PII: S0021-9797(17)30100-5
DOI: http://dx.doi.org/10.1016/j.jcis.2017.01.077
Reference: YJCIS 21983
Please cite this article as: J. Tang, J. Sisler, N. Grishkewich, K.C. Tam, Functionalization of cellulose nanocrystals
for advanced applications, Journal of Colloid and Interface Science (2017), doi: http://dx.doi.org/10.1016/j.jcis.
2017.01.077
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Functionalization of cellulose nanocrystals for advanced applications
Abstract
Aside from the investigation on emulsion systems stabilized by pristine CNCs, various
modification strategies have been used to manipulate the surface functionalities of CNCs in
controlling the physical properties of Pickering emulsions. This was achieved through the
incorporation of surfactants [30], functional groups or surface active polymers, for example
TEMPO oxidation and adsorption [31], periodate oxidation and amination [32], esterification
[33], as well as long alkyl chain grafting [34]. Two types of cationic charged surfactants
didecyldimethylammonium bromide (DMAB) and cetyltrimethylammonium bromide (CTAB)
were adsorbed on the CNCs surface to tailor the hydrophobicity of the nanoparticles, and their
capability to stabilize emulsions was investigated by Cranston and coworkers [30]. They
observed a double transitional phase inversion (from oil-in-water to water-in-oil and then back to
oil-in-water) for emulsions stabilized by CNCs with increasing amounts of DMAB (a more
hydrophobic molecule). However, no phase inversion could be induced for CNCs modified by
CTAB (Figure 3C). Similarly, Capron and coworkers reported a simple method to prepare
hydrophobic CNCs by adsorbing quaternary ammonium salts onto the TEMPO-oxidized CNCs,
and the modified nanoparticles were capable of stabilizing inverse water-in-oil emulsions [31].
Pelton and coworkers studied the effects of both surfactant and water-soluble polymers
(hydroxyethyl cellulose or methyl cellulose) on the properties of Pickering emulsions stabilized
by cellulose nanocrystals [35]. The polymer coated CNCs nanoparticles produced emulsions
with smaller droplet sizes, and the emulsions could resist coalescence when subjected to multiple
cycles of heating and cooling.
Compared to systems modified by physical adsorption, covalent chemical modifications
can provide a more robust and versatile platform. Capron and coworkers tailored the
hydrophobicity of CNCs and nanofibrillated cellulose (NFC) by chemical modification with
lauroyl chloride (C12) [34]. They observed that the Pickering emulsions stabilized by the
combination of two types of modified nanocellulose could be formulated into oil-in-water-in-oil
(o/w/o) emulsions depending on the degree of substitutions. Sebe and coworkers modified the
CNCs surface with vinyl acetate (VAc) and vinyl cinnamate (VCIn) and observed that the
esterification treatment may significantly impact their utilization as Pickering emulsifiers [33].
VCIn-treated particles could only stabilize the cyclohexane-in-water emulsions, while the acetyl
modified CNCs could be used to prepare stable ethyl acetate-in-water, toluene-in-water, and
cyclohexane-in-water emulsions. Furthermore, in order to tailor the control of Pickering
emulsions for specific applications, much research has been devoted to the development of
emulsifiers that activate and deactivate in response to external stimuli. Zoppe et al. grafted
thermo-responsive Poly(N-isopropylacrylamine) (PNIPAM) onto CNCs surface and compared
the different nanoparticles in stabilizing emulsion systems [36]. They found that modified
cellulose nanocrystals could stabilize the emulsions for a period of 4 months compared to
unmodified CNCs nanoparticles. Tang and coworkers reported a dual-responsive (pH and thermo)
system based on poly(dimetheylamino ethylmethacrylate) (PDMAEMA) grafted cellulose
nanocrystals [37]. They demonstrated the feasibility of stabilizing both toluene- and heptane-in-
water emulsions under basic conditions. Decreasing the pH values lead to the protonation of
tertiary amines on PDMAEMA chains, that promotes the electrostatic interaction between CNCs
particles and polymer chains, resulting in a reversible particle aggregation and emulsion
instability (Figure 3D). Following this, they grafted binary polymer brushes consisting of
poly(oligoethylene glycol) methacrylate (POEGMA) and poly(methacrylic acid) (PMAA) on the
surface of CNCs nanoparticles [38]. This would permit the control of the stability of Pickering
emulsions using two types of triggers, i.e., POEGMA for temperature and PMAA for the pH.
