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org/acssensors Review

A Review on the Role and Performance of Cellulose Nanomaterials


in Sensors
Kelcilene B. R. Teodoro, Rafaela C. Sanfelice, Fernanda L. Migliorini, Adriana Pavinatto,
Murilo H. M. Facure, and Daniel S. Correa*

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ABSTRACT: Sensors and biosensors play a key role as an


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analytical tool for the rapid, reliable, and early diagnosis of human
diseases. Such devices can also be employed for monitoring
environmental pollutants in air and water in an expedited way.
More recently, nanomaterials have been proposed as an alternative
in sensor fabrication to achieve gains in performance in terms of
sensitivity, selectivity, and portability. In this direction, the use of
cellulose nanomaterials (CNM), such as cellulose nanofibrils
(CNF), cellulose nanocrystals (CNC), and bacterial cellulose
(BC), has experienced rapid growth in the fabrication of varied types of sensors. The advantageous properties are related to the
supramolecular structures that form the distinct CNM, their biocompatibility, and highly reactive functional groups that enable
surface functionalization. The CNM can be applied as hydrogels and xerogels, thin films, nanopapers and other structures interesting
for sensor design. Besides, CNM can be combined with other materials (e.g., nanoparticles, enzymes, carbon nanomaterials, etc.) and
varied substrates to advanced sensors and biosensors fabrication. This review explores recent advances on CNM and composites
applied in the fabrication of optical, electrical, electrochemical, and piezoelectric sensors for detecting analytes ranging from
environmental pollutants to human physiological parameters. Emphasis is given to how cellulose nanomaterials can contribute to
enhance the performance of varied sensors as well as expand novel sensing applications, which could not be easily achieved using
standard materials. Finally, challenges and future trends on the use of cellulose-based materials in sensors and biosensors are also
discussed.
KEYWORDS: natural polymers, cellulosic materials, optical sensor, piezoelectric sensor, electrical sensor, electrochemical sensor, biosensor,
chiral nematic organization, electrode modification, electrospinning

T he investigation and application of sensors and biosensors


as an analytical tool for monitoring analytes related to
environmental contamination and human diseases have
components and in some cases can render biocompatibility to
the final sensors. This is the case of cellulose, the fundamental
skeletal component in the plant kingdom and the most
drastically increased in the past years.1,2 When compared to abundant biopolymer on Earth.15 More specifically, the
conventional spectroscopic and chromatographic analytical number of investigations on cellulose nanomaterials (CNM)
techniques, sensors and biosensors offer advantages in terms of have experienced a dramatic increase in the last two decades,
simplicity of procedures, cheaper reactants, and flexibility for and the remarkable advances enabled the first industries to
on-site analysis.3,4 Besides, the detection of various analytes at produce CNM in commercial large scale.16 In the past few
very low concentrations can be improved by using nano- years, several young companies worldwide have started to
engineered materials with increased surface area-to-volume bring CNM-based products to the market.16,17 The remarkable
ratio and specific functionalities to improve chemical and/or progress in the CNM field is reflected by the large number of
biological recognition. Such a goal is required for the publications and patents in this field,18 including some
transduction mechanism,5−8 having a positive impact on the excellent review papers reporting the use of CNM in
sensitivity, specificity, reproducibility, and portability of varied
sensors.8−10 Received: March 4, 2021
Among the myriad materials available for sensor fabrication, Accepted: June 10, 2021
recently efforts have been conducted on natural polymers as Published: June 29, 2021
substrates or even as components of the sensor active
layer.11−14 Such materials can add to sustainability by
minimizing the use of nonrenewable and toxic/hazardous

© 2021 American Chemical Society https://doi.org/10.1021/acssensors.1c00473


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sensors.12,19−25 However, there is still room for a critical report


on the advantageous use of CNM and their composites applied
in sensors and biosensors and how they influence the final
devices’ performance, which is the aim of the review, as
illustrated in Scheme 1.

Scheme 1. Schematic Illustration of CNM and CNM-Based


Nanocomposites Applied in the Design of Optical,
Electrical, Electrochemical, and Piezoelectric Sensors and
Biosensors

