduction
In today's age we have seen a large improvement in the quality of life
resulting from the innovation and development of more sustainable
products and more efficient processes. In order to meet this growing
trend, there is a need to exploit resources that are renewable and
sustainable. Cellulose is by far the most abundant biopolymer on
earth, and is being produced at a rate of 1.5 × 1012 tonnes per year [1].
In its native form, such as cotton or wood, it can be used to clothe and
shelter us, and through additional chemical and mechanical treatments,
pulp fibers are extracted to make paper. Additionally, these pulp fibers
can undergo further mechanical and chemical treatments to yield a
more useful class of materials, nanocelluloses.
Nanocelluloses are rod-like nanoparticles that can be derived from
many sources such as, cotton, wood, tunicate, wheat straw or ramie
[2]. The type of nanocellulose produced is determined by the processing
conditions: cellulose nanocrystals (CNCs) are produced from chemical
treatments, and cellulose nanofibrils (CNFs) are obtained by either
mechanical or chemical treatments [3,4]. The main differences between
CNC and CNF are their dimension and crystallinity. CNFs consist of
mixtures of amorphous and crystalline cellulose chains with length of
up to several microns, while CNCs are highly crystalline with length
typically less than 500 nm. Both materials have immense potential
⁎ Corresponding author.
E-mail address: mkctam@uwaterloo.ca (K.C. Tam).
for various applications, and this review will focus on cellulose
nanocrystals.
CNCs are produced from fine pulp cellulose fibers via an acid
hydrolysis process that disrupts the hydrogen bonds and cleaves the
amorphous domains of the fiber to yield well-defined crystalline rods
(Fig. 1). CNCs have been produced using various types of acid
treatments, such as hydrochloric, sulfuric, and phosphoric acids, with
each treatment bestowing specific functional groups on the nanoparti-
cle surface that impacts their colloidal stability. For example, CNCs
produced from hydrochloric acid display poor colloidal stability,
whereas those produced with sulfuric acid possess negatively charged
sulfate ester groups on their surface that induces electrostatic repulsion
to yield a highly stable colloidal dispersion. The source of cellulose will
determine the dimensions of CNC nanoparticles. For example, CNCs
derived from hard wood possess a lateral and length dimension of 3–
5 nm and 100–300 nm respectively, whereas CNCs extracted from
tunicate possess a lateral and length dimension of 15–30 nm and
1000–1500 nm respectively [5,6].
CNCs possess many desirable properties, both physical and chemical,
such as high surface area (~ 250 m2/g), high tensile strength
(7500 MPa), high stiffness (Young's modulus up to 140 GPa), and an
abundance of surface hydroxyl groups [7]. These surface hydroxyl
groups offer a facile platform for chemical modification, which may
include converting them to carboxylic acid, amine, aldehyde, or thiol
groups. They could then be used for further modifications, such as
grafting smaller molecules, e.g. biomarkers or metal nanoparticles, and

http://dx.doi.org/10.1016/j.cocis.2017.01.005
1359-0294/© 2017 Elsevier Ltd. All rights reserved.
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
Fig. 1. (a) Scanning Electron Microscopy (SEM) of wood fiber, (b) TEM of wood CNCs, (c) TEM image of tunicate-CNCs [3].
larger macromolecules, such as polymers or proteins. In addition, these
hydroxyl groups impart hydrophilic characteristics to pristine CNCs [8],
which may improve their dispersability within polymer matrices.
The superior properties and facile modification of CNCs have
facilitated their use as functionalized nanoparticles in systems, such as
oil–water emulsions, colloidal complexes, 2-D films and membranes,
and 3-D hydrogel and aerogels. While their chemistry and the applica-
tion of these structures have been documented in several reviews
[2,9–11], the present review examines the advances over the last
5 years, and also discusses the impact and applications of CNCs in
specific industrial sectors. We will analyze the recent use of CNCs in
three main sectors: the biomedical, wastewater treatment, and energy
& electronics sectors.
2. Biomedical engineering
CNCs have been widely adapted for use in biomedical engineering.
The surface of CNCs are modified, and used as antibacterial and antiviral
agents, tissue engineering scaffolds, biomarkers or sensors, gene
vectors, drug delivery vehicles, and biocatalyst scaffolds. The toxicity
of CNCs via various pathways, such as inhalation into the lungs and
cellular uptake was examined as this is a critical property that deter-
mines the utility of the nanoparticles in the biomedical sector [12,13].
Cationic fluorescent probe conjugated to CNC possessed no cytotoxicity,
and CNCs with negative surface charges showed no significant cell
internalization [12]. Inhalation studies revealed that the high aspect
ratio CNCs (such as those derived from tunicate) are more difficult to
clear from the cell surface, whereas smaller CNCs derived from cotton
are readily engulfed by the cell [13]. Recent advances of CNCs in this
field [14,15], and a recent report by Sunasee et al. [16] provide a good
overview on the application of CNCs in the biomedical sector. We will
provide a more recent update on the state of the research activity and
the advances of several promising applications.
2.1. Antimicrobial/antiviral systems
CNCs are promising antibacterial agents when appropriately
derivatized. The surfaces of CNC have been modified with silver
nanoparticles (AgNPs) [17,18], polymers [19], rosins [20], porphyrin
[21], lectin [22], functional groups that bind to viruses [23] and those
that inhibit viral infection [24•]. Silver nanoparticles are well-known
for their antibacterial properties, but they are prone to aggregation in
aqueous solution, thus stabilization of AgNPs on a highly stable sub-
strate is critical when used as antibacterial agents. Tam and coworkers
[17] immobilized AgNPs on polydopamine coated CNCs (PD-CNCs)
and examined their antibacterial characteristics. The adhesive property
of PD promotes the adhesion of PD-CNCs to the surface of bacteria,
displaying an attractive inhibitory concentrations (MICs) of 2–4 μg/mL
and 4–8 μg/mL for Escherichia coli (Gram-negative) and Bacillus subtilis
33
(Gram-positive) bacteria respectively. In contrast, the MIC of AgNPs
was 4 times higher than AgNP-PD-CNCs since PD-CNC reduces the
aggregation of AgNPs, thereby improving their ability to inhibit bacterial
growth. These systems could also be exploited for various catalytic
applications, such as glucose sensing. Wang et al. [18] prepared AgNP
coated CNCs via Tollen's reagent and glucose, and demonstrated their
antibacterial properties against E. coli, multidrug resistant E. coli,
Staphyloccocus aureus, and Methicillin-resistant S. aureus. In addition,
the system can also be used for aqueous glucose detection, where a
solution of CNC and Tollen's reagent turned from colorless to yellow in
the presence of glucose, permitting the quantification of glucose of
between 0.116 to 35 μM. Other methods of incorporating antibacterial
functionality to CNCs can be achieved by coating CNC with
polyrhodanine [19]. The green synthesis of polyrhodanine onto CNC
(CNC@PR) bestows a positive charge onto its surface that promotes
the binding to negatively charged bacteria that induces cell lysis. The
CNC@PR possessed MICs of 0.5–1 mg/mL and 1–2 mg/mL for E. coli
and B. subtilis bacteria respectively. This CNC@PR performed better
than other spherical silica-polyrhodanine nanoparticles because of
their comparatively higher surface areas. de Castro et al. [20] prepared
antimicrobial CNC by grafting rosins on its surface, and they tested
their antimicrobial properties against E. coli and B. subtilis. The rosin
modified CNCs displayed excellent antibacterial performance against
the Gram-positive B. subtilis, but they were less effective against
Gram-negative E. coli, due to the difference in their interaction with
Gram-positive B. subtilis cell wall. Feese et al. [21] produced porphyrin
cellulose nanocrystals for photobactericidal applications. Porphyrin,
when exposed to white light, produces singlet oxygen, which is an
effective bactericide. Photodynamic inactivation studies conducted
with CNC-Por on E. coli, Mycobacterium smegmatis, and S. aureus
revealed % viable cell losses of 99%, 99.99%, 99.9999% respectively after
illuminating 20 μM CNC-Por (with respect to bound Porphyrin) for
30 min. These modified CNCs could be applied to photobactericidal
fabrics, coatings, papers, food packaging and healthcare products.
Ramström and coworkers developed functionalized CNCs for bacterial
imaging and lectin recognition [22]. CNCs were oxidized with (2,2,6,6-
tetramethylpiperidine-1-yl)oxyl (TEMPO) reagent, and conjugated to
fluorescent dye and a carbohydrate ligand (C-CNCs) that formed aggre-
gates upon binding to lectin. This characteristic was further applied
toward E. coli strain recognition. The C-CNCs bind to E. coli ORN178
because they expressed fimbrial lectin FimH, and do not bind to E. coli
ORN 208 since they are devoid of lectin. The modification of CNCs for
virus binding was recently reported by Rosilo et al. [23]. Cationic
modified CNC-g-P(QDMAEMA) was used to bind cowpea chlorotic
mottle virus (CCMV) and norovirus-like particles (NoV-VLPs) via
electrostatic interaction to form micron size aggregates (Fig. 2A).
These aggregates were concentrated at low speeds in a centrifuge for
facile separation and the removal of virus particles from the solution.
Seppälä and coworkers [24•] modified CNCs with tyrosine sulfate
34 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45

Fig. 2. (A) CCMV and NoV-VLP viruses and their complexes with polymer modified CNCs (a) TEM of CCMV viruses in water (b) CCMV/CNC-g-P(QDMAEMA) complexes in water (c) TEM of
NoV-VLP virus in 500 mM NaCl (d) NoV-VLP/CNC-g-P(QDMAEMA) complex in 200 mM NaCl [23] (B) Schematic and SEM images of CNC coating onto bioactive glass (a) Following
electrophoretic deposition onto 316 L stainless steel (b) Formation of hydroxyapatite crystals layer on substrate after 12 h exposure to simulated body fluid [31•] (C) Preparation and
schematic illustration of pDNA delivery via CNC-g-PPEG/PDMA@Au nanoparticles [45••].

mimetic ligands for alphavirus inhibition in Vero (B) cells. CNCs were
desulfated and modified with phenyl sulfonate via direct surface conju-
gation or the incorporation of a molecular spacer. Both the pristine and
modified CNCs were incubated with VA7-EGFP (Semliki Forest virus
vector) prior to using them to infect Vero (B) cells. Pristine CNCs could
inhibit alpha virus infection, whereas phenyl sulfonate CNCs performed
significantly better. Even at virus concentrations 100 times that of
pristine CNC, only 7% viral activity remained. Cytotoxicity tests
conducted with sulfonate modified CNCs on human corneal epithelial
(HCE-T) cells showed negligible cytotoxicity, and they could be used
as inhibitors for HIV and herpes simplex viruses. Ehmann et al. devel-
oped surface modified CNCs that displayed anticoagulating properties
[25]. Sulfated CNCs were coated on glass substrates containing adsorbed
PEI, to yield a highly negative surface (zeta potential of −37 mV) that is
comparable to heparin (−39 mV), a natural anticoagulant. The coagu-
lating time of blood was extended to 9 ± 1 min, which is slightly
below the performance of heparin. They could be readily incorporated
onto plastic substrates to produce anticoagulating surfaces.
2.2. Tissue engineering
CNCs have been widely investigated for use in tissue engineering
due to their capability to reinforce polymer matrices and promote cell
proliferation [26]. Their use has been explored in several applications,
such as injectable tissue scaffolds, bone tissue regeneration, vascular
grafts, improving bone implant adhesion, as well as drug release. CNCs
can reinforce polymer matrices, such as alginate/gelatin, poly(lactic
acid), silk fibronin, in conjunction with hydroxyapatite, or in
electrospinning to produce strong fibers. Yang et al. developed inject-
able hydrogels utilizing pristine and aldehyde modified CNCs, adipic
acid dihydrazide-modified carboxymethyl cellulose and aldehyde
modified dextran [27]. Hydrogels containing CNCs possessed 140%
higher elastic moduli than those without. They were structurally stable
when immersed in water for 60 days. Moreover, they are not cytotoxic
to 3T3 fibroblast cells, making them viable candidates for tissue
scaffolds. Wang et al. used CNCs as a reinforcing agent in alginate/
gelatin matrices for injectable tissue scaffolds [28]. The incorporation
of CNCs reduced cell proliferation, due to the CNCs' increased hydropho-
bicity which decreased cell adhesion. However, these scaffolds demon-
strated sustained cell growth over a longer duration, suggesting that
CNCs promote cell proliferation over the long term. In addition, CNCs
reduced the enzymatic degradation of hydrogels by trypsin, showing
weight loss of only 20% after 7 days compared to 50% for hydrogels
without CNCs. CNCs have also been used directly for bone tissue
regeneration. Fragal et al. [29] developed hybrid materials containing
CNCs and hydroxyapatite (HAp) via a biomimetic method in simulated
body fluid. They investigated the relationship between CNC surface
chemistry and HAp growth, where CNCs with surface charged groups
(sulfonate and phosphonate) promoted the nucleation of HAp, whereas
nucleation of HAp was not observed for CNC produced with hydrochlo-
ric acid. CNCs served as an excellent scaffold for the nucleation of hy-
droxyapatite crystals, and in one instance they increased the viability
of L929 fibroblast cells by 6% over synthetic hydroxyapatite prepared
via the wet chemical precipitation, making it an excellent candidate
for bone tissue regeneration. Chen et al. [30••] produced Nano(HAp)/
CNC/silk fibroin (SF) scaffolds for bone regeneration of calvarial defects
in rats. It was found that the ternary composite of (HAp/CNC/SF) per-
formed better than HAp/SF, CNC/SF, and plain SF scaffolds, possessing
a compressive modulus ~ 43% higher than HA/SF due to the smaller
pore sizes and a more uniform pore size distribution. HAp/CNC/SF
showed no inflammatory response 4 weeks after implantation within
rat calvarial defects, rendering the composite biocompatible, making it
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45 35

Fig. 3. (A) Alginate/CNC hydrogel beads used for the removal of methylene blue (a) formation of hydrogel beads (b) MB dye removal in batch (c) and in fixed bed column configuration
[75] (B) Coagulation-flocculation process utilizing CNC to remove Kaolin clay particles [61•] (C) CNF/CNC membranes for metal ion capture (a) Image of final acetone treated membrane
(b) Schematic illustration showing cumulative metal ion capture (grey spheres) on CNCs (green rods) (c) SEM of nucleated metal ions on membrane surface [83].