They demonstrated a reversible emulsification-demulsification process controlled by pH using
the binary brush grafted nanoparticles, where the emulsification and oil-water separation could
be repeated 5 times without any loss in efficiency (Figure 3E).
Cellulose nanocrystal based Pickering emulsions could be formulated for use in
encapsulation systems. Marquis and coworkers described a two-step approach to encapsulate oil
microdroplets within alginate microgels [39]. The microdroplets were oil-in-water Pickering
emulsions that were stabilized by cellulose nanocrystals and calcium carbonate. They further
demonstrated that the CNCs layer could provide an ideal shell to prevent the coalescence of oil
droplets. The Ca2+ released from the CaCO3 particles could be used for the gelation of alginate to
form the microgel. Nile Red was used as a model compound to trace the release profile after
encapsulation, and the double encapsulation protocol could provide better protection as well as
sustained release when compared to the traditional method of encapsulation. Hu et al. has also
reported another encapsulation system, which was based on emulsions stabilized by
hydroxyethyl cellulose (HEC) modified CNCs nanoparticles [40]. They further coated emulsified
corn oil in water emulsions with tannic acid, which can be transformed into solid dry emulsions
(powders) via freeze-drying (Figure 3F). This work extended the use of surfactant free emulsions
for food, cosmetic and pharmaceutical applications.
[46] TEOS or TMOS Remove CNCs +Ag NPs filled Ag assembled in chiral nematic Silica film
[47] TEOS or TMOS Pyrolysis-remove SiO2 Mesoporous Carbon
Mesoporous silica+TiCl4
[48] TMOS and TiCl4 Mesoporous TiO2
infiltration + silica etching
Ethylene-bridged organosilica Improving mechanical properties and flexibility
[49] Remove CNCs
precursors compared to pure silica
[50] TMOS Remove CNCs Ionic strength for color changing
EISA (evaporation induced self-
[51] PAAm hydrogel precusors Hydrogel sensor
assembly)
[52] Phenol-formaldehyde Remove CNCs Chiral mesoporous photonic resin
Adding Polyols such as glucose to eliminate the
[53] TMOS Remove CNCs
crack
Detailed investigation on the conditions for film (pH
[54] TMOS Remove CNCs
and ratio)
[55] Phenol-formaldehyde Remove CNCs Chiral nematic Structures and Actuator Properties
[56] TMOS PVA to reduce the crack Remove CNCs+ CdS QDs Mesoporous, chiral nematic order and luminescence
Alkaline treatment to remove UF Mesoporous chiral cellulose material displaying
[57] Urea formaldehyde
resin dynamic photonic properties
Chiral nematic SiO2 for Gas Chromatographic
[58] TMOS Remove CNCs
separation
[59] TEOT (Ti) Remove CNCs Mesoporous TiO2 film for solar cell
Precusor for prussian blue, organosilica Remove CNCs and silica
[60] precursors, TMOS Mesoporous coordination polymers
Porous semiconducting material with chiral nematic
[44] TMOS Magnesiothermic reduction structures
Remove PF, Photonic Patterns
[61] Phenol-formaldehyde Printed (dry or wet) Anticounterfeiting materials
Inverse emulsion polymerization Noval mesoporous silica microsphere for optical
[45] PAAM, TMOS and romove CNCs device and chiral separation
Urea formaldehyde, cobalt ferrite
[62] precusor Remove UF and CNCs Electromagnetic interference (EMI) shielding
The deposition of nanoparticles onto the surface of cellulose nanocrystals can generate
new hybrid materials that are suitable for use as heterogeneous catalysts in engineering
applications, especially for wastewater treatment. By using rod-like pristine cellulose
nanocrystals as substrate, various types of catalysts have been prepared including nickel
nanocrystals [63], palladium nanoparticles [64,65], TiO2 nanocubes [66], and alloy nanoparticles
[67]. They have been widely used in chemical reduction reactions (e.g. 4-nitrophenol to 4-
aminophenol; oxygen reduction reaction; hydrogenation of C-C and C-O multiple bonds),
oxidations (benzyl alcohol to benzaldehyde), coupling reactions (Mizoroki-Heck coupling
reaction) and photo degradations (methylene blue or methyl orange). Two excellent review
articles on this topic have recently been published [68,69].