Figure 1. (A) Supramolecular structure of cellulose in a superior


vegetal fiber and the organization of its main components. Adapted
with permission from ref 36. Copyright 2018 Springer Nature. (B)
Representation of a cellulose molecule with the 4 C1 chair
conformation, pointing out the cellobiose as the repeating unit and
the reducing and nonreducing end chains. (C) Representation of
Cellulose: A Brief Introduction. Paper, fabric, and wood cellulosic amorphous and crystalline phases in a microfibril. (D)
are currently the most common materials associated with Micrographies of (D1) MCC and the different types of CNM: (D2)
cellulose; they have been explored since ancient civilizations, CNF, (D3) wood CNC, (D4) tunicates CNC, and (D5) BC. Adapted
over 3500 years ago. Indeed, the first plastics were derived with permission from ref 37. Copyright 2011 The Royal Society of
from cellulose in the mid-19th century (cellulose nitrate), and Chemistry. (E) Cellulose crystallites arranged as a screw-like pack and
during the depression in the 1930s and World War II, the helical twist normal to the long axis of the rod. Adapted with
industrial supplies were limited, and so the use of natural permission from ref 38. Copyright 2019 Spring Nature. (F)
Iridescent/pearlescent visual aspect between crossed polarizers
materials such as cellulose was again disseminated.26 However, showing the birefringent domains. Adapted with permission from
nowadays cellulose is known as an easily functionalizable ref 39. Copyright 2019 John Wiley and Sons. (G) Fingerprint pattern
polymer with many other industrial applications, such as in the chiral nematic phase of a sulfuric acid hydrolyzed CNC
mechanical reinforcement of composites,27 a biomedical and aqueous suspension. Adapted with permission from ref 39. Copyright
pharmaceutical component (excipient, drug delivery, or wound 2019 John Wiley and Sons.
healing dressing material, among others),28 additive in the food
industry,29 packaging,30 conductive paper as a component for
energy devices,31 etc. This scenario has inspired cellulose fibrils). The protofibrils, in turn, pack into larger units called
extraction from other sources than conventional wood and microfibrils, whose cross-sectional dimensions usually range
cotton, including agricultural residues,32 bacteria (e.g., from 2 to 20 nm, depending on the cellulose source, while the
Acetobacter xylium), marine animals (e.g., tunicates), algae length is on the micrometer scale.17 It is important to
(e.g., Valonia), and even amoeba (Dictyostelium discoideum).33 emphasize that celluloses from different sources may pack
In plants, polysaccharides represent about 90% of the dry themselves in different ways, and such organizations are ruled
mass of the plant cell wall, composed mainly of cellulose (from by the biosynthesis conditions.34
40% to 90%) and fractions of hemicelluloses, pectins, and Another promising cellulose source is the bacterial cellulose
lignin, whose cellulose percentage vary accordingly to the (BC), which displays a chemical and supramolecular structure
source.32 The supramolecular structure of superior plants is similar to that of cellulose obtained from plants, being
illustrated in Figure 1A. The lowest level of hierarchical composed of ultrafine cellulose fibrils with a diameter in the
structure of a cellulosic fiber is the cellulose polymer chain, range of 80−150 nm.35 However, unlike plant-based cellulose,
preceded by the network of intra- and intermolecular BC is free of hemicellulose, pectin, and lignin, which provides a
interactions between them, assembling individual cellulose very pure material and well-organized nanofibrillar network
molecules into larger units, called elementary fibrils (proto- structure.33
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The isolation of cellulose was first reported by the French CNM can be synthesized by using bottom-up and top-down
Chemist Anselme Payen, in 1838, who named the fibrous approaches.17 Regarding the top-down approach, two typical
material cellulose and defined its molecular formula as classes of CNM can be obtained by deconstructing the
(C6H10O5)n,40 as shown in Figure 1B. The cellulose structure hierarchical structure of a cellulosic microfibril, which is
comprises linear homopolymer chains, whose physical− illustrated in Figure 1A: CNF through mechanical processes,
chemical properties are overwhelmingly given by the and CNC through chemical/enzymatic hydrolysis. Specifically,
cohesiveness arising from the large amounts of hydroxyl CNF are generated from top-down mechanical procedures
groups available and due to the strong intra- and applied to microfibrils (pretreated or not), in which high shear
intermolecular hydrogen bonds. Resulting properties include and impact forces are applied to vegetal fibers, leading to
low water solubility, elevated crystallinity index, and high mechanical cleavage along the longitudinal direction of the
thermal stability.41,42 The degree of polymerization (DP) of cellulose microfibrillar structure.59 As a result, part of
natural cellulose of various sources is in the range of 1000− noncellulosic compounds are eliminated, but considering that
30,000, which corresponds to chain lengths of 500−15,000 no corrosive reactant is added, the cellulosic amorphous phase
nm.35 The manner whereby the cellulose chains are arranged remains, yielding more flexible and longer nanostructures
can result in six interconvertible allomorphic forms, identified (length >1 μm, cross section ca. 5 nm), constituted by
as cellulose I to cellulose VI, albeit cellulose I presents a alternate association of highly ordered and amorphous
thermodynamically metastable structure and can be converted cellulosic domains.60 The morphological features of CNF
to other allomorphs.37 easily induce entanglement at extremely low concentrations,
Cellulose functionality can be increased by surface chemical which opens a wide window of applications for paper,
modifications, the strategy of which has been successfully membranes, hydrogel, and xerogel.61
implemented in several studies in order to adapt CNM to their Additionally, artificial cellulose nanofibers can be engineered
final use. In general, the surface modifications aim to decrease by applying versatile top-down spinning techniques (electro-,
the hydrophilic nature of CNM in order to better disperse in wet , dry, and solution blow spinning) with distinct
hydrophobic matrices.43 However, the strategy of chemical morphologies, dimensions, and functionalities.62−64 These
modification can also be explored in order to enhance some of methods consist basically of the ejection of a droplet of the
the cellulose properties aimed at sensor application.8,12,44 For polymer solution/melt due to driving forces (e.g., electrical, gas
instance, controlled reaction conditions can modify the pressurized, and centrifugal forces) followed by the rapid
cellulose chains located at the CNM surface by replacing the solidification by precipitation or solvent evaporation.65,66 The
spun fibers network is collected as a nanofibrous mat, rich in
exposed hydroxyl groups by other chemical groups relevant to
pores and channels, facilitating their configuration as a high-
the intended application, while preserving the internal CNM
surface-area membrane, nanopaper, aerogels, and thin films
structures. Cellulose active sites are the −OH of the C2 and
that can also be directly deposited onto the electrode surfaces
C3 positions, which correspond to secondary alcohols, and the
for sensor application.67,68 Due to the insolubility of cellulose
−OH of the C6 position as a primary alcohol. The relative
in water and in most organic solvents, caused by its
reactivity of these groups follows OH−C6 ≫ OH−C2 > OH−
supramolecular structure, researchers have also worked with
C3.41 Moreover, CNM can be surface tailored by physical cellulose derivatives. In general, a cellulosic polymer structure
adsorption of functional materials, resulting in hybrid can be solubilized by solvents not suitable to spinning
materials, such as CNM−silver nanoparticles and CNM− techniques, as LiCl in DMA (DMA/LiCl), tetrabutylammo-
graphene hybrid materials.45−47 nium fluoride trihydrate in DMSO (DMSO/TBAF), or
Fundamentals of Cellulose Nanomaterials. According cuprammonium hydroxide.40 Cellulose derivatives include
to the international organization for standardization (ISO/TS cellulose acetate, hydroxypropyl cellulose, hydroxypropyl
20477:201748), the term cellulose nanomaterials (or nano- methylcellulose, and ethyl-cyanoethyl cellulose, which can be
celluloses) comprises materials composed predominantly of dissolved in volatile solvents suitable for most of the spinning
cellulose with at least one dimension at the nanoscale, and techniques. Cellulose acetate, in particular, has been electro-
comprises three categories: bacterial cellulose (BC, also known spun under a wide variety of conditions and subsequently
as microbial cellulose or biocellulose),42,49,50 cellulose nano- deacetylated to form cellulose nanofibers or functionalized
fibrils (CNF, also called nano/microfibrillated cellulose),18,51,52 with other side groups.68,69
and cellulose nanocrystals (CNC, also previously referred to as Owing to the semicrystalline nature of a microfibril (as
nanocrystalline cellulose and cellulose whiskers).15,40,53 illustrated in Figure 1C), controlled acid or enzymatic
Morphological aspects of all these CNM, as well as those of hydrolysis conditions lead to amorphous domain removal
commercial microcrystalline cellulose (MCC) and CNC from and isolation of very thin single crystals called CNC.
sea animals (tunicates), can be observed in Figure 1D. CNM Hydrolysis kinetics is faster for noncrystalline regions than
are distinct from the commercial MCC, where the latter for crystalline domains, as it is the hydrolytic cleavage of
comprises a fine, white, and odorless crystalline powder glycosidic linkages promoted by the penetration of the
extensively applied in pharmaceutical, food, paper, and hydronium ions into noncrystalline regions.70 The conven-
composite manufacturing.35 Such products are typically tional use of sulfuric acid in hydrolysis promotes the
derived from the sulfuric acid treatment of bleached kraft esterification of the CNC surface hydroxyl groups, leading to
wood fibers or cotton, followed by washing and spray-drying, a high number of negatively charged sulfate groups on the
reagglomerating the smaller cellulosic crystalline domains surface of CNC, which limits the agglomeration and
through hydrogen bonding, which results in particles with flocculation of CNC in aqueous medium.50,71 Needle-like
minimum dimensions of 1 μm (see Figure 1D1).54 MCC has CNC structures are thereby obtained whose diameters vary
been used as the starting material of several pioneering studies from 5 to 20 nm and length from 100 nm to 1−2 μm.37,72
in NC isolation.55−58 CNC are traditionally applied as mechanical reinforcement to
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nanocomposite materials, but more recently, CNC have been Furthermore, the interest in fabricating low-cost, self-
explored in diverse applications, including sensors and standing, flexible, biodegradable, and high-surface-area sensing
optoelectronic devices.17,22,73−75 platforms has promoted the application of CNM as substrates
BC is considered a bottom-up approach employed to and biotemplates/scaffolds for hosting functional materials
produce CNM with the aid of microorganisms such as through varied approaches. CNM can also be employed as
Gluconacetobacter xylinus, Bacillus megaterium, grobacterium, flexible and transparent films and coatings in optical and
Alcaligenes, Pseudomonas, Rhizobium, or Sarcina, where the first electronic devices. Films exclusively constituted by CNM are
presents the highest capacity of cellulose production.42,76,77 A so-called nanopaper, which can show optical transparency if
cellulosic 3D network is collected as planar gel-like films the cellulose nanofibers are densely packed and the interstices
(fleeces/pellicles) with the same shape and dimensions of between the fibers are small enough to avoid light scattering.15
cultivation reservoir or can be brought into a complex 3D In addition, the chemical composition and structure of foams,
shape by the use of templates.17 Its gel nature effortlessly aerogels, and biofilms based on CNM can perform important
moves the BC toward hydrogel and xerogel configuration for roles in sensing and biosensing.92−94
several applications, mainly in the biomedical area. Especially An interesting growing trend is the use of paper and
due to its purity and ideal biocompatibility, BC shows an nanopaper as substrates for electrode fabrication, allowing the
unprecedented potential as a substrate for wearable substitution of traditional glass- or plastic-based material by
sensors.78−80 It is important to mention that BC can also be cheaper and disposable materials. In this direction, standard
applied as a starting material for CNC production.81 paper has received great attention for application in the printed
It is also important to emphasize that the final properties and sensors field seeking improvements offered by (i) easy load
features of BC, CNF, and CNC are highly affected by the and delivery of reagents in the 3D cellulose network; (ii)
cellulose source and experimental conditions. Thus, pretreat- capability to perform the analysis using small volumes of
ments are usually required to purify and homogenize the samples, largely reducing reagents and sample quantities; (iii)
starting material, removing noncellulosic materials, namely, pores and channels of cellulosic substrate developing an
lignin and hemicelluloses for plants, the bacteria and the important role for sample treatment, avoiding the interference
culture media for BC, and protein matrix for tunicates.82−84 of particulates present in the sample, which keeps them
The purification of the starting material is important to entrapped at the substrate surface enabling the analyte to flow
guarantee that the functional groups of cellulose are more toward the electrode surface; (iv) microfluidics without the
exposed for surface interaction with other materials. Besides, need of micropumps for flow generation, as well as
purified cellulose materials have more uniform properties, circumventing bubble formation (which is a common issue
higher Young’s modulus85,86 (important for wearable and in classical microfluidic systems).95 Once it was observed that
nonwearable flexible sensors), dimensional stability87,88 (for thin films produced with CNM presented properties different
piezoelectric sensors), and transparency89,90 (also required for from those of common paper, a new field of investigation was
some types of sensors and electronic devices).37,43,71 developed toward flexible optoelectronic devices. A milestone
Cellulose Nanomaterials in Sensors: Structure− study was reported by Revol et al.,96,97 who obtained
Properties−Application. CNM possess many interesting nanopaper by drying a CNC aqueous suspension through
properties for the development of chemical sensors, including simple evaporation.97,98 Afterward, CNF extracted from vegetal
molecular polarization, electrostatic interactions, and switch- and animal sources was employed in nanopaper fabrica-
able hydrogen bonds.20 Besides, CNM anisotropy attained by tion99−101 and also the BC, which was explored by Morales-
controlled self-assembly CNC suspensions can yield optical Narvaez and co-workers102 in configuring several nanopaper-
birefringence and bright iridescent materials for colorimetric based optical sensing platforms.
sensors and biosensors. Specifically, well-dispersed CNC For BC, the advantageous properties for sensing application
separate into a lower chiral nematic liquid crystalline phase are based on its similarity to the extracellular matrix of the skin,
(a state of matter with characteristics between a liquid and a including in fiber diameter and porosity, and a high degree of
solid) and an upper isotropic phase above a critical purity. This mimicking reflects preferential binding of
concentration of ca. 4.5 wt %.43 According to ref 37, the biomolecules with the BC substrate instead of the electrodic
crystallites arrange themselves in a helical twist down the long surface.78 Besides, proper chemical modification of BC can
axis normal to the rod, at an angle which intertwines the lead to immobilization of biomolecules by covalent linkage,
“threads” (Figure 1E). In this way, the CNC stacked planes which prevents the leaching during the sensing analysis,78
align along a perpendicular axis, with each plane rotating at a enhancing the sensitivity and reproducibility of biosensors. In
phase angle, depending on concentration. Thus, this alignment this direction, BC has been used for biosensing biomarkers
can result in optical band-gaps providing iridescent/pearlescent present in body fluids related to important diseases, as α-
visual aspect between crossed polarizers (displayed in Figure amylase,103 Parkinson’s disease biomarker,104 metal ions,105
1F), due to the birefringence of individual domains, typically and early cancer screening.106
producing fingerprint patterns as shown in Figure 1G. This In addition, there are a plethora of studies reporting the
CNC intrinsic feature has been explored in liquid-phase and immobilization of biomolecules on CNM.8,78,95,106,107 The
solid-phase sensors, in which the optically active arrangement high content of −OH groups available in CNM allows their
is retained in a polymer matrix or in a CNM film.91 The chiral functionalization, enabling adsorption of varied molecules.
nematic organization of CNC is always left-handed, and then However, oxidized or carboxylated CNM are preferred for the
the CNC films selectively reflect left-handed light, showing up immobilization of biomolecules in biosensors, in order to
colorful when the helical pitch (P) is on the order of promote amide linkage between amide groups of proteins and
magnitude of the visible-light wavelength, since P can be nucleic acids, and carboxyl groups grafted onto cellulose
controlled through physical condition changes, and thus, it is molecules.108 The immobilization by covalent bond is
relatively straightforward to modulate the color of the film.15 preferred, in contrast to physical adsorption, because the
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Table 1. Recent Papers Reporting the Application of CNM in Optical Sensor Devices
Analytes or properties under
investigation Role of CNM in the analyte detection Materials employed in the sensor [ref]
Environmental humidity/ Swelling process enlarging the helical pitch of the chiral nematic structure CNC/polyacrylamide composites132
water Chiral nematic CNC/glycerol133,134
CNC135
CNC/poly(ethylene) glycol136
CNM paper/waterborne polyurethane137
Mechanical stress Reduction in the helical pitch Chiral nematic CNC/elastomer composites138
Chiral nematic CNC plasticized with glycerol134
CNC-polyvinyl alcohol-glucose139
CNC chiral nematic liquid crystals140
Vapor sensing Increase of the distance between the film layers owing to the affinity between gas Colloidal CNC128
molecules and CNM Iridescent chiral nematic CNC/PVP
nanocomposites141
Oxidized CNC142
Cellulose/PMMA143
Cu(II)-doped CNC144
CNC functionalized with amine groups91
Biomolecules Analyte immobilization by electrostatic interaction Peptide-CNM145
BC and curcumin (paper-based)146
CNC and carbon quantum dots147
Temperature Relationship between surface structure and temperature CNC−4′-(hexyloxy)-4-biphenylcarbonitrile148
CNC-assisted carbon dots grafted SrAl2O4, Eu2+,
Dy3+ phosphors111
Metals Chelation of metal BC paper with curcumin149
AuNPs supported by CNC110
H2O2 Catalytic deposition of AgNPs CNC and AgNPs47
TNT SERS detection through the Meisenheimer complex formed by the interaction Au nanorods/Ag CNM150
between AuNT@AgNCs and TNT
Fungicide and pesticide Amplification of SERS signals caused by interaction between AgNPs and the AgNPs/CNC151
malachite green analyte