ideal for bone tissue engineering applications. CNC coated bioactive
glass (BG) were developed by Chen et al. as an implant coating on stain-
less steel for bone regeneration [31•]. Bioactive glasses have the poten-
tial to act as bone substitute materials, and the combination of BG and
CNC would mimic a composite of hydroxyapatite crystals and fibrous
collagen. Their results indicated that the presence of CNC stabilized
the BG particles in solution, and acted as a template that accelerated
the formation of a nanostructured hydroxyapatite coating from simulat-
ed body fluid compared to bare BG (Fig. 2B). Enhanced adhesion and
proliferation of MC3T3-E1 cells was also observed on CNC coated
BG during cell culture tests, proving this method to be highly
applicable toward bone implant coatings. Kampeerapappun developed
polyhydroxybutyrate (PHB)/CNC electrospun nanocomposite mats for
cell support and proliferation [32]. It was demonstrated that the
introduction of CNCs improved the water absorptivity of the
nanocomposite mat, promoting the formation of more crystalline
domains in the PHB matrix, and decreasing the fiber diameter, improv-
ing their mechanical properties (up to 8 wt.% CNC). Cell viability tests
conducted with L929 fibroblasts showed that the addition of up to
22 wt.% CNCs did not affect the cell viability when compared to pure
PHB fibers, making them excellent candidates for tissue scaffolds.
Brown et al. produced nanocomposites of oxidized-CNC/fibrin for
small-diameter replacement vascular grafts [33•]. CNC was oxidized
via periodate oxidation (OCNC) to facilitate strong interactions with fi-
brin that were enhanced by imine bond formation. The degree of oxida-
tion and OCNC to fibrin ratio were varied to assess their impact on the
composite structure. Using a ratio of 1:1 of OCNC/fibrin, the
nanocomposites possessed the same strength and elasticity of porcine
coronary arteries, which was a great improvement over previous stud-
ies that utilized bacterial cellulose/fibrin composites. The ability to mod-
ify the strength and elasticity of nanocomposites could mimic various
native arteries, making them ideal candidates for small diameter vascu-
lar grafts. Zhou et al. investigated CNC/maleic anhydride grafted
poly(lactic acid) (MPLA) electrospun nanocomposites for bone tissue
application [34]. The CNC/MPLA composite demonstrated high tensile
strength (10 MPa) as a result of CNC alignment in the fibril direction
during the electrospinning process, and the addition of CNC slowed
the in vitro degradation rate of MPLA fibers in PBS buffer due to a
lower porosity. The biocompatibility of the composite fibers was tested
with hA stem cells, confirming that CNCs were not cytotoxic when com-
pared to pure PLA fibers, and they could promote the development of
nanofibrous microstructure in the extracellular matrix (ECM). CNC rein-
forced cellulose electrospun (ECCNN) fibers were prepared by Zhang
and coworkers for tissue scaffolds [35]. Cellulose was first dissolved in
lithium chloride/dimethyl acetamide for electrospinning, and 20 wt.%
CNCs were added and uniaxially oriented, which increased the elastic
modulus of the fibers. MTT assays performed with human dental follicle
cells showed cell proliferation on the ECCNN scaffolds along the aligned
fiber, and ECM expression was evident on the fibers after 4 days. This
aligned cell growth could be adapted to artificial blood vessels since it
can endure high-shear stress conditions of arterial blood flow. Wang &
Chen developed multifunctional protein/CNC scaffolds through
electrospinning for tissue scaffolds and controlled drug release [36]. To
improve their dispersability in Hordein/Zein protein composite
36 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45

Fig. 4. (A) Illustration of lightweight supercapacitors prepared from CNC aerogels, (a) Constituents of aerogel supercapacitors (b) Formation procedure for aerogels via sol–gel process
(c) Hybrid aerogel produced with corresponding capacitive nanoparticle (d) Demonstration of light-weight characteristic of aerogel (balanced on top of feather) (e) Schematic of
symmetric supercapacitor incorporating CNC based aerogel [100••] (B) Fabrication of flexible organic solar cell on CNC/glycerol substrate (a) Schematic representation of solar cell
(b) Chemical structure of PBDTTT-C and PCBM, (c) Fabricated solar cell [113••] (C) Templated material of PR-CNC doped with N and S (a) Synthesis of Polyrhodanine coated CNCs
(b) SEM of self assembled PR@CNC, precursor for NSC (c) SEM of sulfur loaded NSC/S-70 composite [19,119••].

matrix, the CNCs were made hydrophobic by the adsorption of
phenyltrimethylammonium groups on their surface. Next, riboflavin
was added to the protein/CNC solution to produce fibers with bioactive
molecules, and their release behavior in PBS buffer was studied. It was
found that the incorporation of hydrophobic CNCs allowed for a more
sustained release of riboflavin, with over 3 wt.% incorporation of CNC,
the release was larger due to the CNCs disrupting the protein network
in the fibers. Composites with 3 wt.% CNCs layered in different align-
ment directions (tangential and normal) exhibited tensile strength of
21.99 ± 1.19 and 15.78 ± 0.27 MPa in the fiber tangential and normal
directions respectively, giving rise to more robust fibers.
2.3. Drug/Gene delivery
Because of their excellent colloidal stability, CNCs can be used for the
encapsulation and delivery of biomolecules. The loading of charged and
neutral drugs, and the controlled release of active compounds as well as
the transport of genes to target cells have been studied. Akhlaghi et al.
investigated the use of CNC for pH dependent drug release of cationic
drug molecules [37]. Chitosan oligosaccharide was grafted onto the
surface of CNCs (CNC-CSOS) and subsequently loaded with procaine
hydrochloride (PrHy) and imipramine hydrochloride (IMI) at pH of 8
and 7 respectively. In vitro drug release studies conducted with CNC-
CSOS in PBS buffer demonstrated a slower release profile than pure
CNC, and sustained release profiles were demonstrated at a pH of 6 for
PrHy and 7.4 for IMI, with a burst release for IMI at a pH of 5.7. Mohanta
et al. investigated the use of CNC and chitosan in layer-by-layer (LbL)
assembled films for drug delivery [38]. CNCs loaded with curcumin
were coated with chitosan alternating layers via LbL assembly followed
by DOX deposition on the LbL film, and the films were examined for
their sustained release at neutral (pH = 7.4) and acidic (pH = 6.4)
PBS buffers. Microcapsules were also formed using the LbL process
that utilized melamine formaldehyde as a sacrificial template to prepare
hollow capsules that could encapsulate DOX in its interior and curcumin
within the capsule walls. Their sustained release at slightly acidic
pH demonstrated their potential to treat tumors found in acidic
environment. CNCs grafted with poly(ethyl ethylene phosphate)
(PEEP) were developed by Wang et al. for the loading and delivery of
antitumor drug doxorubicin (DOX) to cancer cells [39]. PEEP-g-CNCs
demonstrated excellent biocompatibility with both L929 and HeLa
cells, and DOX loaded PEEP-g-CNCs displayed faster release at pH 5.0
compared to pH 7.4. This result indicated that the drug would be
retained in the PEEP-g-CNCs as it circulates within the body. The DOX
loaded PEEP-g-CNCs displayed anticancer activity, having a LC50 of
9.95 mg DOX equiv. L−1 for HeLa cells compared to 6.38 mg DOX
equiv. L− 1 for free DOX. You et al. produced injectable hydrogels
consisting of quaternized cellulose (QC) and cationic CNCs crosslinked
by β-glycerophosphate [40]. The role of CNCs is two-fold, acting as
both a filler and crosslinker for the matrix. These hydrogels were also
loaded with DOX for in vivo studies of liver cancer tumor growth in
mice, and the sustained release of DOX from the hydrogels slowed the
tumor growth over a longer period compared to pure DOX. Double
membrane hydrogels incorporating cationic CNCs and sodium alginate
were developed by Dufresne and coworkers for the controlled release
of two separate drug compounds [41•]. The intent was to produce an
outer membrane that would rapidly disintegrate resulting in a burst
release of the drug, followed by a controlled release of a growth factor
from the inner membrane. They demonstrated a rapid release of ceftaz-
idime hydrate (antibiotic) from the outer alginate membrane, followed
by a sustained release of epidermal human growth factor from the inner
alginate/cationic CNC membrane at physiological pH. The presence of
cationic CNC induced a slower release due to greater interaction with
alginate, resulting in a steric effect. Ndong Ntoutoume et al. [42] loaded
CNCs with curcumin (cur)/β-cyclodextrin (β-CD) complexes to target
colon and prostate cancer cells. Cationic β-CD would bind to sulfated
CNCs, and curcumin was encapsulated by β-CD via the host-guest
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
process. Cur–β-CD/CNC complexes were tested against PC-3, DU145
and HT-29 cancer cell lines to examine their antiproliferative effect,
and they were found to be 3 to 4 times more effective against these
cells than curcumin alone. Folic acid-conjugated CNCs were prepared
by Dong et al. for cancer targeting [43]. Folic acid and fluorescein
isothiocyanate were conjugated to CNCs (FITC-CNC-FA) to selectively
target and bind to folate receptor-positive cancer cells. They demon-
strated that the uptake into rat (C6) and human (DBTRG-05MG and
H4) brain tumor cells was 46, 976 and 1452 times higher than with
FITC-CNC, illustrating their capability of targeting folate receptor posi-
tive cancer cells. Xu and coworkers developed CNCs modified with
cleavable PDMAEMA side chains for pDNA delivery to cancer cells
[44]. The PDMAEMA grafted CNCs formed complexes with the suicide
gene system CD/5-FC that could then be cleaved by reducing agents,
such as glutathione to release the complexed pDNA. The delivery was
successfully demonstrated in tumors of mice, where the complexes
were transfected to the tumors and initiated cell death. They also devel-
oped gold nanoparticle (AuNP) conjugated to CNC with binary polymer
brushes for gene delivery [45••]. Poly(2-(dimethylamino)ethyl methac-
rylate) (PDMAEMA) and poly(poly(ethylene glycol)ethyl ether methac-
rylate) (PPEGEEMA) grafted CNCs were complexed with plasmid DNA
(pDNA), and conjugated with AuNPs for in vivo CT imaging. This multi-
functional CNC was able to condense pDNA via the cationic PDMAEMA
brushes, and the steric stabilization provided by the PPEGEEMA de-
creased its interaction with anionic cell membranes (Fig. 2C). This re-
sulted in an overall low cytotoxicity of the CNC based vector, making
it an ideal candidate for gene delivery applications.
2.4. Biosensors
CNCs have been used as biomarkers/biosensors for over a decade,
with the most notable work originating from Roman and coworkers in
2007 [46]. These systems have become useful tools for tracking how
CNCs are internalized by cells, for sensing biomolecules, as well as
diagnosing disease. Bi et al. [47•] used TEMPO oxidized CNC (TOCNC)
in TOCNC/L-Cys/Au electrodes to detect enantiomers of Phe, Leu and
Val amino acids. The TOCNC displayed higher adsorption capacities for
D-amino acids as opposed to L-amino acids, due the inherent chirality
of TOCNC. The limits of detection for L-amino acids and D-amino acids
were 5.6 × 10−6 M and 9.0 × 10−6 M respectively. The practical use
of the sensor was demonstrated by detecting the serum of both healthy
individuals and those with type 2 diabetes, since these three amino
acids are more prevalent in the serum of individuals with the disease.
CNC-poly(vinyl alcohol) (PVA) scaffolds functionalized with fluorescein
were developed by Schyrr et al. for various biosensing applications [48].
CNC/PVA nanocomposite films were prepared on glass substrates, and
subsequently modified with thiolated fluorescein-substituted lysine
(FL-SH) and thiolated fluorogenic peptide (FP-SH) for pH sensing and
trypsin detection respectively. The large amounts of surface hydroxyl
groups allowed for a high degree of surface bound fluorophores, facili-
tating the rapid detection of pH change using FP-SH modified films. In
addition, the films could monitor protease activity through the quantifi-
cation of trypsin concentration using FL-SH modified CNC/PVA films
that are useful for wound diagnosis. Colombo et al. also developed
fluorescent dye modified CNCs and concluded that they were excellent
biomarkers in immune-competent mice [49]. The authors found that
the modified CNCs tended to migrate to the bones in limbs due to the
electrostatic interaction with Ca2 + in bone matrix, and this can be
exploited for targeting bone related diseases.
2.5. Protein scaffold/biocatalyst
CNCs have also been extensively used in protein immobilization
scaffolds, which are useful as biocatalysts. CNC provides a stable scaffold
that enhances the activity of protein in extreme environments, and it
facilitates easy separation from the media, allowing for multiple uses.