Figure 5 Schematic illustration on application of nano-catalysts (reducing 4-nitrophenol) using
modified cellulose nanocrystals as carriers via different protocols, (A) Mussel-inspired
polydopamine coating [70]; (B) PAMAM dendrimer grafting [71] and (C) Porous melamine-
formaldehyde resin coating [72].
Aside from the most developed approach on using pristine CNCs nanoparticles, other
modification methods have been developed that introduce metal affinity groups or polymers on
the surface of CNCs for the purpose of loading inorganic nanoparticles. Tang et al. reported a
simple and facile approach using mussel-inspired polydopamine to deposit silver nanoparticles
onto cellulose nanocrystals [70]. The catechol-rich polydopamine can be utilized as chelating
groups as well as reducing agents, which has the added benefit of not requiring harsh conditions
or toxic reducing agents to synthesize the nanoparticles (Figure 5A). By using the model reaction
of 4-nitrophenol to 4-aminophenol, they found that the catalytic rate constants were 6 times
faster than pristine silver nanoparticles reduced by dopamine. Chen et al. covalently grafted
poly(amidoamine) (PAMAM) dendrimers onto the surface of oxidized CNCs using peptidic
coupling [71]. The incorporated PAMAM dendrimers provided a well-defined hyper-branched
structure, from which the cavities could be used as nano-reactors to control the size of gold
nanoparticles (Figure 5B). By optimizing the synthesis conditions, the best performance of the
gold nanocatalyst to reduce 4-nitrophenol was reflected by a turnover frequency (TOF) of 5 400
h-1, which was exceptionally greater than other systems that used modified CNCs as supports.
Very recently, Wu et al. extended these ideas to prepare highly porous cellulose nanocrystal
support systems [72]. Mesoporous structures were achieved by coating a layer of melamine-
formaldehyde resin (MF) using polycondensation reactions. The nitrogen enriched resin
provided chelating sites that can improve metal ion binding and the porous structure can confine
the growth of nanoparticles with a uniform size distribution (Figure 5C). After depositing the Pt
or Pd nanoparticles onto MF-CNCs, the hybrid material displayed superior catalytic properties
towards the reduction of 4-nitrophenol with a TOF of up to 3168 h-1. In an effort to combat the
problem of water pollution, rapid and recyclable treatment materials based on cellulose
nanocrystals were prepared by Chen et al. [73]. They deposited superparamagnetic Fe3O4
nanoparticles onto the surface of cellulose nanocrystals, resulting in nanorods that could respond
to external magnetic triggers. In order to improve the stability of CNCs against oxidation, a
uniform silica layer was coated onto the hybrids. This coating layer could increase the onset
decomposition temperature by 60 oC when compared to pristine CNCs. Through further grafting
of -cyclodextrins (-CD), the resulting CNCs@Fe3O4@SiO2 @-CD hybrids exhibited good
adsorption properties towards model pharmaceutical residues in water, such as procaine
hydrochloride and imipramine hydrochloride, with an adsorption capacity of 13 mg/g and 14.8
mg/g, respectively.
Another example of inorganic-CNCs hybrid application is the use of such system as anti-
microbial agent. Silver or zinc oxide nanoparticles (Ag or ZnO) have been widely investigated
for this purpose. Drogat et al. reported an approach to deposit silver nanoparticles onto aldehyde
functionalized cellulose nanocrystals, where the aldehyde groups were used to reduce Ag+ to Ag0
in mild conditions [74]. The silver nanoparticles were in the size range of 20 to 45 nm and the
composite exhibited excellent antimicrobial properties. Shi et al. developed a method to load
silver nanoparticles using polydopamine coated cellulose nanocrystals [75]. The hybrid material
exhibited improved antimicrobial properties towards gram negative Escherichia coli, and gram
positive Bacillus subtilis bacteria with a minimal inhibition concentration (MIC) of 4 g/ml and
8 g/ml, respectively. TEM studies were conducted to understand the improved antimicrobial
properties of the hybrid materials. They attributed this result to the high concentrations of silver
ions released from the silver nanoparticles near the surface of the organisms, which kill the
bacteria. This process was assisted by the adhesive properties of polydopamine towards the cell
membranes. Yao and coworkers prepared ZnO/cellulose nanocrystal hybrids through a one-pot
green synthesis method, in which the modified carboxyl groups could function as stabilizing and
supporting agents for the deposition of ZnO nanoparticles [76]. Carboxyl groups were introduced
during the hydrolysis process using citric and hydrochloric mixed acids (C6H8O7/HCl). The
obtained ZnO nanoparticles with a hexagonal wurtzite structure and the smallest average
diameter of 42.6 nm displayed promising antimicrobial properties against the model bacteria;
Escherichia coli and Staphylococcus aureus.