physical−chemical changes in environmental conditions can orientation and lead to a permanent polarization, giving rise to
disturb the system.109 Besides, CNM surfaces show low the piezoelectric effect, which is related to changes in
adhesion of nontarget interfering molecules present in polarization density and the manifestation of dipole mo-
physiological fluids.108 ments.22,124,125 The shear piezoelectricity in cellulose is
Electrical and electrochemical sensors have also taken comparable to that in quartz crystal125 and has enabled
advantage of CNM-based materials for designing sensors. many applications in sensors, as illustrated in the next sections.


For instance, the design of conductive CNM-based nano-
composites can be achieved by efficiently combining CNM to ROLE AND PERFORMANCE OF CELLULOSE
plasmonic NPs,75,110 photoluminescent NPs,102,111 inorganic NANOMATERIALS IN SENSORS
NPs,112 carbon-based nanomaterials,45,113 conductive nano-
materials,107,114 and biological compounds.58,115,116 The CNM Cellulose Nanomaterials in Optical Sensors. Optical
surface functionalization can be achieved through physical sensors can detect changes in the materials’ optical properties,
adsorption of conductive materials using solution/vapor like color, absorbance, fluorescence, reflectance, and refractive
deposition, sputter coating, layer-by-layer and other methods, index to monitor different analytes.20,126−131 This section will
as well as by in situ polymerization. Additionally, CNM have survey recent representative studies of CNM applied to optical
also been employed in the synthesis of graphene and metal sensors using techniques such as colorimetry, fluorescence,
nanoparticles by taking advantages of the CNM functional absorbance, and surface-enhanced Raman scattering (SERS),
groups and high specific surface area. Such a combination of as summarized in Table 1. It is possible to note that the chiral
properties allows the production of well-dispersed metallic nematic properties of CNC have been widely employed in
nanoparticles without using conventional toxic and expensive optical sensors, and several types of materials can decorate
reactants (e.g., hydrazine and borohydride).45,46,117,118 CNM for modulating the sensor response for a given
Piezoelectricity is another interesting property arising from application.
the CNM structure suitable for the design of piezoelectric As previously mentioned, under certain conditions, CNM
sensors. In piezoelectric materials, an electric charge is can form a liquid crystal phase, which is promising for the
generated as result of the application of mechanical stress preparation of photonic nanomaterials, mainly because they
(direct effect) or, conversely, a mechanical strain the material combine biocompatibility with self-assembly behavior, produc-
experiences under an the application of an electric field.119,120 ing chiral nematic superstructures with interesting optical
The piezoelectricity in wood, the discovery of which dates back properties.152 The structure of CNM chiral nematic liquid
to 1955,121,122 arises from the oriented asymmetric arrange- crystals observed in suspensions can be preserved in solid films,
ment of cellulose crystals.123 The hydrogen bonds in the providing stable platforms with a helical structure and bright
cellulose structure contribute to the formation of a dipolar iridescent color. Because of the hydrophilicity, when these
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Figure 2. (A) CNC-based color sensor with the incorporation of 1-butyl-3-methylimidazolium. Different film thicknesses, due to the change in the
traction speed during assembly, resulted in different colors. Reprinted (adapted) with permission from ref 91. Copyright (2018) American
Chemical Society. (B) Schematic mechanism for the reversible humidity-responsive structural color change of CNC-based films. Reprinted
(adapted) with permission from ref 134. Copyright (2018) American Chemical Society. (C) Illustration of CNC/polyacrylamide synthesis and the
change in the iridescent composite films due to humidity increase. Reprinted (adapted) with permission from ref 132. Copyright (2017) American
Chemical Society. (D) Photographs of AgNP/CNC solutions exposed to various concentrations of H2O2, where the catalytic decomposition of
AgNP in the presence of H2O2 caused a decrease in the AgNP absorption band at 410 nm. Reprinted (adapted) with permission from ref 47.
Copyrigth (2019) Elsevier.