37
Uth et al. [50••] reported an efficient chemoenzymatic method for
immobilizing proteins onto CNC scaffolds. Following the conversion of
the surface hydroxyl to aldehyde groups, an oligo-Gly sequence was
conjugated to its surface that could be recognized and cleaved by
sortase A to allow for protein immobilization. The benefits of this
approach is that the protein grafting can be site specific and region-
specific at physiological conditions, allowing the protein to retain its
structure and not compromise its activity. The method is applicable to
a wide range of proteins as well as bioactive molecules, taking advan-
tage of the highly dispersible CNC scaffold. Glucose oxidase (GOx) was
immobilized on CNCs by Incani et al. [51]. CNCs were coated with PEI,
followed by the deposition of AuNPs and chemisorption of carboxyl-
terminated thiol before the covalent grafting of GOx on the surface of
CNC. GOx loading of 25.2 mg/g was achieved using a short thiol linker,
where the system was applicable for biosensing. Papain is a popular
enzyme for protein immobilization to assess whether its activity will
be affected when conjugated to a surface. Mahmoud et al. immobilized
papain enzyme on the surface of magnetite coated CNCs for facile sepa-
ration [52]. CNCs were first functionalized with Fe3O4 NPs to facilitate
magnetic separation, followed by the deposition of AuNPs prior to the
grafting of papain enzyme. An optimal enzyme loading of 186 mg/g
was achieved, and the immobilized enzyme retained 95% of its original
activity after storage for 35 days at 4 °C (compared to 41% residual
activity for free enzyme). Recycling experiments indicated the
immobilized enzyme retained 80% of its original activity after
12 cycles of magnetic separation. In another work, Cao et al.
immobilized papain on magnetic CNCs (MCNC) for enhanced stability
[53], where a higher loading of the enzyme was achieved (333 mg/g
MCNC). This system demonstrated enhanced stability over wider
pH and temperature ranges, and retained 88% of its original activity
after 5 repeated uses. Furthermore, the biosynthesis of Z-Ala-Gln
dipeptide with a high yield in a deep eutectic solvent was achieved,
demonstrating the potential of the papain immobilized CNC as an
efficient biocatalyst. They also prepared Pseudomonas cepacialipase
(PCL) immobilized on magnetic CNCs [54•], where the immobilized
PCL displayed enhanced relative activities over a wide temperature
and pH range compared to free PCL, which could be separated via a
magnetic field for repeated used in batch experiments. PCL immobilized
on CNC could be reused after 6 subsequent cycles, and maintained
62.5% of its original activity after the 6th cycle. The system was also
effective in catalyzing asymmetric hydrolysis of keptoprofenethyl
ester, exhibiting a high yield of 43.4% with a product enantiomeric in
excess of 83.5%.
3. Wastewater treatment
Considering the increasing interest in sustainability and nanotech-
nology, the use of CNCs in water treatment applications has gained
increasing attention. CNCs have been actively researched for their use
in various water treatment systems, such as adsorption, absorption,
flocculation, membrane filtration, catalytic degradation and disinfec-
tion. CNCs are attractive candidates because of its high specific surface
area, high specific strength, hydrophilicity, biodegradability and surface
functionalization capabilities [6]. The major types of pollutants present
in water bodies include organic dyes, heavy metal ions, pharmaceutics,
pesticides, polycyclic aromatic hydrocarbons, and biomolecules.
Adsorption is an attractive and economical technique, and when
implemented using a well-designed system, it can offer excellent
results. The production of conventional adsorbents, such as activated
carbons, can be energy intensive, expensive, and emit greenhouse
gases. Thus, producing alternative low cost adsorbents from industrial
and agricultural by-products offers many new opportunities [55,56,
57]. The use of sustainable nanomaterials, such as CNCs will reduce
our dependence on activated carbons and also reduce the carbon foot
print as several CNCs based adsorbents have demonstrated excellent
adsorption capacity [58,59].
38 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
3.1. Adsorbents
He et al., Batmaz et al. and Yu et al. have reported on the adsorption
characteristics of CNCs for methylene blue (MB). He et al. prepared
carboxylated CNCs from microcrystalline cellulose (MCC) using ammo-
nium persulfate (APS) and the CNCs possessed negative carboxyl
groups that bind to positively charged MB molecules. The maximum
adsorption capacity (qmax) was 101.2 mg/g, and these CNCs could
remove more than 90% of dyes even after 7 adsorption–desorption
cycles using suitable eluent like ethanol [60]. Batmaz et al. used pristine
CNCs derived from sulfuric acid hydrolysis of pulp fiber for the adsorp-
tion of MB. The CNCs are decorated with negative sulfate ester groups
serving as binding sites for the adsorption of MB molecules. The qmax
can be enhanced by introducing more negative carboxyl groups via
TEMPO oxidation of pristine CNCs. The qmax for pristine CNCs and
carboxylated CNCs were found to be 118 and 769 mg/g respectively
[58]. Carboxylated CNCs produced by citric acid/hydrochloric hydrolysis
of MCC was used for adsorption of MB [61•]. Novel carboxylate function-
alized CNCs produced by grafting maleic anhydride was used for the
adsorption of multiple cationic dyes, such as MB, crystal violet, mala-
chite green and basic fuchsin [62]. CNCs have also been functionalized
with cationic moieties for adsorbing anionic dyes. Eyley et al. used
imidazolium grafted CNCs for the adsorption of anionic dye, Orange II.
Here the cationic imidazolium groups were introduced via a heteroge-
neous Cu(I) catalyzed azide-alkyne cycloaddition reaction on CNCs
[63]. Jin et al. prepared amino functionalized CNCs by grafting
ethylenediamine on sodium periodate oxidized pristine CNCs and
the adsorption of anionic dyes, such as Congo red 4BS, acid red GR and
reactive yellow K-4G was evaluated [64]. Mathew and co-workers
studied the adsorption of Ag+ ions using CNCs extracted from cellulose
sludge via sulfuric acid hydrolysis and the qmax was estimated to be
34.4 mg/g [65]. They have also prepared phosphorylated CNCs for the
adsorption of Ag+, Cu2 + and Fe3 + ions from aqueous solution.
Enzymatic phosphorylation of CNCs introduced phosphate groups
on CNC surface that act as binding sites for heavy metal ions. Phosphor-
ylated CNCs displayed an enhanced adsorption capacity compared to
pristine CNCs. The qmax for Ag+, Cu2+ and Fe3+ were found to be 56,
20 and 6.3 mg/g respectively for pristine CNCs, 136, 117 and 115 mg/g
respectively for phosphorylated CNCs [66••]. Yu et al. developed surface
functionalized CNCs, such as SCNCs and NaSCNCs for the adsorption of
Pd2+ and Cd2+ in aqueous solutions. Succinic anhydride modification
of pristine CNCs yielded carboxyl group bearing SCNCs, which upon
further treatment with sodium bicarbonate produced NaSCNCs that
possessed higher adsorption capacity compared to SCNCs. This is
because of the conversion of carboxyl groups to carboxylates which
has better binding affinity to heavy metal ions [67]. Similarly, several
research groups have used pristine CNCs and a wide variety of function-
alized CNCs for the adsorption of heavy metal ions from aqueous
solutions [68–73].
CNCs have also been incorporated into composites as demonstrated
by Mohammed et al., who prepared CNCs incorporated alginate hydro-
gel beads for the adsorption of MB (Fig. 3A). This nanocomposite
was prepared by ionic crosslinking of alginate chains using CaCl2
(Fig. 3A(a)). The adsorption characteristics were studied using both
batch and column adsorption processes (Fig. 3A(a,b). The negatively
charged sulfate ester groups of the CNC and carboxyl groups on the al-
ginate contributed to the adsorption of cationic MB molecules and the
qmax was found to be 256 mg/g. They also demonstrated that these ad-
sorbents were re-usable with negligible loss in adsorption capacity even
after five adsorption–desorption cycle when regenerated using 1:1 hy-
drochloric acid: ethanol mixture [59,74,75]. In another study, porous
nanocomposite hydrogels based on pristine CNCs and partially hydro-
lyzed polyacrylamide prepared by Zhou et al. have been used for the ad-
sorption of MB from aqueous solution. Here, the adsorption of MB
occurs as a result of exchange or sharing of electrons between the cat-
ionic groups on MB molecules and anionic groups on the hydrogels
viz., sulfate ester groups from CNCs and carboxyl groups from HPAM
[76,77]. Jin et al. prepared a novel microgel based on CNCs and ampho-
teric polyvinylamine (PVAm) for the adsorption of anionic dyes, such as
acid red GR, Congo red 4BS and reactive yellow K-4G. Dialdehyde func-
tionalized CNCs were first synthesized by sodium periodate oxidation
and the aldehyde-CNCs acted as cross-linkers for PVAm chains to pro-
duce a pH-responsive microgel bearing high density of free amine
groups. The negatively charged dye molecules bind to the protonated
amine groups via electrostatic interaction during the adsorption process
[78]. Anirudhan et al. prepared 2-mercaptobenzamide modified itaconic
acid-grafted-magnetite CNCs and poly(itaconic acid/methacrylic acid)-
grafted-CNCs/nanobentonite composite for the adsorption of Hg2 +
and Co2 + [79•,80]. Mohammed et al. reported on a novel CNC based
nanocomposite system that can simultaneously sense and scavenge
heavy metal ions in water. The nanocomposite comprises of CNCs,
bovine serum albumin protected gold nanoclusters and alginate that
contribute to their adsorption and sensing characteristics. This nano-
composite was selective to mercury ions in water and their diffusion
controlled simultaneous adsorption and sensing property was used as
a tool to probe diffusion. They also demonstrated the practical applica-
bility of this nanocomposite system using a dip pen device for in situ
monitoring of heavy metal ions in water [81]. Chen at al. prepared
a novel class of recyclable magnetic CNCs composites viz., β-
cyclodextrin modified CNCs@Fe3O4@SiO2 superparamagnetic nanorods
for the adsorption of two model pharmaceutical compounds, namely
procaine hydrochloride and imipramine hydrochloride. These
adsorbents captured pharmaceuticals in the hydrophobic cavity of
β-cyclodextrins, which could be recovered using a magnetic field. The
qmax for imipramine hydrochloride and procaine hydrochloride was
found to be 14.8 ± 0.16 and 13.0 ± 0.09 mg/g respectively [82].
3.2. Additional water treatment techniques
Absorbents based on CNCs are gaining attention for their use as
superabsorbents for oil/water separations. Yang et al. prepared
chemically crosslinked CNCs based aerogels via hydrazone crosslinking
chemistry. Here the aerogels were prepared by crosslinking the hydra-
zide and aldehyde modified CNCs followed by freeze drying. Although
these aerogels possessed good absorption capacity for all polar and
non-polar liquids, they also demonstrated preferential absorption of
water in dodecane/water mixtures [84]. Flocculants based on CNCs
are ideal alternatives to petroleum derived polymers for use in
coagulation-flocculation water treatment processes [85]. Early research
efforts by Yu et al. have shown that CNCs produced via a one step citric/
hydrochloric acid hydrolysis of MCC are good flocculants for kaolin clay
particles suspended in water (Fig. 3B). The flocculation performance of
these CNCs depends on the anionic carboxyl functional groups present
on its surface acting as binding sites for the flocculation of suspended
particles through charge neutralization [61•]. Sun et al. examined the ca-
pability of CNC to flocculate Gram negative bacteria via depletion mech-
anism. Pseudomonas aeruginosa PAO1 bacterium cultures were
suspended in water with CNCs in ratios of 1:100 and 1:100,000
(bacterium:CNCs by number), and following the incubation for 24 h,
the aggregation % of the bacterium was determined to be 80% and
100% respectively, with 15% aggregation for a control study of
bacterium in 10 mM NaCl. Rod-like colloidal particles are more effective
than spherical colloidal particles as they can deplete larger colloids
when used in lower concentrations. CNCs having lengths of 100–
200 nm are ideal for the depletion of P. aeruginosa PAO1 bacterium,
which are on average 1.2 μm in length and 0.2 μm in diameter [86].
CNCs also find application in water filtration membranes by virtue of
its ability to alter the membrane characteristics, such as surface hydro-
philicity, tensile strength, selectivity, pore size, porosity, permeability,
and biofouling resistance (Fig. 3C) [87]. Cladophora CNC based filter pa-
pers have been developed by Mihranyan and coworkers for the removal
of viruses, such swine influenza virus, xenotropic murine leukemia virus
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
and Au nanoparticles from aqueous solutions [88,89,90]. Karim et al.
have also prepared CNCs based nanoporous membranes for the removal
of dyes and heavy metal ions [83,91,92]. Advanced water treatment
systems employing CNCs for catalytic degradation of contaminants
and for the disinfection of microbial contaminants have not been exten-
sively studied. Several composites comprising of CNCs were found to be
effective for the catalytic degradation of model organic compounds and
in killing microorganisms [7,93,94]. There is an enormous potential in
developing these systems for use in functional water treatment
processes.
4. Energy and electronics sector
Nanocellulosic materials have received increasing attention in the
field of organic electronics and energy storage [11,95,96]. CNCs them-
selves are electrically insulating, however, those derived from wood
possess interesting piezoelectric properties, and a strong dipole that
allow them to align in the presence of a strong electric field [97]. In
addition, they offer strength through templating to yield conductive
composites. Some conducting polymers, such as polypyrrole, suffer
from poor processability and mechanical properties [98,99]. Coating
CNCs with conductive polymers [98] or conducting nanoparticles
[100••] yielded composites with moderate conductivity, lower thermal
expansion coefficient, and high strength. The high aspect ratio of CNCs
and their ability to form networks will lower the percolation threshold
of conductive materials [99,101]. Likewise, CNFs have found application
in electrical devices, such as conductive papers [102] or energy storage
systems [103] due to their higher aspect ratio and flexibility. CNCs,
with their enormous surface area, optical properties and ability to
strengthen matrices have found applications in supercapacitors, con-
ductive films, sensors, substrates in electrical devices, and separators
in energy storage devices. We will summarize the recent advances in
these areas and the benefits of using CNCs.
4.1. Supercapacitors
CNCs have great potential in the field of supercapacitors due to their
large surface area that facilitates charge storage. Liew et al. synthesized
nanocomposites consisting of CNC-Polypyrrole (PPy) for use as stable
supercapacitors [104]. CNCs were first carboxylated via TEMPO oxida-
tion to facilitate the coating of PPy on their surface. A symmetrical
supercapacitor composed of two CNC-PPy electrodes was constructed
that retained 47% of its initial capacity after 50,000 cycles of 0.01 V/s
between 0 and 1 V. The stability of the supercapacitor was attributed
to the strength offered by the rigid CNCs, as well as the porous structure
of the nanocomposite that facilitated diffusion of ions and solvent
molecules, making the structure more stable. The CNC-PPy material
further demonstrated a high capacitance (CM) of 240 F/g. CNC-PPy com-
posites were also synthesized by Tam and coworkers for conductive
film and supercapacitor applications [98]. In-situ polymerization of pyr-
role monomers on the surface of individual CNCs yielded well-dispersed
conductive nanoparticles in aqueous solution or pressed into films. The
resulting PPy-CNCs also exhibited capacitances and conductivities of
248 F/g and 4.5 S/cm respectively, making them ideal for supercapacitor
applications. With the end product being a redispersible nanoparticle,
it had the advantage where it could be easily added as a filler into
matrices, and the synthesis was also scalable from 100 mL to 4 L, capable
of producing 10–12 g of the final product. Wu et al. improved the
synthesis by polymerizing PPy on poly(N-vinylpyrrolidone) (PVP)
coated CNCs [105]. The incorporation of PVP on the surface of CNCs
produced an even coating of PPy, resulting in improved conductivity
(36.9 S/cm) and capacitance (322.6 F/g) than its predecessor. The
improved material displayed higher cycling stability, with only 8.9%
capacitance loss after 1000 cycles at 0.1 V/s. N-doped carbon nanorods
templated by CNC were also developed by Tam and coworkers [106•].