Other applications could also be found in bioimaging/biosensing, such as quantum dots
(QDs) or carbon dots being the most well-known. Chen et al. demonstrated a one-pot synthesis
to prepare well-dispersed QDs in aqueous solution using oxidized cellulose nanocrystals [77]. A
co-precipitation method was introduced to synthesize the CdS@ZnS core-shell quantum dots.
The carboxylate groups provided the sites for coordinating Cd2+ ions that allow for the in-situ
nucleation and growth of QDs on the CNCs surface. The coating of a ZnS shell was introduced
to reduce the toxicity of hybrid materials as well as enhance the photo-emission intensity. They
further demonstrated that HeLa cells can uptake the composite nanoparticles effectively, with
intense red photoluminescence mostly observed in cytoplasmic regions (Figure 6A). In addition,
they reported a quantum dot-cellulose nanocrystal system that can be used for anti-counterfeiting
applications [78]. Structural colorful films were fabricated via layer-by-layer self-assembly of
oppositely charged CdS quantum dot modified cellulose nanocrystals on a flexible poly(ethylene
terephthalate) substrate. CNCs-COOH@CdS and CNCs-PEI@CdS were utilized in the assembly
process, with the emission peaks around 650 nm (size 4 nm) and 480 nm (size 2.1 nm),
respectively. The fabricated films displayed tunable structural colors from film interference and
adjustable emission colors from the quantum dots, which demonstrates their promising
applications in anti-counterfeiting devices (Figure 6B).
Figure 6 (A) Confocal fluorescence micrographs of HeLa cells showing the uptake of
CNCs/CdS@ZnS quantum dots with red emissions. The cytoskeleton actin was stained green
[77]. (B) Schematic illustration showing the quantum dot-cellulose nanocrystal films for the
purpose of anti-counterfeiting application. The film was fabricated via a layer-by-layer self-
assembly process and the thickness and roughness were characterized by scanning electron
microscopy [78].
We will first discuss the application of CNCs in wastewater treatment. Environmental pollution
in developing countries is becoming more severe. Water is one of the basic necessities needed to
sustain and support life. CNCs is nontoxic and possesses high surface area, which is a key
characteristic for its application in wastewater treatment, especially as an adsorbent. Luong and
coworkers were the first to report the use of pristine CNCs to adsorb a cationic dye, methylene
blue, with the maximum capacity determined to be 101 mg/g determined from the Langmuir
isotherm [79]. Following that, Batmaz et al. modified the CNCs surface through TEMPO
oxidation to increase the surface charge density, which increased the maximum adsorption
capacity of methylene blue to 769 mg/g [80]. However, it should be noted that using
nanoparticles as adsorbents could be problematic for downstream separation processes (i.e.
coagulation or high speed centrifugation), which limit their large scale applications. Mohammed
et al. incorporated high surface area CNCs into a negatively charged biopolymer (alginate)
matrix [81,82] (Figure 7). A further ionic crosslinking process was introduced to produce macro-
size hydrogel beads. With this composite material, the CNCs adsorption capability was retained,
and the use of hydrogel beads facilitated the easy separation in batch adsorption or in a
continuous flow packed bed system [82]. Also, by impregnating CNCs into the hydrogel matrix,
it can contribute to a higher surface area for adsorption as well as enhanced mechanical
properties. Cranston and coworkers designed crosslinked cellulose nanocrystal aerogels ultilizing
the Schiff-base chemistry. The ultralightweight (5.6 mg/cm3) and porous (99.6%) aerogels
exhibited enhanced mechanical properties and shape recovery capability in water [83]. More
interestingly, they further demonstrated that the aerogels could be used as superabsorbents for
oil-water separations as they have strong affinity towards different solvents. Aside from the
decontamination techniques, such as adsorption or absorption, another promising large scale
process to explore and exploit is flocculation. Cranston and colleagues functionalized the surface
of CNCs with poly(4-vinylpyridine), a pH-responsive polymer that can tune the
hydrophilic/hydrophobic properties of the nanoparticle [84]. At pH values lower than the pka, the
pyridine motifs were protonated, resulting in a positive charge on the nanoparticle surface that
ensured a stable colloidal dispersion. While increasing the pH values, the deprotonation of the
pyridyl groups led to more exposed hydrophobic groups, causing the nanoparticles to flocculate
and precipitate from aqueous dispersions.