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films are exposed to environments with high relative humidity, low cost, and the possibility of forming hybrid compounds
they swell due to the water absorption, causing changes in the with different classes of molecules or ions.
CNM pitch. Specifically, when the films swell, the chiral The color modification process of CNC-based films can be
nematic step increases linearly with an increase of the better understood by observing Figure 2B134 and C.132 CNM
interspaces between the CNM pseudoplanes, causing color can exhibit the properties of chiral nematic liquid crystals and
changes. The color change is smaller at low humidity values, therefore can reveal distinct colors without the use of
since CNM have a limited capacity to capture moisture.20 chromophores. Such materials can behave like a self-
Thanks to this characteristic, the CNM chiral nematic films organizing, one-dimensional chiral photonic crystal, whose
have been widely used in humidity sensors.135,136,153,154 In this axis rotates in the plane around a perpendicular helix, as
direction, Bumbudsanpharoke et al. recently reported two demonstrated in Figure 1E. As a result, a periodic variation in
studies involving humidity detection using colorimetric sensors the refractive index leads the material to behave like a circularly
based on CNM chiral nematic liquid crystals.135,154 In the first polarized incident light filter. When the functionalized film
study,135 the sensor was developed by adding NaCl to the absorbs vapors, it swells, and the chiral nematic structure step
CNM suspension, yielding a pink-colored film. As the material is expanded. Then, the expanded film will reflect light with
absorbs moisture, the pink color is shifted 160 nm toward greater bandwidth than single-pitch films without expansion,
longer wavelengths, visually changing the film color to bluish. changing the material reflectance and color. Additionally, the
The developed optical sensor could monitor humidity in a variation in the material pitch can occur reversibly or
precise and reversible way, with potential application in smart irreversibly, depending on the type of analyte.153
packaging of products that suffer deterioration when exposed Due to its selectivity and sensitivity, SERS is considered a
to humidity. The same principle of detection using chiral powerful technique for biomolecule detection. In this case,
nematic liquid crystals can be used for sensing volatile organic CNM can be used as flexible platform with multilayer and 3D
compounds (VOC). The fixing of VOCs in the film induces nanonetworks for the immobilization of metallic nanoparticles,
swelling of the cellulose-based platform, altering the cholesteric minimizing agglomeration and aggregation effects. Thus, the
pitch, similarly to what happens with the absorption of role of CNM can be used not only as a sensing layer but also as
humidity.155 In the work by Shidong et al.,144 a gaseous a flexible, stabilizing support that allows the uniform
ammonia sensor based on CNC chiral nematic films doped distribution of nanoparticles on its surface.150,151,156,157 For
with copper(II) was developed. The presence of positively instance, in the study reported by Nabeela et al.,158 the authors
charged copper ions chelated negatively charged CNC and investigated the role of CNF in increasing the SERS signal in
the detection of organophosphate pesticide methyl parathion.
red-shifted the film absorbance by more than 50 nm. The
Plasmonic silver nanoconstructs obtained using CNF were able
developed platform was sensitive to ammonia gas, since the gas
to produce sensors with sensitivity higher than that obtained
molecules were allocated in the nematic layers of CNC,
with neat silver nanoparticles. This behavior was ascribed to
binding to chelated copper ions, yielding to a redshift in the
the presence of the CNF, which enabled a high density of
reflective wavelength as well as a visible colorimetric transition.
hotspots provided by the local enrichment of analytes driven
The authors also developed a kinetic model that quantitatively by the nanocellulose-silver after drying. Other interesting
related the effects of ammonia gas kinetic detection to the works using cellulose-based platforms for SERS devices can be
change in the reflective wavelength. found in the literature.159−161 For instance, Wu et al.150
The modifier and processing steps employed in the reported the use of nanocellulose in the detection of TNT.
fabrication of films can promote characteristic color changes The sensor platform was composed of a three-dimensional
suitable to be employed in the detection of specific analytes for (3D) dispositive containing AuNR@AgNCs on bacterial
varied application. For instance, in the work of Song et al.,91 cellulose aerogels, which could detect 2,4,6-trinitrotoluene
CNC were used to form a solid substrate displaying different (TNT) through SERS analyses. The detection limit for TNT
color patterns without adding chemical pigments, which was obtained in this work was 8 × 10−12 g/L, and the improvement
achieved by selecting film thickness. This parameter was factor of the SERS signal was high, up to 1.87 × 108.
controlled by adjustments in the film assembly process and the Although CNM-based sensors can present advantageous
addition of 1-butyl-3-methylimidazolium, as shown in Figure properties, in some cases the detection is achieved with low
2A. These films were functionalized with amine groups to selectivity, which can be tackled using dopants in the
obtain a low-cost and biocompatible colorimetric sensor matrix.20,148 Ruiz-Palomero et al.162 reported a fluorimetric
capable of changing color in the presence of formaldehyde sensor based on sulfur, quantum dots of graphene encoded
or propanal gases without interference from other molecules. with nitrogen immersed in nanocellulosic hydrogels, which was
The detection limit achieved was less than 0.5 ppm, and for applied in the detection of the laccase enzyme. The presence of
observations with the naked eye, this value increased to 7.3 the nanocellulose hydrogel promoted the increase of the
ppm. Similarly, other works have employed CNM as a fluorescence signal of graphene quantum dots through the self-
protagonist in the fabrication of colorimetric films by different quenching process. In addition, it stabilized the fluorescence
techniques using other molecules to functionalize substrates signal, which caused a rise in the sensitivity to laccase. Another
for varied analytes, such as copper doped CNM for ammonia interesting property of CNM is its capability to stabilize
gas sensing,144 organic solvent detection using a nano- metallic nanoparticles in the solution,110,163,164 enabling the
composite containing CNC and polyvinylpyrrolidone,141 composite material to be used in the design of sensing
introduction of small plasticizer molecules onto CNC to platforms for monitoring varied analytes. For instance,
improve the humidity sensing,134 and humidity sensing using a Teodoro et al. developed a colorimetric sensor based on
nanocomposite based on CNC and polyacrylamide,132 among CNC/AgNP hybrid material displaying high sensitivity
others.133,136,142,145 The significant advantages of these (detection limits of 0.014 μM) and selectivity toward H2O2
colorimetric sensing platforms include their biocompatibility, detection in water and milk matrices. The mechanism of
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Table 2. Examples of CNM-Based Electrical and Electrochemical (Bio)Sensors for the Detection of Varied Analytes
detection
materials analyte method LOD/linear range ref
Screen-printed carbon electrodes on microbial CNM Cd2+ DPV 1.01 μM 80
Pb2+ 0.43 μM
uric acid 1.8 μM
17β-estradiol 0.58 μM
PA6/CNC:rGO hybrid platform Hg2+ DPV 0.52/2.5−200 μM 45
Nanocomposites based on electrospun nanofibers modified with CNC:AgNPs, isoborneol electrical 25 ng L−1a/25−100 ng 189
CNC:AuNPs, and CNC:rGO L−1
Cellulose-Modified Pencil Graphite Electrode herbicide atrazine SWV 0.008/5−320 ng mL−1 190
methyl cellulose (MC) buffer layers and pentacene NO2 electrical 1 ppm 191
TEMPO-nanocrystalline cellulose/PNAa/rGO Mycobacterium DPV 3.14 × 10−14/1 × 10−8− 192
tuberculosis 10−13 M
Silylated Graphene oxide−grafted-chemically modified nanocellulose cholesterol DPV 7.4 μM/5.18−25.9 μM 193
Nanocrystalline cellulose-CTABb/Tyrc/CdS quantum dots phenol DPV 0.082 μM/5.0−40.0 μM 194
cathecol 0.125 μM/1.0−25.0 μM
o-cresol 0.007 μM/2.0−10.0 μM
4-chlorophenol 0.021 μM/5.0−25.0 μM
TEMPO oxidized-cellulose nanocrystals/GOxd glucose amperometry 0.004 mM/0.1−2 mM 195
Nanocellulose/Graphene oxide-Pt-nanocauliflower/GOxe glucose amperometry 0.08 μM/0−500 μM 196
Nanocellulose/Graphene oxide- Pt-nanocauliflower/RNA aptamer for E. coli E. coli O157:H7 4 CFUf mL−1/ 4−105
detection CFU/mL
Bacterial cellulose-Au nanoparticles/laccase hydroquinone DPV 5.71 nM/30−100 nM 197
Cellulose nanocrystal/polypyrrole/GOx glucose DPV 50 μM/1.0−20.0 mM 107
Fibers (TCNFg/CNTh) NO2 electrical 0.5% to 0.125 ppm 198
a
PNA: peptide nuclide acid. bCTAB: cetyl trimethyl ammonium bromide. cTyr: tyrosinase. dGOx: glucose oxidase. ePt: platinum. fCFU: colony-
forming unit. gTCNF: nanocellulose extracted from tunicate. hCNT: carbon nanotube.

detection was based on the catalytic decomposition of silver some ions, such as Hg+2167 and Cu2+,168,169 leading to changes
nanoparticles (AgNP) in the presence of H2O2, causing a in color observable by the naked eye, which makes these
decrease in the AgNP absorption band at 410 nm as the H2O2 materials widely used in colorimetric sensors for metal ions. In
concentration was increased. The solution color changes were such cases, CNM can act as a scaffold for rhodamine
observable by the naked eye, according to Figure 2D, without immobilization, usually by grafting rhodamine derivates and
the interference of some common interferents, such as Cu2+, cellulose. Besides, the use of CNM with rhodamine is
Zn2+, Au+, glucose, and Fe2+, proving the sensor was selective. interesting due to the biocompatibility of these materials,
The sensor performance was associated with the dispersion since rhodamine is extensively applied in the bioimaging and
and stabilization of AgNP onto CNC surface, given by the detection of analytes in a biological system.167
interactions during the synthesis of silver ions and negatively Since CNM can be modified with fluorescent dyes, the final
charged groups (hydroxyl and sulfate) present on the CNC conjugated system can be applied in the monitoring of some
surface. Other metallic materials can also be used to decorate analytes capable of interacting with the modified CNM. In this
CNM to obtain colorimetric sensors, such as copper for direction, Xiong et al.170 reported the use of fluorescent carbon
ammonia detection,144 AgNP for the monitoring of water quantum dots (CQDs) for decorating the surface of CNM
pollution,156 and AuNP for monitoring cadmium.110 Collins et chiral structures. The chiral organization of the needle-like
al.165 described CNM surface modification using the cobalt- CNC allowed the self-organization of the CQDs, avoiding
(II)-bis-terpyridine complex to prepare colorimetric cyanide particle aggregation. As a consequence, it was possible to
sensors. The attached cobalt-based complex exhibited red- obtain highly organized and homogeneous films whose
orange color in aqueous solution, and the color disappeared in flexibility and characteristic fluorescent fingerprint signature
the presence of cyanide ions. were suitable for designing luminescence-based optical sensors.
A combination of metals can be an interesting alternative to Other interesting works developed using CQD for the
decorate CNM and expand their application in colorimetric preparation of fluorescent platforms based on CNM can be
sensors. Such an alternative was reported by Nwosu et al.,166 found elsewhere.111,147,171
who developed a hybrid material composed of CNM-Ag-Cu CNM can also be used in optical sensors as the substrate for
for the colorimetric detection of urea in solution. The authors fixing the sensor active layer. As a substrate, cellulose
obtained a detection limit around 0.8 ppm and selectivity nanopaper comprises an internal network structure formed
toward other analytes commonly found in human urine. by several layers of cellulose fibers. For being highly flexible,
Besides, the reproducibility, evaluated by three consecutive light, cheap, and biodegradable, paper is advantageous
measurements, resulted in a relative standard deviation (RSD) compared to other substrates, such as glass and plas-
of 2.61%. tic.139,172,173 In the work by Faham et al.,149 an analytical
Dyes such as rhodamines have also been widely used in device based on cellulose nanopaper was produced through the
synergy with CNM to prepare opto-chemical sensors, due to incorporation of curcumin by laser printing technology. The
their remarkable absorbance and fluorescence properties. For biocompatible and biodegradable platform was used for
instance, rhodamine can form a complex in the presence of monitoring Fe(III) and deferoxamine (DFO) as an iron-
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Figure 3. (A) Transmission electron microscope (TEM) images of CNF (I), GN (II), and GN-CNF nanocomplexes (III); (IV) macroscopic
pictures of pure GN and GN-CNF dispersions after a 12 h rest. Reprinted with permission from ref 203. Copyright 2019 MDPI. (B) (I) DPV
curves for different concentrations of Hg(II) using PA6/CNC:rGO hybrid platform, in 0.1 mol L−1 acetate buffer, and (II) the linear relationship
between the peak current versus Hg(II) concentrations. Reprinted with permission from ref 189. Copyright 2019 Elsevier. (C) PCA plots for the
electrical capacitance responses (experimental data collected with the electronic tongue) at 1 kHz for the analysis of different Isoborneol solutions
and distilled water (DW). Reprinted with permission from ref 189. Copyright 2019 MDPI. (D) Transfer characteristics of the pentacene OFET-
based sensors (I) without and (II) with MC toward 20 ppm of NH3 gas flow. Reprinted with permission from ref 191. Copyright 2019 Royal
Society of Chemistry.