CNCs were coated with melamine formaldehyde (MF) and pyrolyzed
39
to produce N-doped porous carbon nanorods that displayed high
capacitances in 1 M H2SO4, 6 M KOH and 2 M KCl electrolytes. They
reported an improved capacitance of 352 F/g (in 1 M H2SO4), which
was contributed by the highly porous network of carbonized CNC that
enhances the double layer capacitance. In addition, the material
exhibited improved stability, displaying only 4.6% capacitance loss
after 2000 cycles at a current density of 20 A/g. Yang et al. developed
modified CNCs to form lightweight, flexible aerogel substrates for
supercapacitor systems [100••]. The modified CNCs were similar to
those employed in injectable hydrogels [27], and they were loaded
with one of three capacitive nanoparticles: PPy nanofibers (PPy-NF),
PPy-coated CNTs (PPy-CNT), or MnO2 nanoparticles at a mass ratio of
1.5:1 (CNP:CNC) (Fig. 4A). Shape recovery experiments in both air and
Na2SO4 electrolyte indicated that each aerogel possessed a height
recovery rate of 0.05 cm/s after 400 compressions to 80%, which is
suitable for flexible electronic applications. They also exhibited
excellent capacitance retention, and due to the highly porous nature
of the material, very low internal resistance was observed. They devel-
oped CNC/MWCNT/PPy composite compressible aerogels for use as
supercapacitors [107]. PPy was polymerized in-situ within CNC/
MWCNT aerogels, and when used to form lightweight, bendable
supercapacitors they achieved maximum capacitances of 2.1 F/cm2
with an active PPY loading of 17.8 mg/cm2 having a mass ratio of active
material/current collector of 0.57. They also demonstrated no loss in
performance at 80% compression, and a capacitance retention of 86.9%
after 5000 cycles, indicating good electrochemical cyclic stability.
4.2. Conductive films
Despite the insulating characteristics of CNCs, its strength and
surface area can aid in the preparation of conductive films. One of the
first instances of this was demonstrated by Weder and coworkers
on cellulose nanowhiskers extracted from tunicate [108], where
polyaniline was coated on the nanoparticles and formed into films. By
coating CNCs with polymers or integrating them within a matrix, they
provided significant advantages to the composite material, both by
lowering the percolating threshold and increasing their strength.
Thielemans and coworkers used CNCs as templates in conductive poly-
mer nanocomposites [99]. CNC was added in formulations to decrease
the percolation threshold in PEDOT:PSS/Polystyrene (PS) composites,
and the incorporation of 0.8 wt.% CNC lowered the percolation thresh-
old of 2.2 (for PEDOT:PSS/PS) to 0.4 wt.%. The lower percolation thresh-
old was attributed to the conducting polymer physically adsorbing onto
the CNCs yielding a high aspect ratio network in the PS latex matrix,
allowing the efficient transport of charges. Conductive films based on
CNC and polyaniline (PANI) were produced by Hamad & Atifi [109].
They were produced by either in-situ polymerization or emulsion
polymerization, and the films containing a 2:1 mass ratio of CNC:PANI
exhibited an optimized balance of mechanical and electrical properties.
The incorporation of CNC affords the composite its strength and flexibil-
ity, as PANI itself tends to be brittle, and composite films exhibited con-
ductivities up to 1.88 × 10− 2 S/cm and a tensile strength of 9.74 ±
1.797 MPa. Wang et al. incorporated CNC@PANI nanoparticles into
CNF/PVA composites to form conductive films [110•]. Additionally,
CNFs were used to improve the dispersion of CNC@PANI nanoparticles,
and films containing 10 wt.% PVA were prepared. By modulating
the ratio between the CNF and CNC@PANI, the mechanical properties
and electrical conductivity could be altered. Films having the greatest
ratio of CNC@PANI to CNF (81/9) had an electrical conductivity of
104.7 S/m, but they suffered from low tensile strength (26.7 MPa). Safari
& van de Ven investigated the impact of water vapor adsorption on the
electrical properties of CNT/CNC composites [111]. Electrosterically
stabilized CNCs (ECNCs) (that contains carboxylated polymers on either
ends of the nanocrystals) and CNCs were dispersed in CNT dispersions
and formed into thin films to yield conducting composites. It was deter-
mined that a 1–2 wt.% loading of CNT in CNC matrices was sufficient to
40 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
display a small conductivity variation toward relative humidity (stable
at ~ 10−2 S/cm), whereas with the same loading in ECNC matrices, an
abrupt increase in the conductivity was observed from 59% RH
(2.6 × 10−4 S/cm) to 85% RH (0.7 S/cm), making it a viable humidity
sensor switch. Flexible laminated conductive membranes composed of
CNCs and graphene oxide (GO) were prepared by Xiong et al. [112•].
CNCs were modified with PEI to yield a highly positive surface charge,
which were used to form nano-membranes in a LbL fashion, alternating
between GO and CNC-PEI. They were further electrochemically reduced
to form CNC-rGO membranes. The resulting 60 nm thick membranes
possessed high conductivities of 5000 S/m and enhanced mechanical
properties resulting from a combination of 1D stiff CNCs and 2D flexible
GO nanosheets. The membranes exhibited specific strengths and stiff-
ness values of 382 MPa/g cm3 and 100 GPa/g cm3 respectively, making
them suitable for applications, such as electromagnetic interference
shielding and wearable electronic devices.
4.3. Substrates
CNCs have also been investigated for use as lightweight, flexible
substrates in many electronic devices. Substrates could be easily
produced by mixing CNCs with a plasticizer in solution, and casting to
form a film yielding a flexible substrate for device assembly. Kippelen
and coworkers used CNCs as substrates for solar cells, organic LEDs,
and organic field effect transistors, which is the first reported study
involving recyclable solar cells utilizing CNC substrates [113••]. CNCs
were blended with glycerol to form a flexible film with a MoO3/Ag
layer as the top electrode and Ag as the bottom electrode (Fig. 4B).
The combination of optically transparent and low surface roughness of
CNC substrates permitted the solar cell to have a low reverse leakage
current as well as a large rectification ratio in the dark. A power
conversion efficiency (PCE) of 2.7% was attained with this polymer
solar cell with a substrate derived from renewable resources. They
also demonstrated the facile separation of every component of the
polymer solar cell, as the CNC substrate would swell and disintegrate
after being immersed in water for 30 min. They further improved
their design by employing a PEDOT:PSS PH1000 as the top electrode
and Ag/PEI as the bottom electrode on CNC substrate [114]. This
polymer solar cell achieved a PCE of 3.8%, which is comparable to
the performance of a similar polymer electrode fabricated on a polye-
thersulfone (PES) substrate. In addition, Kippelen and coworkers
formulated organic LEDs (OLEDs) [115] and top-gate organic field-
effect transistors [116] on CNC/glycerol substrates. OLEDs fabricated
on CNC substrates achieved similar current efficacies (42.7 ± 9.8 cd/A
at 100 cd/m2) compared to those fabricated on glass substrates
(45.5 ± 10.0 at 100 cd/m2), with the added ability of the substrate
being readily dispersible in water, allowing the device to be recycled.
To minimize the impact of CNC's poor barrier properties, Al2O3 was
coated on the substrate via atomic layer deposition, and the resulting
OFET displayed improved environmental stability with comparable
performance to one fabricated on a glass substrate having the same
geometry [116]. Inverted organic solar cells were prepared by Costa
et al. [117] on both CNC and CNF substrates. The PCE of solar cells
containing CNC and CNF substrates were 1.4 and 0.5% respectively,
with the CNCs performing better due to the lower roughness, higher
crystallinity and homogeneity of the substrates.
4.4. Sensors
CNCs have also been used in sensors to measure ambient conditions,
proximity of an object, or concentration of chemicals. Kim and co-
workers fabricated proximity sensors based on CNC and reduced GO
(rGO) [118•]. Following the dispersion of CNC and GO in DMF, they
were connected together using isophorone diisocyanate, followed by
the reduction of GO with anhydrous hydrazine. The composite film
could detect human fingers at a distance of 6 mm, with CNCs improving
the optical transparency of the film when compared to pure m-rGO
films. Kim and coworkers also produced flexible humidity sensors
based on composites of CNC and GO [120]. The sensor operated based
on the presence of hydroxyl groups on both CNC and GO, which
would adsorb water molecules and increase the capacitance of the
composite. This sensor was calibrated to measure humidity from 25 to
90% RH at temperatures ranges of between 25 to 45 °C without a
reduction in the sensitivity. In addition, they produced sensors for NO2
using CNC/iron oxide nanoparticles [121]. Iron oxide NPs were grown
on CNCs via in-situ synthesis, and deposited onto polyethylene
substrates with an interdigital electrode pattern to form sensor films.
The presence of CNC improved the electrical percolation sites between
the iron oxide particles that possessed better performance than pure
iron oxide films. The electrical resistance of the films was correlated to
the amounts of NO2 adsorbed on the film, and the sensors displayed
a response time of 50 s for a 200 ppm step change in NO2 gas concentra-
tion, which increased as the concentration decreased, with a 30 s recov-
ery time after each measurement. The sensor had a limit of detection of
2 ppm for NO2, and bending tests yielding a slight increase in the sensor
responses. Similar to the study by Thielemans and coworkers [99],
Wang et al. demonstrated a similar approach on using CNC to reduce
the percolation threshold to construct a strain sensor [101]. CNTs were
coated onto CNCs, and added to natural rubber (NR) composites to im-
prove the formation of 3D charge percolating networks, thus lowering
the percolation threshold of CNT 4-fold compared to CNT/NR compos-
ites. Composites containing CNCs experienced high sensitivity to strain
and demonstrated the recovery of their initial resistance after undergo-
ing stretch/release with 100% strain, compared to CNT/NR composites
that experienced a flat response in resistance with increasing strain.
These properties would allow the composite to be used in wearable
communication devices and stretchable electronics. CNC/PEDOT con-
ductive nanocomposites were developed by Luo and coworkers for
use as dopamine sensors [122]. PEDOT was polymerized both chemical-
ly and electrically onto CNC, with the electrochemically polymerized
PEDOT/CNC composite exhibiting 78% storage capacity retention fol-
lowing 1500 cyclic voltammetry cycles at 50 mV/s between −0.6 V to
0.6 V. A CNC/PEDOT electrode was prepared by oxidizing dopamine at
its surface, and it was able to sense dopamine at a concentration range
of 0.2–62 μM. In addition Luo and coworkers also developed chemical
sensors from CNC for detecting nitrite ions [123]. CNCs were carboxylat-
ed using ammonium persulfate, assembled with poly(diallyldimethyl
ammonium chloride) (PDDA) onto a glassy electrode, and varying
amounts of PEDOT were electrodeposited onto the surface to form the
sensing electrode. The electrode could detect nitrite within the range
of 0.2 to 1.73 mM, with a limit of detection of 57 nM, which was also ap-
plied to determine nitrite levels in pickled vegetables. Chen et al. devel-
oped indicators based on CNC for anti-counterfeiting applications [124].
Two types of modified CNCs were produced, carboxylayed CNCs with
CdS quantum dots (CNC-COOH@CdS) and partially desulfated CNCs
coated with polyethyleneimine and CdS quantum dots (pdsCNC-PEI@
CdS), and nanothin films were formed by electrostatic layer-by-layer
deposition by first depositing a layer of CNC-COOH@CdS, followed by
a layer of pdsCNC-PEI@CdS. When deposited on PET substrates, the
films exhibited excellent stability in water and ethanol, and tunable
structural colors could be obtained by varying the film thickness, ob-
serving a red shift in the reflectance spectra as the number of layers
were increased from 20 to 30 and tunable emission colors could be ob-
tain by altering the concentration of modified CNC. Tang et al. prepared
optical pH indicators by coating polyrhodanine onto CNC [125]. CNC@
PR core-shell nanoparticles were produced via in-situ polymerization
in aqueous solution that displayed reversible pH sensing capabilities,
changing from pale red at a pH of 2.04 to blue violet at 12.04. These
CNC@PR nanoparticles displayed excellent mechanical strength
and good dispersability, and they could be formulated into 1D
printable inks, 2D thin films, and 3D hydrogel beads for various
applications.
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
4.5. Templating material/Separator for energy storage
In addition to supercapacitors, CNCs have been employed as
separators for use in batteries and fuel cells. Their use in separators for
batteries has been under development since the last decade [126], and
significant improvements have been advanced. The potential of using
nanocellulosic materials as catalytic supports for electrochemical
reductions has also been realized, which could then be applied to
fuel cells [93]. Lalia et al. utilized CNC composite mats as separators
in Li-ion batteries [127]. The addition of 2 wt.% CNCs to
poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP) com-
posite mats not only increased the storage modulus by 15%, but induced
a higher uptake and retention of 1 M LiTFSI/BMPyrTFSI electrolyte, an
increase of 63% compared to the mats without CNC. This resulted in a
higher conductivity, and the composite mats were electrochemically
stable up to 5 V, making them suitable for use in lithium ion batteries.
Mastragostino and coworkers prepared PVdF-CNC membranes for
use in high-voltage batteries for hybrid electric vehicles (HEV) [128•].