Figure 7 (A) Schematic showing the preparation of CNCs-alginate hydrogel beads [81]; (B)
Comparison of the adsorption capability of pure alginate and CNCs-alginate hydrogel beads
towards methylene blue [81]; (C) Schematic diagram of a fixed bed adsorption column process
for removing methylene blue from contaminated water [82].
Figure 9 (A) Schematic illustration of the synthesis pathway of CNCs-g-PEEP via (CuAAC)
click reaction and the formation of DOX-loaded cellulose nanocrystals; (B) In vitro drug
release profile of DOX-loaded CNCs-g-PEEP at pH 5.0 and 7.4 [92].
that the CNCs-based carrier showed good biocompatibility towards both HeLa cells and L929
cells, with average cell viabilities above 90%, even at high concentrations. Aside from specific
drugs for therapy or drug delivery, an antioxidant Vitamin C was formulated with modified
CNCs. CNCs-CSos was used to complex Vitamin C (VC) via a further ionic gelation through
triphosphate crosslinking [93]. The encapsulation efficiency of VC into a complex approached
up to 71.6% and 91% at pH 3 and 5, respectively. The system displayed a sustained release of
active components (Vitamin C) up to 20 days and showed promising radical scavenging and
antioxidant activity. Apart from drug delivery systems, Tang et al. reported on a stable
antimicrobial system that is based on a polyrhodanine coated cellulose nanocrystal [93]. The
coating procedure was easy and feasible using an in-situ oxidation polymerization procedure.
The optimized sample exhibited promising antimicrobial properties towards both E. coli (Gram
negative) and B. subtilis (Gram positive). Also, their toxicity towards HeLa cells were
demonstrated to be low within the concentrations that displayed favourable antimicrobial
properties. In addition to antimicrobial properties, they found that the modified nanoparticle
displayed a pH-dependent optical characteristic [94]. The color of the dispersion gradually
changed from pale red to blue violet when the pH was increased from 2.04 to 12.04. The redox
reversibility of the hybrid nanomaterial in response to pH was retained when transformed into
different geometries, such as 1D printable inks, 2D flat films and membranes, and 3D hydrogel
beads (Figure 10). They anticipated that the modified material could be processed into vacuum
packaging materials, with the effective antimicrobial properties providing long-term protection
for fresh meat or vegetables. The pH-dependent optical property may also be used to assess the
quality of food as the metabolism of microorganisms may lead to pH changes.
Figure 10 (A) Summary of the UV-Vis spectra of a 0.01 wt% CNCs@PR dispersion at different
pH values; (B) Sigmoidal plots of maximum absorption wavelength and absorbance@peak
versus pH. (C) Schematic illustrating the redox reversibility of the hybrid nanomaterial in
response to pH was retained when transformed into different geometries [94].
The purpose of CNCs as potential carriers for cell uptake originates from its size,
hydrophilic nature and chemical composition. Modifying the surface with fluorophores can
generate nanoscale biomarkers that could be used for the localization and quantification of
nanoparticles within the cell. Roman and coworkers were the first report the fluorescence
characteristic using modified CNCs by conjugating the surface with fluorescein-5-
isothiocyanate (FITC) [95]. They used spectrofluorometry, fluorescence microscopy and flow
cytometry to study the in-vivo interaction of modified CNCs within cells. Luong and co-workers
compared the application of negatively charged FITC and positively charged rhodamine B
isothiocyanate (RBITC) modified cellulose nanocrystals in cell internalization [96]. They found
that the negatively charged FITC-CNCs could not be internalized by the cells due to the strong
electrostatic repulsions between the anionic CNCs and anionic cellular membrane. However,
RBITC-CNCs exhibited low cytotoxicity and excellent membrane permeability in various cell
lines, which suggests that the surface charge and conjugated elements are essential factors when
functionalizing the nanoparticle as carriers to cells for bioimaging and drug delivery.
Acknowledgements
The research funding from CelluForce and AboraNano facilitated the research on CNCs. K. C.
Tam wishes to acknowledge funding from CFI and NSERC.
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Graphical Abstract