chelator in biological fluids such as blood, saliva, and urine. In and various metallic ions. The detection limit toward iron was
the presence of Fe(III), the color intensity of the CNM-based around 7.8 nM, and DFO was around 8.2 nM.
paper with curcumin decreased due to the formation of a Cellulose Nanomaterials in Electrical and Electro-
complex between iron and curcumin. This sensor showed high chemical Sensors. Electrical and electrochemical sensors
selectivity compared to the response of other interferents have been successfully employed for the efficient detection of
present in the human blood (limit of detection around 7.5 nM varied analytes. What differentiates one from another is the
for Fe(III) and 8.0 nM for DFO), such as creatinine, uric acid, way the detection is carried out. Generally, electrical sensors
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detect variations in electrical properties, such as an increase/ kPa), rapid self-healing ability (20 s), and high healing
decrease in electrical current or even a change in electrical efficiency (97.7 ± 1.2%). Due to the effective electric pathways
voltage,174 whereas the electrochemical sensor converts the provided by GN-CNF nanocomplexes, the strain sensors
effect of the analyte−electrode interaction, which is due to a integrated by GN-CNF@PVA hydrogel with good responsive-
process of oxidation or reduction, in an electrical signal.175,176 ness, stability, and repeatability could identify various human
Both techniques have many advantages, such as, for example, motions with the gauge factor (GF), showing promising
high sensitivity and selectivity, simplicity, moderate cost, and applications in the field of wearable sensing devices. These
portability.177,178 results are presented in Figure 3A, where it is possible to
A key feature for both techniques is the choice of material to observe transmission electron microscope (TEM) images of
be deposited onto the electrode surface, since this material will CNF (i), GN (ii), and GN-CNF nanocomplexes (iii), and (iv)
be directly related to the surface area of the electrode, as well macroscopic pictures of pure GN and GN-CNF dispersions
as to the sensitivity, specificity, and detection limits of the after a 12 h rest.
proposed sensor.179 Thus, a suitable strategy to improve the A novel electrochemical sensor for detecting Hg2+ using a
sensor performance in terms of sensitivity, specificity, and green hybrid nanoarchitecture composed of reduced graphene
detection limit is the use of nanomaterials to modify the oxide (rGO), CNC, and polyamide 6 (PA6) electrospun
electrode surface, including the ones obtained from renewable nanofibers was developed by Teodoro et al.45 In this work, the
sources, such as CNM.180−182 The great interest in applying CNC were used as an alternative reducing agent for graphene
CNM in electrical and electrochemical sensors is due to its oxide (GO). The surface molecules of cellulose led to a partial
advantageous features, which include thermal stability,183,184 reduction of oxygen organic functions of graphene oxide,
high aspect ratio,37 good mechanical and optical properties, resulting in well-dispersed rGO onto the CNC surface. The
and large surface area.185 Besides, cellulose is an excellent CNC:rGO hybrid material was applied in the functionalization
bonding agent, as it has readily available surface functional of insulating electrospun nanofibers deposited onto the
groups, which can provide selectivity and sensitivity compared working electrode. The results revealed that the sensor was
to other molecules with no functional groups available, with capable of detecting Hg2+ with a low limit of detection (LOD)
impact on the long-time stability of the modified elec- of 0.52 μM in a concentration range of 2.5−200 μM. Figure
trode.186−188 Table 2 summarizes some interesting electro- 3B(i) shows the DPV curves for different concentrations of
chemical and electrical (bio)sensors based on CNM and its Hg2+ using the PA6/CNC:rGO hybrid platform, in 0.1 mol
characteristics. L−1 acetate buffer, and (ii) shows the linear relationship
Silva et al.80 reported the application of BC nanosheets as a between the peak current versus Hg2+ concentrations. The
proof-of-concept skin-like platform for noninvasive monitoring proposed sensor also proved to be selective in the presence of
of body fluids in sweat using screen-printed carbon electrodes common interfering metals (Cd2+, Pb2+, and Cu2+) and was
(SPCEs). BC is an excellent skin-substitute natural polymer able to detect Hg2+ in real samples, including in river and tap
routinely used for wound dressing and offers unprecedented water. Regarding electrical sensors using cellulose material,
potential as a substrate for wearable sensors. The sensing Migliorini et al.,189,204 in two different studies, evaluated the
platform obtained with BC can help in solving the adhesion performance of nanocomposites based on electrospun nano-
problem, thus allowing skin integration in wearable devices. fibers modified by CNC hybrid materials with AgNP, AuNP,
The electrodes were used to detect the toxic metals cadmium and rGO to be used as sensing layers of an electronic tongue
(Cd2+) and lead (Pb2+) with limits of detection of 1.01 and (e-tongue) to detect water contaminants. In these two works,
0.43 μM, respectively, which are sufficient to detect these the use of CNC in the synthesis of CNW:Ag and CNC:Au
metal ions in human sweat and urine. SPCEs functionalized hybrid materials allowed obtaining small and well-dispersed
through anodic pretreatments were used for detecting uric acid metal nanoparticles onto the electrospun nanofibers surface,
and 17β-estradiol in artificial sweat, with detection limits of 1.8 which would not be achievable without using CNC. In another
μM and 0.58 μM, respectively. The electrochemical treatment approach, Ivanova et al.112 developed a resistive gas sensor
created oxygen groups on the carbon surfaces, thus improving based on CNC templated tin dioxide. The authors
wettability and hydrophilicity. The authors achieved a demonstrated that the structural features of CNC-templated
detection limit similar to other works reported in the tin dioxide films strongly depend on the precursor
literature 199−202 but using BC as a highly adherent composition. The precursor properties were studied by using
biocompatible skin-like platform, which can transport species low-temperature NMR spectroscopy of tin tetrachloride in
such as toxic metals from sweat to the printed carbon ink solution. In addition, they also demonstrated that it was
through a capillary effect. possible to optimize the precursor conditions to obtain
Another interesting approach was proposed by Zheng et homogeneous precursor mixtures and therefore highly porous
al.,203 who developed a new class of strain sensors using CNF thin films with pore dimensions in the range of 10−20 nm.
and graphene (GN) coincorporated poly(vinyl alcohol)-borax The sensor showed high sensitivity to carbon monoxide (CO)
(GN-CNF@PVA) hydrogel. The borax could reversibly and in ppm concentrations and low cross-sensitivity to humidity.
dynamically associate with poly(vinyl alcohol) (PVA) and GN- Besides, both the response to the analyzed gas and the signal
CNF nanocomplexes, acting as a cross-linking agent, providing decay after gas exposure occurred within a few seconds, which
a tough and flexible network with the hydrogels. In this case, is faster than in standard SnO2-based CO sensors, which was
the CNF acted as a biotemplate and dispersant to support GN attributed to the high gas accessibility of the very thin porous
to create homogeneous GN-CNF aqueous dispersion, endow- film.
ing the GN-CNF@PVA gels with mechanical flexibility, In the work reported by Migliorini et al.,189 nanocomposites
strength, and conductivity. The resulting composite gels based on electrospun nanofibers modified with the hybrid
presented remarkable stretchability (breakup elongation up materials CNC:AgNP, CNC:AuNP, and CNC:rGO were
to 1000%), excellent viscoelasticity (storage modulus up to 3.7 employed in the design of an e-tongue sensor array, in order
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Figure 4. (A) Design strategy used in the fabrication of CNM-AU-Ab2-ALP (I), the sandwich-type immunosensor (II) and the calibration curve for
ALV-J detection (III). Adapted with permission from ref 218. Copyright 2018 Elsevier. (B) Schematic view of the TEMPO−CNC oxidation and
enzyme immobilization process. Adapted with permission from ref 195. Copyright 2018 Elsevier. (C) Digital images of the test-strips in the
presence of different glucose concentrations using ABTS as colorimetric indicator, prepared with different concentrations of GOx covalently bound
(I) and the analytical calibration curves (II) plotting the color coordinates collected against the glucose concentration (right − the assay
corresponds to 1 mg mL−1 GOx). Adapted with permission from ref 58. Copyright 2020 Elsevier. (D) Translucency (I) and magnetic property (II)
of the self-supporting S-CNC-5% Fe3O4 film, and the dependence of (N-CNC)-5% Fe3O4 and (S-CNC)-5% Fe3O4 catalytic activity on glucose
concentration (III). Adapted with permission from ref 224. Copyright 2020 Elsevier. (E) SEM image of BC nanofibers (I), TEM image of BC-
AuNP hybrid nanofiber (II), and calibration curve of current vs concentration for hydroquinone detection (III). Adapted with permission from ref
197. Copyright 2016 Elsevier.