CNCs were loaded at 8 wt.% in PVdF to form macroporous membranes
and tested against Celgard® 2400 separators in Graphite/LiNi0.4Mn1.6O4
cells with LF30 electrolyte. Cells utilizing PVdF-CNC separators could
provide 101 W h/kg at C/1 effective rate compared with 85 W h/kg for
Celgard® 2400 separators, which was attributed to the higher porosity
of PVdF-CNC separators. The PVdF-CNC cells also exhibited desirable
shutdown at higher temperatures, which is critical for the safe use of
the device. The PVdF-CNC separator cell exceeded the power and energy
goals for minimum and maximum power-assist HEVs outlined by the
US DOE FreedomCAR specifications, making it suitable for use in high
voltage cells. Bolloli et al. further investigated porous and dense CNC/
PVdF membranes as separators in lithium ion batteries [129]. The incor-
poration of CNCs at 20 wt.% into dense (hot-pressed) and macroporous
membranes greatly improved their Young's modulus, and facilitated the
formation of polar β phase in the PVdF in the macroporous membrane
that improved the wettability of the matrix. The addition of CNCs slight-
ly decreased the porosity and conductivity of PVdF separators, but they
outperformed commercial grade Celgard® 2400 separator, making it vi-
able for lithium ion batteries. Pang et al. employed the use of CNCs as a
host material for a sulfur electrode in lithium sulfur batteries [119••].
Dual-doped mesoporous nitrogen and sulfur carbon templates
were prepared by dispersing CNC@PR nanorods with a tetraethyl
orthosilicate (TEOS) spacer, followed by evaporating the solvent to
form a free-standing film with a disrupted chiral nematic structure.
The film was pyrolyzed to yield a porous structure (NSC) with a tunable
porosity and surface area based on the weight ratio of CNC@PR to TEOS
used (Fig. 4C). This material could effectively adsorb polysulfides,
outperforming N single-doped carbons and undoped carbon materials.
It acted as a sulfur host in the sulfur electrode, and was capable of deliv-
ering 1370 mA h/g at C/20, and could discharge/charge at 2C for
1100 cycles while experiencing only 0.052% capacity fading per cycle.
Liu et al. utilized pyrolyzed CNCs doped with urea as high performance
electrocatalysts for oxygen reduction reactions (ORR) in fuel cells [130].
CNCs were mixed with urea at a 1:15 ratio and pyrolyzed at 1000 °C, and
the resulting NCN (Nitrogen-doped carbon nanosheets) possessed a
very high specific surface area of 1362.4 m2/g and a pore volume of
3.36 cm3/g. Cyclic voltammetry tests in an O2 and N2 saturated alkaline
electrolyte (0.1 M KOH) revealed that the NCN electrode possessed a ki-
netic current density of 9.04 mA/cm2 at 0.15 V, which is nearly double
that of commercial Pt/C (4.56 mA/cm2 at − 0.15 V). In addition, the
NCN showed improved tolerance to methanol crossover effect, demon-
strating great promise for this material as an ORR electrocatalyst. Ozcan
and coworkers investigated the use of CNC composite polymer films as a
solid electrolyte in alkaline fuel cells [131]. Films were prepared
by mixing trimethoxy(methyl)silane with polyvinylalcohol (PVA)
to produce a binder, followed by mixing with CNC and preparing a
membrane via evaporation for 12 h, followed by 48 h of oven curing.
The incorporation of CNCs limited the swelling of membrane, which is
41
ideal for this application, and films containing 60 wt.% CNC and
40 wt.% binder exhibited an excellent balance between tensile strength
and water uptake. When immersed in 1 M KOH, the membranes dem-
onstrated electrical conductivities of 0.044 and 0.065 S/cm at 20 °C
and 60 °C, which satisfies the basic requirement of N 10− 2 S/cm for
use in an alkaline fuel cell. This membrane also outperformed the
commercial FAA anion exchange membrane, exhibiting lower swelling
and a slightly higher conductivity (0.038 S/cm).
5. Emerging applications for CNCs
Cellulose nanocrystals are not limited to the industrial sectors
outlined above, and various research efforts have extended the use of
this nanomaterials for other sectors, such as oil & gas, personal care,
food additives and packaging. They can be utilized as rheological modi-
fiers, Pickering emulsion stabilizers, free radical scavenging as well as
reinforcing food packaging films. A more comprehensive treatment of
the emulsion systems stabilized by nanocellulose is reported in this
issue by Capron and co-workers.
5.1. Oil & gas
CNCs possess several properties that make them excellent candi-
dates for use in the oil & gas industry. They are both biocompatible
and biodegradable, and the production of these nanomaterials has a
low carbon footprint and they do not cause secondary pollution
that poses a serious threat to the environment. CNC can be used as a
Pickering emulsifier in enhanced oil recovery, or rheology modifiers in
drilling fluids. CNCs produce very stable Pickering emulsions due to
their nano-dimension and rigid rod like structure. Because of the
various surface functionalization possibilities, CNCs can be tailored to
respond to various stimuli with the grafting of stimuli-responsive
moieties to stabilize/destabilize emulsions extracted from oil reservoirs.
Recent studies have indicated the promising application of CNCs for use
in Pickering emulsions and water-based drilling fluids.
5.1.1. Enhanced oil recovery – Pickering emulsifier
Kalashnikova et al. have studied Pickering emulsions stabilized by
CNCs, which were found to stabilize the oil/water interface. They also
promoted the formation of stable monodispersed oil in water droplets
for several months. The influence of amphiphilic properties and aspect
ratio of CNCs in the stabilization and emulsification of oil droplets was
examined [132–134]. The use of CNCs to stabilize various types of
emulsions and the effect of surface functionalization on the properties
of Pickering emulsions were reported [135–137]. In the context of
EOR, surface functionalized CNCs are considered superior candidates
as they can be de-emulsified by an external stimulus to extract oil
from emulsions recovered from oil reservoirs. Zoppe et al. grafted
poly(N-isopropylacrylamide) (PNIPAM) brushes on the surface of
CNCs via surface-initiated single-electron transfer living radical
polymerization to impart temperature responsive characteristics to
the CNCs. The emulsions stabilized by these particles destabilized
rapidly from the oil/water interface at temperatures greater than the
LCST of PNIPAM [135]. Tam and coworkers prepared a dual responsive
CNC system by grafting poly(2-(dimethylamino)ethyl methacrylate)
(PDMAEMA) to stabilize oil in water emulsions [136]. A weak polyelec-
trolyte (PDMAEMA) brush was grafted on the surface of CNCs via
free radical polymerization. This resultant PDMAEMA-grafted-CNC
possessed both pH and temperature responsive properties due to the
inherent characteristics of PDMAEMA. It was observed that the modi-
fied CNCs significantly reduced the interfacial tension of the oil–water
interface compared to pristine CNCs. The PDMAEMA chains on the
CNCs enhanced the stability of emulsion droplets and the variation in
the chain conformation and hydrophobic-hydrophilic balance of the
nanorods with pH and temperature triggered the emulsification and
de-emulsification of oil droplets. In addition, Tang et al. developed
42 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
an improved stimuli-responsive CNC system for surfactant free oil
harvesting [137]. These CNCs system were prepared by grafting binary
polymer brushes poly(oligoethylene glycol) methacrylate (POEGMA)
and poly(methacrylic acid) (PMAA) using cerium-mediated polymeri-
zation in aqueous solution. The physical properties of this system can
be controlled by external triggers, such as temperature and pH. The
bi-functional CNCs were found to diffuse to the oil/water interface and
stabilize the oil droplets at high pH conditions. However, when the pH
was reduced to 2, the emulsion droplets coalesced due to the strong hy-
drogen bonding between POEGMA and PMAA chains grafted on the
CNCs resulting in phase separation of oil and water. Studies also showed
that the emulsion became destabilized with increasing temperature due
to the conformational change of POEGMA chains. They have also dem-
onstrated the successive stabilization and destabilization over 5 cycles
by modulating the pH with the addition of acid or base without any
loss in efficiency.
5.1.2. Drilling fluid
Li et al. investigated the use of CNC in bentonite (BT) water-based
drilling fluids (WDF) [138,139]. CNCs were added to enhance the
rheological and filtrating properties of these fluids, and the fluids with
CNC possessed enhanced viscosity, shear stress and yield point that
are beneficial to drill fragments transport. The creation of core-shell
structures between the CNC and positively charged BT reduced the
fluid loss and thickness of the filter cakes produced in the drilling
process, and the incorporation of small amounts of CNC would reduce
the amount of BT needed to achieve the same performance.
5.2. Personal care – antioxidant
There are new untapped sectors where CNCs are beneficial, such as
personal care. Akhlaghi et al. [140] reported on the use of CNC-CSOS
for Vitamin C delivery and antioxidant activity. Complexes were formed
between CNC-CSOS, tripolyphosphate, and Vitamin C (VC), and demon-
strated gradual release over 20 days at pH 5 with higher stability of the
VC, as opposed to pure VC at pH 3. Antioxidant experiments demon-
strated that CNC-CSOS had a higher rate constant compared to oxidized
CNCs, CSOS, and physical mixtures of the two, indicating a synergistic
activity of the CNC-CSOS nanoparticle against free radicals. In another
work, Yao and Tam developed CNCs grafted with fullerenes stabilized
by β-cyclodextrin [141]. The authors claimed that the CNC based
antioxidant displayed improved radical scavenging capability than a
commercial polymer-fullerene system trademarked as Vitamin C60.
More recently, Awan et al. developed free radical scavenging CNCs,
where fullerols were anchored onto CNCs, resulting in an increased
scavenging ability of 2,2-diphenyl-1-picrylhydrazyl (DPPH) free
radicals [142]. There is the potential for these three systems to be
formulated into antioxidant skin care products, thereby creating new
market opportunities for CNC.
5.3. Food sector – food additive/packaging films
Another potential use for CNCs is in the design and formulation of
engineering food products. Hu et al. developed Pickering emulsions
stabilized by polymer adsorbed CNC that could be dried and redispersed
easily [143]. Utilizing methyl cellulose or hydroxyethyl cellulose with
tannic acid, oil could be encapsulated using only 6 wt.% of solids,
which is beneficial in replacing the solid fats that are necessary to
prepare soft edible oil containing foods. In addition, the ability to
dry and redisperse the emulsion would reduce transportation costs.
This would be similar to the commercially available, FDA approved
Nata de coco food derived from bacterial cellulose [144]. In addition,
biodegradable food packing films based on CNCs and poly(3-
hydroxybutyrate-co-3-hydroxyvalerate) (PHVB) were prepared by Yu
et al. [145]. The nanocomposites exhibited optimal properties at CNC
loading of 20 wt.%, displaying better barrier, migration, and mechanical
properties compared to pure PHBV films. In another study, Cheng et al.
developed water-soluble films with excellent oxygen barrier properties
for food packaging [146]. CNC was incorporated into guar gum films,
which increased both the modulus and hardness of the films, as well
as decreasing oxygen permeability. The resulting films could dissolve
in water within 5 h.
6. Concluding remarks and future prospects
This article summarizes the potential of CNCs in biomedical,
wastewater treatment, energy & electronic and various other sectors.
Cellulose nanocrystals are attractive materials for these applications
due to their relatively low cost and unlimited supply. The ability to
harvest cellulose from both land and sea ensures a continual supply to
meet the growing demand for products in these industrial sectors.
Cellulose nanocrystals have been studied and evaluated for a
plethora of applications. Their stiffness and biocompatibility facilitate
their use as tissue scaffolds for bone regeneration and when loaded
with bioactive molecules, the sustained release of drugs after implanta-
tion could improve the outcome of such medical treatments. Antimicro-
bial products could be formulated due to the colloidal stability and
enormous surface area of CNC, and active antimicrobial agents could
be formulated and delivered to inhibit the growth of pathogenic
organisms. In addition, they can be used as scaffolds for biocatalysts or
biomarkers to extend the activity of active compounds to higher
temperatures and pH conditions, as well as prolong their shelf life.
In the area of wastewater treatment, using renewable products from
the environment to remove waste and toxic contaminants will improve
the well-being of society exposed to such contaminants. Their large
surface area is critical to the design and development of efficient
bio-adsorbents that ensure the efficient and optimal removal of toxic
contaminants. Their ability to be destabilized by contaminants makes
them efficient flocculants, and they can impart strength to membranes
for filtration applications.
In the energy sector, CNCs offer many of the same advantages to
matrices used to prepare such devices. Their ability to form percolating
networks enhances and improves the transport of electrons and
charges. For applications, such as supercapacitors, the large surface
area improves charge storage, while the porous structures make them
ideal for use as separators in batteries. The utilization of CNCs as
substrates in organic electronics will advance the development of
truly cheap and disposable devices that will be environmentally
friendly, and contribute to the capture of CO2 entrapped within the
cellulose nanostructure.
The development and transformation of CNCs into useful products
will usher the era of resource utilization that will significantly reduce
the carbon footprint since CNC is an efficient carbon storage system.
For large-scale processes, such as water treatment, the post treatment
of CNCs to remove non-toxic impurities may be bypassed since pure
CNCs are not necessary.
The increasing research into green synthesis that averts the use of
organic solvents can reduce toxic byproducts and waste streams when
producing specialized products involving CNCs. Modifications of CNCs
in aqueous solutions and subsequent post treatment via dialysis consti-
tute a sustainable approach to develop nanomaterials for the future.
The market potentials for CNC in the field of biomedical science,
water treatment, energy and electronics are enormous, however they
are new opportunities in other value added and specialty chemical
sectors. Due to the benign characteristics of CNCs and their low toxicity,
opportunities exist for the use of CNCs in cosmetics and engineered food
formulations, both of which can improve the health and well-being of
society. The next century will see a plethora of innovations in sustain-
able nanomaterials as we move toward the integration of these mate-
rials by replacing non-renewable materials with those that are
sustainable and green. CNC can be the engine that drives this innovation
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
and offer solutions that provide a balance between the environment
and needs of consumers.
Acknowledgements
The research funding from CelluForce and AboraNano facilitated the
research on CNCs. K. C. Tam wishes to acknowledge research funding
from CFI and NSERC.