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to detect isoborneol, a compound associated with the advantageous for some cases regarding in vivo applications,
eutrophication process. Additionally, electrical capacitance some concerns are raised when CNM is acting as a support
data measured with the impedimetric e-tongue were treated material for other nonbiodegradable materials, which can be
by Principal Component Analysis (PCA) and revealed that the delivered after its CNM degradation.
sensing system was able to discriminate water samples Regarding biosensors development, CNM have been applied
contaminated with isoborneol at nanomolar concentrations as reinforcement agents of biocomposites,194,196,217,218 as
(Figure 3C), even when real water samples were employed. In biocompatible interface former,80,219,220 as a substrate for
a sequential work, the same authors204 evaluated two distinct biomolecule immobilization58,195,221−223 and in the design of
e-tongues to detect geosmin (GSM) and 2-methylisoborneol self-supporting devices.22,95,224 Regarding applications, consid-
(MIB) in pure and river water. The difference between the e- ering that CNM are natural and nontoxic nanomaterials, they
tongues consisted in the type of polymer processing (electro- can be applied in sensors aimed at food quality control95,210
spinning or drop-casting) used in the fabrication of the sensing and health monitoring,106,225 especially in the development of
units. Specifically, the thin films deposited onto gold point-of-care and wearable devices.80,196,219,224,226 At first,
interdigitated electrodes were based on polyamide 6, CNM-based devices were intended to replace the glass or
polypyrrole, and polyaniline, but fabricated by drop-casting plastic-based devices, but their use offers interesting additional
and electrospinning. The drop-casting and electrospinning advantages, as in the development of (nano)paper-based
were further functionalized with well-dispersed CNC:Ag and support for (bio)sensors, leading to cost-effective, reliable,
CNC:Au hybrids. The differences in the electronic tongue sustainable, and reagent-free devices applied in food quality
performances were correlated to the distinct morphologies of and safety monitoring.95 In addition, its low cost allows the
the sensitive layers. Both devices were able to discriminate production of disposable devices, overcoming fouling issues
pure water from solutions tainted with GSM and MIB in found in food quality application. Regarding the environmental
concentration as low as 25 ng L−1. In addition, the system impact, the use of CNM-based devices brings sustainability and
showed intra- and interelectrode reproducibility and the also allows recycling. The development of devices based on
performance similar to that reported by Braga et al.,205 but CNM also represents a great advantage in the microfluidic
in that case204 using a green synthesis based on CNC. field, where the paper porosity and capillarity effects can be
In another approach, Annu et al.190 developed a cellulose- used for the production of miniaturized devices that require
modified pencil graphite electrode to quantify the herbicide small analyte volumes without the need of micropumps,
atrazine (ATZ). As pointed out by the authors, CNM find avoiding bubble formation.95,106 Besides, the biocompatibility
several applications in electrochemistry owing to the large and nontoxicity of CNM-based biosensors and the possibility
number of hydroxyl groups on its structure, combined to of functionalization allows the successful immobilization of
chemical purity and, in the specific case of this work, easy several biological compounds.106,225
distribution/dispersion and good adsorption on electrode CNM can be associated with inorganic nanoparticles,194,227
surface and reinforcing phase capabilities. The fabricated metal ions and oxides,192,218 carbon-based materials (nano-
sensor could detect ATZ with a low detection limit of 0.008 ng tubes, graphene, graphene oxide, etc.),228−230 conducting
mL−1 without interference of common metabolites. By polymers,231,232 and ionic liquids,233 to improve conductive
comparing the results achieved by his team190 with other and electrochemical properties217 of the nanocomposite. For
studies reported in the literature,206−208 one notes the example, Liu et al.218 developed an electrochemical immuno-
proposed sensor presented equal or superior sensitivity with sensor using a composite formed by CNM and AuNP, named
the advantage of being a cost-effective sensor and easy to CNM/AuNP, for the detection of avian leukosis virus
fabricate, demonstrating that it could be a potential green subgroup J (ALV J). The designed immunosensor was
substitute for conventional pencil graphite electrodes. produced following a sandwich-type scheme, where ALV J,
Cellulose Nanomaterials in Biosensors. A biosensor is a the target molecule, was recognized between two nano-
type of chemical sensor that uses a biological molecule as a composites with immobilized primary and secondary antibod-
recognition element. When nanomaterials are employed in ies, namely, Ab1 and Ab2, respectively (a secondary antibody
biosensors, interesting catalytic properties for detecting varied is an antibody that recognizes a primary antibody). Figure
analytes are observed.209 Besides, nanomaterials can be tailored 4A(I) and (II) show a scheme of the designed immunosensor,
allowing improvements in the immobilization and stabilization where Ab1 is the capture antibody and Ab2 is the detection
step of biological components (enzyme, antibody, aptamers, antibody. The first nanocomposite was formed by a Graphene/
nucleic acids, etc.), which are key elements for efficient perylene-3,4,9,10-tetracarboxylic acid (GR/PTCA) and the
recognition of the target analyte. second one by CNM/AuNP. CNM were used as matrix for
Biosensors using nanostructured hybrid materials can be AuNPs immobilization in order to enhance the electrochemical
employed for different applications such as environmental immunosensors performance, in addition to functioning as a
monitoring,210,211 food industry,212,213 and health care.214,215 carrier to immobilize the antibody Ab2 and alkaline
The latter application, which includes wearable sensors for phosphatase molecules (ALP), which acts as a catalyst. The
disease diagnosis and in vivo health monitoring, raises formation of CNM-Au composites allowed the amplification of
concerns about the possible cytotoxicity of nanomaterials. To the detected signal and favored the catalytic properties of Au
overcome this problem, biocompatible nanomaterials, as and ALP. The calibration curve for the developed immuno-
CNM, are a suitable option to be applied in biosensors for sensor is shown in Figure 4A(III). The sensor showed a LOD
in vivo detection of varied analytes.8,216 CNC, CNF, and BC (calculated by S/N = 3) of 101.98 TCID50 mL−1 (TCID50 =
have been widely applied in biosensing development8 due to 50% tissue culture infective dose), adequate selectivity
their remarkable properties mentioned in the previous sections (according to interference tests using relevant species as
combined with nontoxicity and biocompatibility, which are key vitamin C, glucose, BSA, NaCl, etc.) and reproducibility (RSD
for wearable biosensors. Although CNM’s biodegradability is = 2.01%). Besides, the developed sensor showed long-term
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stability, keeping 93.57% of the peak current detection signal (HRP), and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic
after 15-day storage. acid) diammonium salt (ABTS). The colorimetric sensing
Manan et al.194 reported the fabrication of an electro- mechanism was based on the HRP and ABTS action on
chemical biosensor using CNC decorated with cadmium hydrogen peroxide (H2O2), produced from the reaction
sulfide quantum dots (CdS QDs) for immobilizing Tyrosinase between GOx and glucose, generating a blue product. Figure
(Tyr), aiming at phenol detection. The surface modification of 4C(I) shows the digital images of the developed biosensor test-
CNC was performed using the cationic surfactant cetyltriam- strips in the presence of different concentrations of glucose and
monium bromide (CTAB) in order to overcome its high GOx, while Figure 4C(II) shows the analytical calibration
hydrophilicity and render a moderate hydrophobicity to the curves plotting the color coordinates against the glucose
biosensor matrix. After functionalization, the modified CNC concentration (1 mg mL−1 of GOx). The authors observed
were successfully used for CdS QDs (capped with 3- that modified CNM promoted better color distribution and
mercaptopropionic acid − MPA-QDs) attachment and Tyr increased sensitivity (3.5 times higher) for glucose detection,
immobilization. The CdS QDs provided conductivity and in which a narrower linear response range from 1.5 to 13.0 mM
facilitated the electron transfer to the system, while Tyr was obtained.
catalyzed phenol reduction to ο-quinone. The Tyr/CTAB- Recently, noninvasive wearable biosensors have gained
CNM/QDs biosensor exhibited a good linear response (R2 = considerable interest owing to their plethora of applica-
0.9904) in the concentration range of 5−40 μM showing an tions.177,238−240 Improvements in the performance of wearable
LOD of 0.082 μM toward phenol detection. Besides, the devices have been achieved by using both cellulose-based
developed biosensor showed selectivity for phenol determi- membranes (to avoid the interference from other biofluid
nation in the presence of common interferents (10 times compounds in on-body applications of glucose detection219),
concentration of glucose, ascorbic acid, uric acid, caffeine, and as well as CNM. In this direction, Burrs and collaborators
100 times concentration of heavy metal ions), presenting less developed a conductive nanopaper based on a graphene−
than 5% of interference and accuracy comparable with results platinum (Pt) nanocauliflower hybrid composite for use in
obtained by HPLC. An efficient immobilization capable of point-of-care biosensing for glucose or Escherichia coli (E. coli)
ensuring the exposition of the active sites for the necessary detection.196 First, the device was fabricated through nano-
binding is one of the main challenges in biosensing cellulose modification with graphene oxide, which was reduced
applications.234 In the case of CNM, the surface modification by subsequent thermal and chemical (using ascorbic acid)
is an efficient strategy used for designing the adequate binding treatment, constituting an interesting conductive substrate for
of biological molecules on its surface for biosensors develop- electrochemical measurements. After that, the surface of the
ment. For instance, the use of the oxidant agent 2,2,6,6- substrate was modified through the synthesis and application
tetramethylpiperine-1-oxyl (TEMPO) as a mediator in the of fractal nanoplatinum with cauliflower-like morphology using
oxidation process is a widely used and promising proce- pulsed sonoelectrodeposition, and a high electroactive surface
dure.58,192,195 It enables oxidation of primary hydroxyl groups area was achieved. The platinum surface was further modified
from cellulose in aldehydes, which are further converted (using with the enzyme GOx (via chitosan encapsulation) or an RNA
other reagents) into charged carboxyl groups.235,236 The aptamer (via covalent linking) for the development of an
process is advantageous for being one-step and specific for enzymatic biosensor or aptasensor in the detection of glucose
primary alcohol groups of polysaccharides, keeping secondary or E. coli, respectively. The results showed that the hybrid
ones unaffected.237 In this direction, a biocompatible and inert nanocellulose−graphene−nanoplatinum material is an excel-
nanomaterial based on TEMPO oxidized-CNC, used for lent paper-based platform for electrochemical biosensors
immobilizing and stabilize glucose oxidase (GOx), was targeting small molecules.
designed by Tang et al.195 The TEMPO-mediated oxidation A different strategy was employed by Tracey et al.,224 who
process enabled the hydroxyl groups of CNC to be oxidized reported the development of a noninvasive glucose biosensor
into carboxyl groups, for which the surface chemical based on CNC/magnetite for in vivo or dermal use. In that
functionalization allowed the covalent bonding of the GOx work, the properties of CNC to form self-supporting and
through the reaction with the NHS/EDC (N-hydroxysucci- biocompatible films were employed for the biosensing of
mide/N-(3-(dimethylamino)propyl)-N′-ethylcarbodiimide) glucose from sweat and saliva. For the film formation,
reagents, leading to an effective enzyme immobilization. Figure nonsulfated cellulose nanocrystals (N-CNC) were isolated,
4B shows a schematic view for the derivative procedure and and sulfated cellulose nanocrystals (S-CNC) were produced by
GOx immobilization. The sensor was fabricated on a screen- partial esterification of CNC surface hydroxyl groups using
printed electrode and exhibited a linear range of detection sulfuric acid. Both materials were associated with magnetite
from 0.1 to 2 mM (R2 = 0.999), LOD of 0.004 mM, and limit (Fe3O4) in the development of hybrid composites for the
of quantification of (LOQ) 0.012 mM. The as-prepared formation of (N-CNC)-Fe3O4 and (S-CNC)-Fe3O4 hybrid
platform was successfully used for monitoring the glucose system casting films. A colorimetric transduction system was
concentration (consumption) of a fibroblast cell culture explored by immobilizing GOx and ABTS in the hybrid films
medium. strips. Briefly, the H2O2 molecules from GOx/glucose reacted
In another strategy, Neubauerova et al.58 developed a with ABTS that was oxidized through the catalyst action
glucose colorimetric biosensor using CNM deposited onto a (peroxidase-like) of magnetite, and as a result, the color of the
cellulose paper substrate. Specifically, the authors used MCC film changed. Figure 4D shows the developed self-supporting
as a cellulose source, which was oxidized using TEMPO- biosensor and (I) its translucency and (II) its magnetic
mediated oxidation, leading to the formation of carboxylated properties. Both proposed that hybrid biosensors displayed
groups at the cellulose surface. Next, CNC were extracted by peroxidase-like activity (reducing H2O2 and oxidizing ABTS)
acid hydrolysis and then cast onto a cellulose substrate to and were capable of detecting glucose concentrations as low as
support glucose oxidase (GOx), horseradish peroxidase the level of glucose in biological fluids (5 mM). Figure 4D(III)
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shows the calibration curve on glucose detection for the Table 3. Examples of Cellulose-Based Piezoelectric Sensors
developed biosensors. The color change was almost immedi- Used for Detecting Motion
ate, and the (S-CNC)-Fe3O4 platform was 1.5−2 times more
type of
reactive than (N-CNC)-Fe3O4. sensor materials sensitivitya ref
BC nanofibers have also been used in the development of Force Natural cellulose nanofibrils 4.7−6.4 245
biosensors due to their three-dimensional (3D) nanostructure pCN−1
and high degree of crystallinity, which favors the adsorption of Pressure TEMPO-oxidized cellulose nanofibril 500 Pa−3 256
nanomaterials and biological compounds. In this sense, Li et al. kPa
used BC nanofibers in the development of a biosensor for Strain Carbon nanotube, cellulose GF = 321 257
nanocrystals, and polyurethane
hydroquinone detection.197 Figure 4E(I) shows the BC 3D membrane
structure which was produced by Gluconacetobacter xylinum Strain Cellulose nanofibrils, silver nanowire, GF = 26.07 254
bacteria. After that, a nanocomposite was formed using BC-Au and polyurethane sponge
nanoparticles (NP) by electrostatic assembly and in situ Pressure BaTiO3, multiwalled carbon 2 kPa 258
nanotubes, and bacterial cellulose
chemical reduction methods. The BC-AuNP structure formed
Strain Waterborne polyurethane, carbon GF = 1 259
is displayed in the TEM microscopy image of Figure 4E(II), nanotube, and cellulose nanocrystal
which shows that the BC nanofibers were successfully coated Pressure Porous silver nanowire-bacterial 5.49 MPa−1 260
with AuNP. A glassy carbon electrode (GCE) was modified and cellulose fiber
with BC-AuNPs, and the enzyme laccase (Lac) was then proximity
Strain Silver nanoparticles, carbon nanotubes, GF = 17.1 255
immobilized on its surface with Nafion, forming the GCE- cellulose nanocrystals, tannic acid,
Nafion-BC-AuNPs-Lac biosensor. Hydroquinone was detected and polyurethane
using the DPV method, and a low LOD of 5.71 nM and a a
GF = Gauge factor.
linear analytical range was found for concentration of 30−100
nM, as shown in Figure 4E(III). Moreover, the device was
employed for hydroquinone determination in real samples (tap CNM with ZnO,249 polydimethylsiloxane (PDMS),250 and
and lake water) showing that is a promising sensing platform chitosan251 to obtain piezoelectric devices has been reported.
for environmental pollutant. In piezoelectric sensors,22,245,246,252 mechanical changes are
Cellulose Nanomaterials in Piezoelectric Sensors. converted into electrical signals to be further analyzed. Most of
Piezoelectricity has been a property of interest for the design the works using CNM in piezoelectric sensors are dedicated to
of pressure and strain sensors, which have recently attracted detecting motion, i.e., pressure, flow, vibration, strain,
great attention for applications in human health monitoring, etc.119,253 Some recent examples of works using CNM in
smart devices, human−machine interaction, and wearable piezoelectric motion sensors are also shown in Table 3. For
electronics.241 As previously mentioned, the piezoelectricity of example, Zhang et al.254 used cracked CNF and silver nanowire
cellulose and wood has been known for decades, and more (AgNW) to coat a polyurethane (PU) sponge and endowed it
recently has also been demonstrated in CNC films, with with piezoresistive properties. The use of CNF was important
comparable performance to the reference metal oxide film.124 to enable the dispersion of the AgNWs and facilitate the
In this scenario, CNM has been highly explored in advanced adhesion of the conductive layer and the PU skeleton. The
electrical conductivity and mechanical properties of the
devices as nanogenerators, actuators, gas and humidity sensors,
material were investigated and could be tuned based on the
biosensors, and piezoelectric fillers for strain sensors. Such
amount of CNF and AgNWs coated onto the sponge. The
devices find applications in environmental and human
piezoresistive sensor functioning was based on the application
physiological signal monitoring, such as speech recognition
of pressure or strain, leading to a rearrangement of the
and real-time wrist pulse monitoring.242−244 Table 3 conductive network and consequent changes in the electrical
summarizes some examples of CNM-based piezoelectric resistance. The sensor was able to detect human body motion
sensors used for detecting motion. with different strains. Furthermore, the potential of using the
The enhancement of piezoelectricity in isolated crystalline material as an artificial electronic skin was demonstrated by
parts of cellulose, i.e., CNC,245 combined with biocompati- showing the ability of the sensor to detect the shape and
bility, has led to the large use of CNM in piezoelectric location of an object, as shown in Figure 5A. In another work,
systems.22,125 For instance, Yun et al.246 demonstrated that the Yan et al.255 also used a PU sponge decorated with CNC,
application of an electric field in aligned cellulose films could AgNP, carbon nanotubes (CNT), and tannic acid (TA) to
induce the formation of nanofibers and, by consequence, obtain an ultrasensitive and highly compressive piezoresistive
increase their crystallinity. This effect played the main role in sensor. The brittle CNC were employed to disperse the CNT
the enhancement of piezoelectricity, reaching a value of 10.6 ± and formed a microcracked structure providing a sensor with
0.77 pC N−1, higher than the in-plane piezoelectric charge high sensitivity toward small compressive strains. The
constant of ordinary poly(vinylidene fluoride) (PVDF) films. piezoresistive sensor presented good stability and stable
Csoka et al.124 experimentally showed the piezoelectricity of mechanical compressive recoverability for gentle and large
CNC in thin films, which could be further increased with the deformation tests, as shown in Figure 5B(I). For consecutive
degree of alignment of the CNC in the films. The higher 150 cyclic compressive tests at a strain of 1%, 40%, and 80%
piezoelectric constant value of 2.10 Å/V obtained for the CNC applied to the material, the relative resistance increased
film with a degree of alignment of 88% was superior to that of according to the strain applied and went back to 0% with
the reference film of ZnO (1.3 Å/V). In another strategy, the stress release. Such comportment shows that the AgNPs/
electrospinning PVDF with CNC resulted in a nanocomposite CNTs−CNCs@TA−PU sponge can be used for fabricating
with superior piezoelectric properties compared to those of piezoresistive sensors. The material was applied in the
pure PVDF nanofibers.247,248 In addition, the combination of monitoring of different human motions. As shown in Figure
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Figure 5. (A) (I) Digital photograph of the PU sponge coated with CNF and AgNW used as an artificial electronic skin, with a 100 g weight on it
and (II) the corresponding map of estimated pressure profile based on the change in resistance. Adapted and reproduced with permission from ref
254. Copyright 2019 The American Chemical Society. (B) (I) Stability test of the piezoresistive behavior of AgNPs/CNTs−CNC@TA−PU
sponge under a compression strain of 1%, 40%, and 80% and (II) detection of wrist bending by the piezoresistive sensor. Adapted and reproduced
with permission from ref 255. Copyright 2020 Royal Society of Chemistry. (C) Frequency shifts versus glycine concentration in the presence of the
CNF-coated QCM and unmodified QCM. Adapted and reproduced with permission from ref 267. Copyright 2020 Springer Nature. (D) Response
of the quartz crystal microbalance coated with BC membrane (blue), PEI membrane (green), and PEI/BC membranes with a weight ratio of 0.67/
1 (red) and 1.34/1 (black). Adapted and reproduced with permission from ref 268. Copyright 2011 Elsevier. (E) Detection of the antigen NS1 in
diluted blood serum by the immunoglobulin G immobilized on the surface of QCM coated with cellulose through the frequency shift related to the
amount of NS1 in the solution. Adapted and reproduced with permission from ref 223. Copyright 2017 Elsevier.

5B(II), the sensor was adhered to the wrist and could detect CNC. The CNC based QCM humidity sensor presented high
repeated bending action with excellent stability and repeat- stability in the low and middle humidity range (<84.3%). The
ability, revealing its potential for use as a wearable detection of glycine was performed by Hosseini et al.267 using
piezoresistive sensor. CNF to coat the quartz crystal of the sensor. A thin layer of the
CNM have also been used in the composition of a quartz sensing material was prepared by spin-coating a CNF
crystal microbalance (QCM),261 a mass sensor based on the suspension onto the electrode, resulting in a full-coverage
piezoelectric effect of quartz, in which changes in its resonance film with stability and wettability. As an advantage, the CNF
frequency are used to determine the amount of mass present did not require any further modification to adsorb the glycine
on the crystal.262−264 The sensitivity of a QCM can be molecules. The sensing mechanism was attributed to the
enhanced by coating the quartz with appropriate materials to formation of hydrogen bonds between the CNF and the
provide specific interactions with varied analytes or using analyte. As shown in Figure 5C, the QCM without the CNF
sensing materials with a high specific surface area.262,263,265 For produced no frequency change in the presence of glycine,
instance, Yao et al.266 developed a humidity QCM sensor while the CNF-based QCM showed a linear frequency
based on the asymmetric electrode structure and CNC as the decrease with the increase of glycine concentration, from 6
sensing material. The detection of humidity by the sensor to 500 μg mL−1, presenting a LOD of 8 μg mL−1.
occurred through the changes in mass and in the dielectric Hu et al.268 used BC to enhance the sensitivity of a QCM to
constant of the CNC films due to the adsorption of water by detect formaldehyde, based on its large surface area and high
the CNC. The high adsorption capability was attributed to the porosity. Polyethylenimine (PEI) was used with BC to
abundant hydrophilic functional groups presented by the produce a nanofibrous membrane employed as the sensing
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material. Figure 5D shows the synergic effect of BC and PEI in considering that in many cases the detection mechanism is
the detection formaldehyde when the sensor was exposed to based on color changes arising from a swelling process that
various concentrations of formaldehyde. Compared with enlarges the helical pitch of the cellulose chiral nematic
previously reported works269,270 that also used PEI in the structure. Therefore, for all the cases, in order to achieve higher
composition of the sensing material, the authors showed that selectivity for cellulose-based sensors, a judicious choice of the
incorporation of BC led to higher sensitivity and a lower LOD nanomaterials should be taken.
of 1 ppm, and faster response. The superior performance was In the last years, emphasis has been given to the
attributed to the high specific surface area of the membrane. development of CNM-based wearable sensors for in vivo
Furthermore, the sensor was tested against conventional analysis of human diseases and physiological parameters, taking
VOCs, such as dichloromethane, tetrahydrofuran, trimethyl- advantage of CNM nontoxicity, biocompatibility, and chemi-
amine, toluene, ethanol, benzene, and trichloromethane at 100 cally versatile properties. Therefore, it is expected that such
ppm, and showed very small sensitivity toward ethanol and no CNM-based wearable sensors can in part overcome some
sensitivity toward the other gases, revealing its good selectivity. shortages of traditional analytical systems, which usually
In addition, the sensor was subjected to a test of demand bench equipment as well as extraction of fluids for
reproducibility and reversibility by completely desorbing the in situ analysis of physiological parameters. One important
formaldehyde and then treating again with the previously used aspect that can limit the use of CNM in sensors (as well as in
concentration. The result presented nearly the same frequency other devices) is related to the cost of production and purity of
shifts before and after the desorption of formaldehyde, the as-obtained material. In the case of BC, larger-scale
confirming the high reversibility and good reproducibility for production is still challenging, and the quality of the end
the sensor toward formaldehyde molecules. product depends on the specific bacteria strains as well as
Pirich et al.223 used a QCM coated with thin films of feedstocks employed. For CNF, the costs are more related to
bacterial CNC to immobilize monoclonal immunoglobulin G the type of pretreatment employed, where the more affordable
(IgGNS1) and perform a specific detection of the dengue fever one is the enzymatic pretreatment process. Therefore, we
protein 1 (NS1). The carboxyl groups of the CNC provided an believe this process might be useful for large-scale production
easy and reliable alternative to immobilize bioactive molecules of disposable CNM-based sensors made of pristine CNM or
and a porous surface that increased the available area to even CNM-based composites. For CNC, the most employed
immobilize the IgGNS1, which increased the sensitivity of the method is based on the use of a sulfuric acid hydrolysis
piezoelectric sensors. The authors performed the recognition method, which is commercially available and has enabled the
of the NS1 in PBS and blood serum (ten times diluted in use in some medical products, with potential for wearable
PBS), reaching a LOD of 0.002 and 0.10 μg mL−1, respectively, sensors. In summary, although some important bottlenecks still
for a QCM with dissipation monitoring. Figure 5E shows the need to be overcome, recent and continuous advances in the
frequency shift of the QCM with dissipation monitoring for scalability of industrial production of some types of CNM and
the NS1 recognition by the IgGNS1 immobilized on the CNM-based composites point out for their utilization in the
cellulosic surface in diluted blood serum, showing its potential design of optical, electrical, electrochemical, and piezoelectric
to be used in clinical dengue diagnosis during the intense phase
sensors in the middle and long-term.