References••,••••
[1] Klemm D, Heublein B, Fink H-P, Bohn A. Cellulose: fascinating biopolymer and
sustainable raw material. Angew Chem Int Ed 2005;44:3358–93. http://dx.doi.org/
10.1002/anie.200460587.
[2] Habibi Y, Lucia LA, Rojas OJ. Cellulose nanocrystals: chemistry, self-assembly, and ap-
plications. Chem Rev 2010;110:3479–500. http://dx.doi.org/10.1021/cr900339w.
[3] Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J. Cellulose nanomaterials
review: structure, properties and nanocomposites. Chem Soc Rev 2011;40:3941.
http://dx.doi.org/10.1039/c0cs00108b.
[4] Nechyporchuk O, Belgacem MN, Bras J. Production of cellulose nanofibrils: a review of
recent advances. Ind Crop Prod 2016;93:2–25. http://dx.doi.org/10.1016/j.indcrop.
2016.02.016.
[5] Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C. The shape
and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native
cellulose. Biomacromolecules 2008;9:57–65. http://dx.doi.org/10.1021/bm700769p.
[6] Peng BL, Dhar N, Liu HL, Tam KC. Chemistry and applications of nanocrystalline
cellulose and its derivatives: a nanotechnology perspective. Can J Chem Eng 2011;
89:1191–206. http://dx.doi.org/10.1002/cjce.20554.
[7] Lam E, Male KB, Chong JH, Leung ACW, Luong JHT. Applications of functionalized and
nanoparticle-modified nanocrystalline cellulose. Trends Biotechnol 2012;30:283–90.
http://dx.doi.org/10.1016/j.tibtech.2012.02.001.
[8] Tingaut P, Zimmermann T, Sèbe G. Cellulose nanocrystals and microfibrillated
cellulose as building blocks for the design of hierarchical functional materials. J
Mater Chem 2012;22:20105–11. http://dx.doi.org/10.1039/c2jm32956e.
[9] Eyley S, Thielemans W. Surface modification of cellulose nanocrystals. Nanoscale
2014;6:7764–79. http://dx.doi.org/10.1039/C4NR01756K.
[10] Salas C, Nypelö T, Rodriguez-Abreu C, Carrillo C, Rojas OJ. Nanocellulose properties
and applications in colloids and interfaces. Curr Opin Colloid Interface Sci 2014;19:
383–96. http://dx.doi.org/10.1016/j.cocis.2014.10.003.
[11] Zhu H, Luo W, Ciesielski PN, Fang Z, Zhu JY, Henriksson G, et al. Wood-derived ma-
terials for green electronics, biological devices, and energy applications. Chem Rev
2016;116:9305–74. http://dx.doi.org/10.1021/acs.chemrev.6b00225.
[12] Mahmoud KA, Mena JA, Male KB, Hrapovic S, Kamen A, Luong JHT. Effect of surface
charge on the cellular uptake and cytotoxicity of fluorescent labeled cellulose
nanocrystals. ACS Appl Mater Interfaces 2010;2:2924–32. http://dx.doi.org/10.
1021/am1006222.
[13] Endes C, Mueller S, Kinnear C, Vanhecke D, Foster EJ, Petri-Fink A, et al. Fate of
cellulose nanocrystal aerosols deposited on the lung cell surface in vitro.
Biomacromolecules 2015;16:1267–75. http://dx.doi.org/10.1021/acs.biomac.
5b00055.
[14] Lin N, Dufresne A. Nanocellulose in biomedicine: current status and future prospect.
Eur Polym J 2014;59:302–25. http://dx.doi.org/10.1016/j.eurpolymj.2014.07.025.
[15] Jorfi M, Foster EJ. Recent advances in nanocellulose for biomedical applications. J
Appl Polym Sci 2015;132:41719. http://dx.doi.org/10.1002/app.41719.
[16] Sunasee R, Hemraz UD, Ckless K. Cellulose nanocrystals: a versatile nanoplatform for
emerging biomedical applications. Expert Opin Drug Deliv 2016;13:1243–56. http://
dx.doi.org/10.1080/17425247.2016.1182491.
[17] Shi Z, Tang J, Chen L, Yan C, Tanvir S, Anderson WA, Berry RM, Tam KC. Enhanced
colloidal stability and antibacterial performance of silver nanoparticles/cellulose
nanocrystal hybrids. J Mater Chem B 2015;3:603–11. http://dx.doi.org/10.1039/
C4TB01647E.
[18] Wang S, Sun J, Jia Y, Yang L, Wang N, Xianyu Y, et al. Nanocrystalline cellulose-
assisted generation of silver nanoparticles for Nonenzymatic glucose detection and
antibacterial agent. Biomacromolecules 2016;17:2472–8. http://dx.doi.org/10.
1021/acs.biomac.6b00642.
[19] Tang J, Song Y, Tanvir S, Anderson WA, Berry RM, Tam KC. Polyrhodanine coated cel-
lulose nanocrystals: a sustainable antimicrobial agent. ACS Sustain Chem Eng 2015;
3:1801–9. http://dx.doi.org/10.1021/acssuschemeng.5b00380.
[20] de Castro DO, Bras J, Gandini A, Belgacem N. Surface grafting of cellulose
nanocrystals with natural antimicrobial rosin mixture using a green process.
Carbohydr Polym 2016;137:1–8. http://dx.doi.org/10.1016/j.carbpol.2015.09.101.
[21] Feese E, Sadeghifar H, Gracz HS, Argyropoulos DS, Ghiladi RA. Photobactericidal
porphyrin-cellulose nanocrystals: synthesis, characterization, and antimicrobial
properties. Biomacromolecules 2011;12:3528–39. http://dx.doi.org/10.1021/
bm200718s.
[22] Zhou J, Butchosa N, Jayawardena HSN, Park J, Zhou Q, Yan M, et al. Synthesis of mul-
tifunctional cellulose nanocrystals for lectin recognition and bacterial imaging.
Biomacromolecules 2015;16:1426–32. http://dx.doi.org/10.1021/acs.biomac.
5b00227.
•
of special interest.
••
of outstanding interest.
43
[23] Rosilo H, McKee JR, Kontturi E, Koho T, Hytönen VP, Ikkala O, et al. Cationic polymer
brush-modified cellulose nanocrystals for high-affinity virus binding. Nanoscale
2014;6:11871–81. http://dx.doi.org/10.1039/C4NR03584D.
[24•] Zoppe JO, Ruottinen V, Ruotsalainen J, Rönkkö S, Johansson L-S, Hinkkanen A, et al.
Synthesis of cellulose nanocrystals carrying tyrosine sulfate mimetic ligands
and inhibition of alphavirus infection. Biomacromolecules 2014;15:1534–42.
http://dx.doi.org/10.1021/bm500229d.
[25] Ehmann HMA, Mohan T, Koshanskaya M, Scheicher S, Breitwieser D, Ribitsch V, et al.
Design of anticoagulant surfaces based on cellulose nanocrystals. Chem Commun
2014;50:13070–2. http://dx.doi.org/10.1039/C4CC05254D.
[26] Domingues RMA, Gomes ME, Reis RL. The potential of cellulose nanocrystals in
tissue engineering strategies. Biomacromolecules 2014;15:2327–46. http://dx.doi.
org/10.1021/bm500524s.
[27] Yang X, Bakaic E, Hoare T, Cranston ED. Injectable polysaccharide hydrogels
reinforced with cellulose nanocrystals: morphology, rheology, degradation, and cy-
totoxicity. Biomacromolecules 2013;14:4447–55. http://dx.doi.org/10.1021/
bm401364z.
[28] Wang K, Nune KC, Misra RDK. The functional response of alginate-gelatin-
nanocrystalline cellulose injectable hydrogels toward delivery of cells and
bioactive molecules. Acta Biomater 2016;36:143–51. http://dx.doi.org/10.1016/j.
actbio.2016.03.016.
[29] Fragal EH, Cellet TSP, Fragal VH, Companhoni MVP, Ueda-Nakamura T, Muniz EC,
et al. Hybrid materials for bone tissue engineering from biomimetic growth of
hydroxiapatite on cellulose nanowhiskers. Carbohydr Polym 2016;152:734–46.
http://dx.doi.org/10.1016/j.carbpol.2016.07.063.
[30••] Chen X, Zhou R, Chen B, Chen J. Nanohydroxyapatite/cellulose nanocrystals/silk
fibroin ternary scaffolds for rat calvarial defect regeneration. RSC Adv 2016;6:
35684–91. http://dx.doi.org/10.1039/C6RA02038K.
[31•] Chen Q, Garcia RP, Munoz J, Pérez de Larraya U, Garmendia N, Yao Q, et al. Cellulose
nanocrystals—bioactive glass hybrid coating as bone substitutes by electrophoretic
co-deposition: in situ control of mineralization of bioactive glass and enhancement
of osteoblastic performance. ACS Appl Mater Interfaces 2015;7:24715–25. http://
dx.doi.org/10.1021/acsami.5b07294.
[32] Kampeerapappun P. The electrospun polyhydroxybutyrate fibers reinforced with
cellulose nanocrystals: morphology and properties. J Appl Polym Sci 2016;133:
43273. http://dx.doi.org/10.1002/app.43273.
[33•] Brown EE, Hu D, Abu Lail N, Zhang X. Potential of nanocrystalline cellulose–fibrin
nanocomposites for artificial vascular graft applications. Biomacromolecules 2013;
14:1063–71. http://dx.doi.org/10.1021/bm3019467.
[34] Zhou C, Shi Q, Guo W, Terrell L, Qureshi AT, Hayes DJ, et al. Electrospun bio-
nanocomposite scaffolds for bone tissue engineering by cellulose nanocrystals
reinforcing maleic anhydride grafted PLA. ACS Appl Mater Interfaces 2013;5:
3847–54. http://dx.doi.org/10.1021/am4005072.
[35] He X, Xiao Q, Lu C, Wang Y, Zhang X, Zhao J, et al. Uniaxially aligned electrospun
all-cellulose nanocomposite nanofibers reinforced with cellulose nanocrystals: scaf-
fold for tissue engineering. Biomacromolecules 2014;15:618–27. http://dx.doi.org/
10.1021/bm401656a.
[36] Wang Y, Chen L. Cellulose nanowhiskers and fiber alignment greatly improve
mechanical properties of electrospun prolamin protein fibers. ACS Appl Mater
Interfaces 2014;6:1709–18. http://dx.doi.org/10.1021/am404624z.
[37] Akhlaghi SP, Tiong D, Berry RM, Tam KC. Comparative release studies of two cationic
model drugs from different cellulose nanocrystal derivatives. Eur J Pharm Biopharm
2014;88:207–15. http://dx.doi.org/10.1016/j.ejpb.2014.04.012.
[38] Mohanta V, Madras G, Patil S. Layer-by-layer assembled thin films and
microcapsules of nanocrystalline cellulose for hydrophobic drug delivery. ACS Appl
Mater Interfaces 2014;6:20093–101. http://dx.doi.org/10.1021/am505681e.
[39] Wang H, He J, Zhang M, Tam KC, Ni P. A new pathway towards polymer modified
cellulose nanocrystals via a “grafting onto” process for drug delivery. Polym Chem
2015;6:4206–9. http://dx.doi.org/10.1039/C5PY00466G.
[40] You J, Cao J, Zhao Y, Zhang L, Zhou J, Chen Y. Improved mechanical properties and
sustained release behavior of cationic cellulose nanocrystals Reinforeced cationic
cellulose injectable hydrogels. Biomacromolecules 2016;17:2839–48. http://dx.doi.
org/10.1021/acs.biomac.6b00646.
[41•] Lin N, Gèze A, Wouessidjewe D, Huang J, Dufresne A. Biocompatible double-
membrane hydrogels from cationic cellulose nanocrystals and anionic
alginate as complexing drugs codelivery. ACS Appl Mater Interfaces 2016;8:
6880–9. http://dx.doi.org/10.1021/acsami.6b00555.
[42] Ndong Ntoutoume GMA, Granet R, Mbakidi JP, Brégier F, Léger DY, Fidanzi-Dugas C,
et al. Development of curcumin–cyclodextrin/cellulose nanocrystals complexes:
new anticancer drug delivery systems. Bioorg Med Chem Lett 2016;26:941–5.
http://dx.doi.org/10.1016/j.bmcl.2015.12.060.
[43] Dong S, Cho HJ, Lee YW, Roman M. Synthesis and cellular uptake of folic acid-
conjugated cellulose nanocrystals for cancer targeting. Biomacromolecules 2014;
15:1560–7. http://dx.doi.org/10.1021/bm401593n.
[44] Hu H, Yuan W, Liu F-S, Cheng G, Xu F-J, Ma J. Redox-responsive Polycation-
functionalized cotton cellulose nanocrystals for effective cancer treatment.
ACS Appl Mater Interfaces 2015;7:8942–51. http://dx.doi.org/10.1021/acsami.
5b02432.
[45••] Hu H, Hou X-J, Wang X-C, Nie J-J, Cai Q, Xu F-J. Gold nanoparticle-conjugated
heterogeneous polymer brush-wrapped cellulose nanocrystals prepared by
combining different controllable polymerization techniques for theranostic
applications. Polym Chem 2016;7:3107–16. http://dx.doi.org/10.1039/
C6PY00251J.
[46] Dong S, Roman M. Fluorescently labeled cellulose nanocrystals for Bioimaging
applications. J Am Chem Soc 2007;129:13810–1. http://dx.doi.org/10.1021/
ja076196l.
44 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
[47•] Bi Q, Dong S, Sun Y, Lu X, Zhao L. An electrochemical sensor based on cellulose
nanocrystal for the enantioselective discrimination of chiral amino acids. Anal
Biochem 2016;508:50–7. http://dx.doi.org/10.1016/j.ab.2016.05.022.
[48] Schyrr B, Pasche S, Voirin G, Weder C, Simon YC, Foster EJ. Biosensors based on po-
rous cellulose nanocrystal–poly(vinyl alcohol) scaffolds. ACS Appl Mater Interfaces
2014;6:12674–83. http://dx.doi.org/10.1021/am502670u.
[49] Colombo L, Zoia L, Violatto MB, Previdi S, Talamini L, Sitia L, et al. Organ distribution
and bone tropism of cellulose nanocrystals in living mice. Biomacromolecules 2015;
16:2862–71. http://dx.doi.org/10.1021/acs.biomac.5b00805.
[50••] Uth C, Zielonka S, Hörner S, Rasche N, Plog A, Orelma H, et al. A chemoenzymatic
approach to protein immobilization onto crystalline cellulose nanoscaffolds.
Angew Chem Int Ed 2014;53:12618–23. http://dx.doi.org/10.1002/anie.
201404616.
[51] Incani V, Danumah C, Boluk Y. Nanocomposites of nanocrystalline cellulose for en-
zyme immobilization. Cellulose 2013;20:191–200. http://dx.doi.org/10.1007/
s10570-012-9805-2.
[52] Mahmoud KA, Lam E, Hrapovic S, Luong JHT. Preparation of well-dispersed gold/
magnetite nanoparticles embedded on cellulose nanocrystals for efficient immobili-
zation of papain enzyme. ACS Appl Mater Interfaces 2013;5:4978–85. http://dx.doi.
org/10.1021/am4007534.
[53] Cao S-L, Xu H, Li X-H, Lou W-Y, Zong M-H. Papain@magnetic nanocrystalline cellu-
lose nanobiocatalyst: a highly efficient biocatalyst for dipeptide biosynthesis in deep
eutectic solvents. ACS Sustain Chem Eng 2015;3:1589–99. http://dx.doi.org/10.
1021/acssuschemeng.5b00290.
[54•] Cao S-L, Huang Y-M, Li X-H, Xu P, Wu H, Li N, et al. Preparation and characterization
of immobilized lipase from Pseudomonas cepacia onto magnetic cellulose
nanocrystals. Sci Rep 2016;6:20420. http://dx.doi.org/10.1038/srep20420.
[55] Ali I, Gupta VK. Advances in water treatment by adsorption technology. Nat Protoc
2007;1:2661–7. http://dx.doi.org/10.1038/nprot.2006.370.
[56] Bhatnagar A, Sillanpää M. Utilization of agro-industrial and municipal waste mate-
rials as potential adsorbents for water treatment—a review. Chem Eng J 2010;157:
277–96. http://dx.doi.org/10.1016/j.cej.2010.01.007.
[57] Crini G. Non-conventional low-cost adsorbents for dye removal: a review. Bioresour
Technol 2006;97:1061–85. http://dx.doi.org/10.1016/j.biortech.2005.05.001.
[58] Batmaz R, Mohammed N, Zaman M, Minhas G, Berry RM, Tam KC. Cellulose
nanocrystals as promising adsorbents for the removal of cationic dyes. Cellulose
2014;21:1655–65. http://dx.doi.org/10.1007/s10570-014-0168-8.
[59] Mohammed N, Grishkewich N, Berry RM, Tam KC. Cellulose nanocrystal–alginate
hydrogel beads as novel adsorbents for organic dyes in aqueous solutions. Cellulose
2015;22:3725–38. http://dx.doi.org/10.1007/s10570-015-0747-3.
[60] He X, Male KB, Nesterenko PN, Brabazon D, Paull B, Luong JHT. Adsorption and de-
sorption of methylene blue on porous carbon monoliths and nanocrystalline cellu-
lose. ACS Appl Mater Interfaces 2013;5:8796–804. http://dx.doi.org/10.1021/
am403222u.
[61•] Yu H-Y, Zhang D-Z, Lu F-F, Yao J. New approach for single-step extraction of carbox-
ylated cellulose nanocrystals for their use as adsorbents and flocculants. ACS Sus-
tain Chem Eng 2016;4:2632–43. http://dx.doi.org/10.1021/acssuschemeng.
6b00126.
[62] Qiao H, Zhou Y, Yu F, Wang E, Min Y, Huang Q, et al. Effective removal of cationic
dyes using carboxylate-functionalized cellulose nanocrystals. Chemosphere 2015;
141:297–303. http://dx.doi.org/10.1016/j.chemosphere.2015.07.078.
[63] Eyley S, Thielemans W. Imidazolium grafted cellulose nanocrystals for ion
exchange applications. Chem Commun 2011;47:4177. http://dx.doi.org/10.1039/
c0cc05359g.
[64] Jin L, Li W, Xu Q, Sun Q. Amino-functionalized nanocrystalline cellulose as an adsor-
bent for anionic dyes. Cellulose 2015;22:2443–56. http://dx.doi.org/10.1007/
s10570-015-0649-4.
[65] Liu P, Sehaqui H, Tingaut P, Wichser A, Oksman K, Mathew AP. Cellulose and chitin
nanomaterials for capturing silver ions (Ag+) from water via surface adsorption.
Cellulose 2014;21:449–61. http://dx.doi.org/10.1007/s10570-013-0139-5.
[66••] Liu P, Borrell PF, Božič M, Kokol V, Oksman K, Mathew AP. Nanocelluloses and their
phosphorylated derivatives for selective adsorption of Ag+, Cu2+ and Fe3+ from
industrial effluents. J Hazard Mater 2015;294:177–85. http://dx.doi.org/10.1016/j.
jhazmat.2015.04.001.
[67] Yu X, Tong S, Ge M, Wu L, Zuo J, Cao C, et al. Adsorption of heavy metal ions from
aqueous solution by carboxylated cellulose nanocrystals. J Environ Sci 2013;25:
933–43. http://dx.doi.org/10.1016/S1001-0742(12)60145-4.
[68] Kardam A, Raj KR, Srivastava S, Srivastava MM. Nanocellulose fibers for biosorption
of cadmium, nickel, and lead ions from aqueous solution. Clean Technol Environ Pol-
icy 2014;16:385–93. http://dx.doi.org/10.1007/s10098-013-0634-2.
[69] Srivastava S, Kardam A, Raj KR. Nanotech reinforcement onto cellulosic fibers: green
remediation of toxic metals. Int J Green Nanotechnol 2012;4:46–53. http://dx.doi.
org/10.1080/19430892.2012.654744.
[70] Kardam A, Raj KR, Srivastava S. Novel nano cellulosic fibers for remediation of heavy
metals from synthetic water. Int J Nanodimens 2012;3:155–62. http://dx.doi.org/10.
7508/ijnd.2012.02.009.
[71] Singh K, Arora JK, Sinha TJM, Srivastava S. Functionalization of nanocrystalline cellu-
lose for decontamination of Cr(III) and Cr(VI) from aqueous system: computational
modeling approach. Clean Technol Environ Policy 2014;16:1179–91. http://dx.doi.
org/10.1007/s10098-014-0717-8.
[72] Sheikhi A, Safari S, Yang H, van de Ven TGM. Copper removal using electrosterically
stabilized nanocrystalline cellulose. ACS Appl Mater Interfaces 2015;7:11301–8.
http://dx.doi.org/10.1021/acsami.5b01619.
[73] Sirviö JA, Hasa T, Leiviskä T, Liimatainen H, Hormi O. Bisphosphonate nanocellulose
in the removal of vanadium(V) from water. Cellulose 2016;23:689–97. http://dx.doi.
org/10.1007/s10570-015-0819-4.
[74] Mohammed N, Grishkewich N, Waeijen HA, Berry RM, Tam KC. Continuous flow ad-
sorption of methylene blue by cellulose nanocrystal-alginate hydrogel beads in fixed
bed columns. Carbohydr Polym 2016;136:1194–202. http://dx.doi.org/10.1016/j.
carbpol.2015.09.099.
[75] Mohammed N, Grishkewich N, Tam KC, Berry RM. Pristine and surface functional-
ized cellulose nanocrystals (CNCs) incorporated hydrogel beads and uses thereof.
US Patent 2016/0175812 A1, 2016.
[76] Zhou C, Lee S, Dooley K, Wu Q. A facile approach to fabricate porous nanocomposite
gels based on partially hydrolyzed polyacrylamide and cellulose nanocrystals for
adsorbing methylene blue at low concentrations. J Hazard Mater 2013;263:
334–41. http://dx.doi.org/10.1016/j.jhazmat.2013.07.047.
[77] Zhou C, Wu Q, Lei T, Negulescu II. Adsorption kinetic and equilibrium studies for
methylene blue dye by partially hydrolyzed polyacrylamide/cellulose nanocrystal
nanocomposite hydrogels. Chem Eng J 2014;251:17–24. http://dx.doi.org/10.1016/
j.cej.2014.04.034.
[78] Jin L, Sun Q, Xu Q, Xu Y. Adsorptive removal of anionic dyes from aqueous solutions
using microgel based on nanocellulose and polyvinylamine. Bioresour Technol 2015;
197:348–55. http://dx.doi.org/10.1016/j.biortech.2015.08.093.
[79•] Anirudhan TS, Shainy F. Effective removal of mercury(II) ions from chlor-alkali
industrial wastewater using 2-mercaptobenzamide modified itaconic acid-
grafted-magnetite nanocellulose composite. J Colloid Interface Sci 2015;456:
22–31. http://dx.doi.org/10.1016/j.jcis.2015.05.052.
[80] Anirudhan TS, Deepa JR, Christa J. Nanocellulose/nanobentonite composite anchored
with multi-carboxyl functional groups as an adsorbent for the effective removal of
cobalt(II) from nuclear industry wastewater samples. J Colloid Interface Sci 2016;
467:307–20. http://dx.doi.org/10.1016/j.jcis.2016.01.023.
[81] Mohammed N, Baidya A, Murugesan V, Avula AK, Ganayee MA, Mohanty JS, et al.
Diffusion controlled simultaneous sensing and scavenging of heavy metal ions in
water using atomically precise cluster – cellulose nanocrystal composites. ACS
Sustain Chem Eng 2016. http://dx.doi.org/10.1021/acssuschemeng.6b01674.
[82] Chen L, Berry RM, Tam KC. Synthesis of β-cyclodextrin-modified cellulose
nanocrystals (CNCs)@Fe3O4@SiO2 superparamagnetic nanorods. ACS Sustain Chem
Eng 2014;2:951–8. http://dx.doi.org/10.1021/sc400540f.
[83] Karim Z, Claudpierre S, Grahn M, Oksman K, Mathew AP. Nanocellulose based func-
tional membranes for water cleaning: tailoring of mechanical properties, porosity
and metal ion capture. J Membr Sci 2016;514:418–28. http://dx.doi.org/10.1016/j.
memsci.2016.05.018.
[84] Yang X, Cranston ED. Chemically cross-linked cellulose nanocrystal aerogels with
shape recovery and superabsorbent properties. Chem Mater 2014;26:6016–25.
http://dx.doi.org/10.1021/cm502873c.
[85•] Vandamme D, Eyley S, Van den Mooter G, Muylaert K, Thielemans W. Highly
charged cellulose-based nanocrystals as flocculants for harvesting Chlorella vulgaris.
Bioresour Technol 2015;194:270–5. http://dx.doi.org/10.1016/j.biortech.2015.07.
039.
[86] Sun X, Danumah C, Liu Y, Boluk Y. Flocculation of bacteria by depletion interactions
due to rod-shaped cellulose nanocrystals. Chem Eng J 2012;198–199:476–81. http://
dx.doi.org/10.1016/j.cej.2012.05.114.
[87] Carpenter AW, de Lannoy C-F, Wiesner MR. Cellulose nanomaterials in water
treatment technologies. Environ Sci Technol 2015;49:5277–87. http://dx.doi.org/
10.1021/es506351r.
[88] Metreveli G, Wågberg L, Emmoth E, Belák S, Strømme M, Mihranyan A. A size-
exclusion nanocellulose filter paper for virus removal. Adv Healthc Mater 2014;3:
1546–50. http://dx.doi.org/10.1002/adhm.201300641.
[89] Asper M, Hanrieder T, Quellmalz A, Mihranyan A. Removal of xenotropic murine leu-
kemia virus by nanocellulose based filter paper. Biologicals 2015;43:452–6. http://
dx.doi.org/10.1016/j.biologicals.2015.08.001.
[90] Quellmalz A, Mihranyan A. Citric acid cross-linked nanocellulose-based paper for
size-exclusion nanofiltration. ACS Biomater Sci Eng 2015;1:271–6. http://dx.doi.
org/10.1021/ab500161x.
[91] Karim Z, Mathew AP, Grahn M, Mouzon J, Oksman K. Nanoporous membranes with
cellulose nanocrystals as functional entity in chitosan: removal of dyes from water.
Carbohydr Polym 2014;112:668–76. http://dx.doi.org/10.1016/j.carbpol.2014.06.048.
[92] Karim Z, Mathew AP, Kokol V, Wei J, Grahn M. High-flux affinity membranes based
on cellulose nanocomposites for removal of heavy metal ions from industrial
effluents. RSC Adv 2016;6:20644–53. http://dx.doi.org/10.1039/C5RA27059F.
[93] Kaushik M, Moores A. Review: nanocelluloses as versatile supports for metal
nanoparticles and their applications in catalysis. Green Chem 2016;18:622–37.
http://dx.doi.org/10.1039/C5GC02500A.
[94] Wei H, Rodriguez K, Renneckar S, Vikesland PJ. Environmental science and
engineering applications of nanocellulose-based nanocomposites. Environ Sci
Nano 2014;1:302–16. http://dx.doi.org/10.1039/C4EN00059E.
[95] Hoeng F, Denneulin A, Bras J. Use of nanocellulose in printed electronics: a review.
Nanoscale 2016;8:13131–54. http://dx.doi.org/10.1039/C6NR03054H.
[96] Hamad WY. Photonic and semiconductor materials based on cellulose nanocrystals.
Adv Polym Sci 2015:287–328. http://dx.doi.org/10.1007/12_2015_323.
[97] Csoka L, Hoeger IC, Rojas OJ, Peszlen I, Pawlak JJ, Peralta PN. Piezoelectric effect of
cellulose nanocrystals thin films. ACS Macro Lett 2012;1:867–70. http://dx.doi.org/
10.1021/mz300234a.
[98] Wu X, Chabot VL, Kim BK, Yu A, Berry RM, Tam KC. Cost-effective and scalable chem-
ical synthesis of conductive cellulose nanocrystals for high-performance
supercapacitors. Electrochim Acta 2014;138:139–47. http://dx.doi.org/10.1016/j.
electacta.2014.06.089.
[99] Tkalya E, Ghislandi M, Thielemans W, van der Schoot P, de With G, Koning C.
Cellulose nanowhiskers templating in conductive polymer nanocomposites
reduces electrical percolation threshold 5-fold. ACS Macro Lett 2013;2:157–63.
http://dx.doi.org/10.1021/mz300597j.
 N. Grishkewich et al. / Current Opinion in Colloid & Interface Science 29 (2017) 32–45
[100••] Yang X, Shi K, Zhitomirsky I, Cranston ED. Cellulose nanocrystal aerogels as uni-
versal 3D lightweight substrates for supercapacitor materials. Adv Mater 2015;
27:6104–9. http://dx.doi.org/10.1002/adma.201502284.
[101] Wang S, Zhang X, Wu X, Lu C. Tailoring percolating conductive networks of natural
rubber composites for flexible strain sensors via a cellulose nanocrystal templated
assembly. Soft Matter 2016;12:845–52. http://dx.doi.org/10.1039/C5SM01958C.
[102] Zhu H, Fang Z, Preston C, Li Y, Hu L. Transparent paper: fabrications, properties, and
device applications. Energ Environ Sci 2014;7:269–87. http://dx.doi.org/10.1039/
C3EE43024C.
[103] Pérez-Madrigal MM, Edo MG, Alemán C. Powering the future: application of
cellulose-based materials for supercapacitors. Green Chem 2016. http://dx.doi.
org/10.1039/C6GC02086K.
[104] Liew SY, Walsh DA, Thielemans W. High total-electrode and mass-specific capaci-
tance cellulose nanocrystal-polypyrrole nanocomposites for supercapacitors. RSC
Adv 2013;3:9158–62. http://dx.doi.org/10.1039/c3ra41168k.
[105] Wu X, Tang J, Duan Y, Yu A, Berry RM, Tam KC. Conductive cellulose nanocrystals
with high cycling stability for supercapacitor applications. J Mater Chem A 2014;
2:19268–74. http://dx.doi.org/10.1039/C4TA04929B.
[106•] Wu X, Shi Z, Tjandra R, Cousins AJ, Sy S, Yu A, et al. Nitrogen-enriched porous car-
bon nanorods templated by cellulose nanocrystals as high performance
supercapacitor electrodes. J Mater Chem A 2015;3:23768–77. http://dx.doi.org/
10.1039/C5TA07252B.
[107] Shi K, Yang X, Cranston ED, Zhitomirsky I. Efficient lightweight supercapacitor with
compression stability. Adv Funct Mater 2016;26:6437–45. http://dx.doi.org/10.
1002/adfm.201602103.
[108] van den Berg O, Schroeter M, Capadona JR, Weder C. Nanocomposites based on
cellulose whiskers and (semi)conducting conjugated polymers. J Mater Chem
2007;17:2746. http://dx.doi.org/10.1039/b700878c.
[109] Hamad WY, Atifi S. Flexible, semiconducting nanocomposite materials based on
nanocrystalline cellulose and polyaniline. US Patent 2014/0203214 A1, 2014.
[110•] Wang S, Wei C, Gong Y, Lv J, Yu C, Yu J. Cellulose nanofiber-assisted dispersion of
cellulose nanocrystals@polyaniline in water and its conductive films. RSC Adv
2016;6:10168–74. http://dx.doi.org/10.1039/C5RA19346J.
[111] Safari S, van de Ven TGM. Effect of water vapor adsorption on electrical properties
of carbon nanotube/nanocrystalline cellulose composites. ACS Appl Mater
Interfaces 2016;8:9483–9. http://dx.doi.org/10.1021/acsami.6b02374.
[112•] Xiong R, Hu K, Grant AM, Ma R, Xu W, Lu C, et al. Ultrarobust transparent cellulose
nanocrystal-graphene membranes with high electrical conductivity. Adv Mater
2016;28:1501–9. http://dx.doi.org/10.1002/adma.201504438.
[113••] Zhou Y, Fuentes-Hernandez C, Khan TM, Liu J-C, Hsu J, Shim JW, et al. Recyclable
organic solar cells on cellulose nanocrystal substrates. Sci Rep 2013;3:1536.
http://dx.doi.org/10.1038/srep01536.
[114] Zhou Y, Khan TM, Liu J-C, Fuentes-Hernandez C, Shim JW, Najafabadi E, et al.
Efficient recyclable organic solar cells on cellulose nanocrystal substrates with a
conducting polymer top electrode deposited by film-transfer lamination. Org
Electron 2014;15:661–6. http://dx.doi.org/10.1016/j.orgel.2013.12.018.
[115] Najafabadi E, Zhou YH, Knauer KA, Fuentes-Hernandez C, Kippelen B. Efficient
organic light-emitting diodes fabricated on cellulose nanocrystal substrates. Appl
Phys Lett 2014;105:63305. http://dx.doi.org/10.1063/1.4891046.
[116] Wang C-Y, Fuentes-Hernandez C, Liu J-C, Dindar A, Choi S, Youngblood JP, et al.
Stable low-voltage operation top-gate organic field-effect transistors on cellulose
nanocrystal substrates. ACS Appl Mater Interfaces 2015;7:4804–8. http://dx.doi.
org/10.1021/am508723a.
[117] Costa SV, Pingel P, Janietz S, Nogueira AF. Inverted organic solar cells using
nanocellulose as substrate. J Appl Polym Sci 2016;133:6–11. http://dx.doi.org/10.
1002/app.43679.
[118•] Sadasivuni KK, Kafy A, Zhai L, Ko H-U, Mun S, Kim J. Transparent and flexible
cellulose nanocrystal/reduced graphene oxide film for proximity sensing. Small
2015;11:994–1002. http://dx.doi.org/10.1002/smll.201402109.
[119••] Pang Q, Tang J, Huang H, Liang X, Hart C, Tam KC, et al. A nitrogen and sulfur dual-
doped carbon derived from polyrhodanine@cellulose for advanced lithium-sulfur
batteries. Adv Mater 2015;27:6021–8. http://dx.doi.org/10.1002/adma.
201502467.
[120] Kafy A, Akther A, Shishir MIR, Kim HC, Yun Y, Kim J. Cellulose nanocrystal/graphene
oxide composite film as humidity sensor. Sensors Actuators A Phys 2016;247:
221–6. http://dx.doi.org/10.1016/j.sna.2016.05.045.
[121] Sadasivuni KK, Ponnamma D, Ko H-U, Kim HC, Zhai L, Kim J. Flexible NO2 sensors
from renewable cellulose nanocrystals/iron oxide composites. Sens Actuators B
2016;233:633–8. http://dx.doi.org/10.1016/j.snb.2016.04.134.
[122] Fan J, Shao W, Xu G, Cui XT, Luo X. Preparation and electrochemical catalytic appli-
cation of nanocrystalline cellulose doped poly(3,4-ethylenedioxythiophene)
conducting polymer nanocomposites. RSC Adv 2014;4:24328–33. http://dx.doi.
org/10.1039/C4RA02796E.
[123] Xu G, Liang S, Fan J, Sheng G, Luo X. Amperometric sensing of nitrite using a glassy
carbon electrode modified with a multilayer consisting of carboxylated nanocrys-
talline cellulose and poly(diallyldimethyl ammonium) ions in a PEDOT host.
Microchim Acta 2016;183:2031–7. http://dx.doi.org/10.1007/s00604-016-1842-3.
45
[124] Chen L, Lai C, Marchewka R, Berry RM, Tam KC. Use of CdS quantum dot-
functionalized cellulose nanocrystal films for anti-counterfeiting applications.
Nanoscale 2016;8:13288–96. http://dx.doi.org/10.1039/C6NR03039D.
[125] Tang J, Song Y, Berry RM, Tam KC. Polyrhodanine coated cellulose nanocrystals as
optical pH indicators. RSC Adv 2014;4:60249–52. http://dx.doi.org/10.1039/
C4RA09043H.
[126] Azizi Samir MAS, Alloin F, Gorecki W, Sanchez J, Dufresne A. Nanocomposite
polymer electrolytes based on poly(oxyethylene) and cellulose nanocrystals. J
Phys Chem B 2004;108:10845–52. http://dx.doi.org/10.1021/jp0494483.
[127] Lalia BS, Samad YA, Hashaikeh R. Nanocrystalline cellulose-reinforced composite
mats for lithium-ion batteries: electrochemical and thermomechanical performance.
J Solid State Electrochem 2013;17:575–81. http://dx.doi.org/10.1007/s10008-012-
1894-1.
[128•] Arbizzani C, Colò F, De Giorgio F, Guidotti M, Mastragostino M, Alloin F, et al. A
non-conventional fluorinated separator in high-voltage graphite/LiNi0.4Mn1.6O4
cells. J Power Sources 2014;246:299–304. http://dx.doi.org/10.1016/j.jpowsour.
2013.07.095.
[129] Bolloli M, Antonelli C, Molméret Y, Alloin F, Iojoiu C, Sanchez J-Y. Nanocomposite
poly(vynilidene fluoride)/nanocrystalline cellulose porous membranes as separators
for lithium-ion batteries. Electrochim Acta 2016;214:38–48. http://dx.doi.org/10.
1016/j.electacta.2016.08.020.
[130] Liu Q, Chen C, Pan F, Zhang J. Highly efficient oxygen reduction on porous nitrogen-
doped nanocarbons directly synthesized from cellulose nanocrystals and urea.
Electrochim Acta 2015;170:234–41. http://dx.doi.org/10.1016/j.electacta.2015.04.
094.
[131] Lu Y, Armentrout AA, Li J, Tekinalp HL, Nanda J, Ozcan S. A cellulose nanocrystal-
based composite electrolyte with superior dimensional stability for alkaline fuel
cell membranes. J Mater Chem A 2015;3:13350–6. http://dx.doi.org/10.1039/
C5TA02304A.
[132] Kalashnikova I, Bizot H, Cathala B, Capron I. New Pickering emulsions stabilized by
bacterial cellulose nanocrystals. Langmuir 2011;27:7471–9. http://dx.doi.org/10.
1021/la200971f.
[133] Kalashnikova I, Bizot H, Cathala B, Capron I. Modulation of cellulose nanocrystals
amphiphilic properties to stabilize oil/water interface. Biomacromolecules 2012;
13:267–75. http://dx.doi.org/10.1021/bm201599j.
[134] Kalashnikova I, Bizot H, Bertoncini P, Cathala B, Capron I. Cellulosic nanorods of
various aspect ratios for oil in water Pickering emulsions. Soft Matter 2013;9:
952–9. http://dx.doi.org/10.1039/C2SM26472B.
[135] Zoppe JO, Venditti RA, Rojas OJ. Pickering emulsions stabilized by cellulose
nanocrystals grafted with thermo-responsive polymer brushes. J Colloid Interface
Sci 2012;369:202–9. http://dx.doi.org/10.1016/j.jcis.2011.12.011.
[136] Tang J, Lee MFX, Zhang W, Zhao B, Berry RM, Tam KC. Dual responsive Pickering
emulsion stabilized by poly[2-(dimethylamino)ethyl methacrylate] grafted cellulose
nanocrystals. Biomacromolecules 2014;15:3052–60. http://dx.doi.org/10.1021/
bm500663w.
[137] Tang J, Berry RM, Tam KC. Stimuli-responsive cellulose nanocrystals for surfactant-
free oil harvesting. Biomacromolecules 2016;17:1748–56. http://dx.doi.org/10.
1021/acs.biomac.6b00144.
[138] Li M-C, Wu Q, Song K, Qing Y, Wu Y. Cellulose nanoparticles as modifiers for
rheology and fluid loss in bentonite water-based fluids. ACS Appl Mater Interfaces
2015;7:5006–16. http://dx.doi.org/10.1021/acsami.5b00498.
[139] Li M-C, Wu Q, Song K, De Hoop CF, Lee S, Qing Y, et al. Cellulose nanocrystals and
polyanionic cellulose as additives in bentonite water-based drilling fluids: rheolog-
ical modeling and filtration mechanisms. Ind Eng Chem Res 2016;55:133–43.
http://dx.doi.org/10.1021/acs.iecr.5b03510.
[140] Akhlaghi SP, Berry RM, Tam KC. Modified cellulose nanocrystal for vitamin C
delivery. AAPS PharmSciTech 2015;16:306–14. http://dx.doi.org/10.1208/s12249-
014-0218-4.
[141] Yao Z, Tam JH. Fullerene-derived cellulose nanocrystal, their preparation and uses
thereof. US Patent 2014/0256832 A1, 2014.
[142] Awan F, Bulger E, Berry RM, Tam KC. Enhanced radical scavenging activity of
polyhydroxylated C60 functionalized cellulose nanocrystals. Cellulose 2016.
http://dx.doi.org/10.1007/s10570-016-1057-0.
[143] Hu Z, Marway HS, Kasem H, Pelton R, Cranston ED. Dried and redispersible
cellulose nanocrystal Pickering emulsions. ACS Macro Lett 2016;5:185–9. http://
dx.doi.org/10.1021/acsmacrolett.5b00919.
[144] Vandamme EJ, De Baets S, Vanbaelen A, Joris K, De Wulf P. Improved production of
bacterial cellulose and its application potential. Polym Degrad Stab 1998;59:93–9.
http://dx.doi.org/10.1016/S0141-3910(97)00185-7.
[145] Yu H, Yan C, Yao J. Fully biodegradable food packaging materials based on function-
alized cellulose nanocrystals/poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
nanocomposites. RSC Adv 2014;4:59792–802. http://dx.doi.org/10.1039/
C4RA12691B.
[146] Cheng S, Zhang Y, Cha R, Yang J, Jiang X. Water-soluble nanocrystalline cellulose
films with highly transparent and oxygen barrier properties. Nanoscale 2016;8:
973–8. http://dx.doi.org/10.1039/C5NR07647A.