of the disease.

■ CONCLUSIONS AND FINAL REMARKS


Herein, we reviewed the fascinating properties of CNM,
AUTHOR INFORMATION
Corresponding Author
including cellulose nanocrystals (CNC), cellulose nanofibrils Daniel S. Correa − Nanotechnology National Laboratory for
(CNF), and bacterial cellulose (BC), that give them potential Agriculture, Embrapa Instrumentaçaõ , 13560-970 São
for the design of sensors and biosensors for detecting varied Carlos, São Paulo, Brazil; PPGQ, Department of Chemistry,
analytes. Specifically, the CNM materials show many Center for Exact Sciences and Technology, Federal University
interesting properties such as molecular polarization, electro- of São Carlos (UFSCar), 13565-905 São Carlos, São Paulo,
static interactions, and switchable hydrogen bonds. Other Brazil; orcid.org/0000-0002-5592-0627;
remarkable properties include high specific surface area, Email: daniel.correa@embrapa.br
renewability, nontoxicity, biocompatibility, and low cost.
More recently, the association of CNM with other nanoma- Authors
terials (e.g., metallic nanoparticles, carbon-based nanomateri- Kelcilene B. R. Teodoro − Nanotechnology National
als, enzymes, etc.) has driven the development of a large Laboratory for Agriculture, Embrapa Instrumentaçaõ ,
number of cellulose-based nanocomposites and hybrid 13560-970 São Carlos, São Paulo, Brazil; orcid.org/
materials in the form of papers, gels, thin films, membranes, 0000-0003-4337-4849
and liquid suspensions. Such a strategy appears to be an Rafaela C. Sanfelice − Science and Technology Institute,
affordable trend for designing multifaceted optical, electrical, Federal University of Alfenas, CEP 37715-400 Poços de
electrochemical, and piezoelectric sensors and biosensors for Caldas, Minas Gerais, Brazil; orcid.org/0000-0002-
detecting physiological parameters and environmental pollu- 2176-7177
tants. Fernanda L. Migliorini − Nanotechnology National
Even though CNM-based optical sensors have experienced a Laboratory for Agriculture, Embrapa Instrumentaçaõ ,
rapid advance, they usually do not present the same 13560-970 São Carlos, São Paulo, Brazil; orcid.org/
performance in terms of the limit of detection and sensitivity 0000-0002-9605-2790
compared to their electrical and electrochemical counterparts. Adriana Pavinatto − Scientific and Technological Institute of
Besides, CNM-based optical sensors are usually more Brazil University, São Paulo 08230-030, Brazil;
susceptible to suffering interference from common interferents, orcid.org/0000-0003-1370-9070
2488 https://doi.org/10.1021/acssensors.1c00473
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ACS Sensors pubs.acs.org/acssensors Review

Murilo H. M. Facure − Nanotechnology National Laboratory (11) Pavinatto, A.; Mercante, L. A.; Leandro, C. S.; Mattoso, L. H.
for Agriculture, Embrapa Instrumentaçaõ , 13560-970 São C.; Correa, D. S. Layer-by-Layer Assembled Films of Chitosan and
Carlos, São Paulo, Brazil; PPGQ, Department of Chemistry, Multi-Walled Carbon Nanotubes for the Electrochemical Detection of
Center for Exact Sciences and Technology, Federal University 17 α -Ethinylestradiol. J. Electroanal. Chem. 2015, 755, 215−220.
(12) Fan, J.; Zhang, S.; Li, F.; Shi, J. Cellulose-Based Sensors for
of São Carlos (UFSCar), 13565-905 São Carlos, São Paulo,
Metal Ions Detection. Cellulose 2020, 27 (10), 5477−5507.
Brazil; orcid.org/0000-0003-0858-0364 (13) Barandun, G.; Soprani, M.; Naficy, S.; Grell, M.; Kasimatis, M.;
Complete contact information is available at: Chiu, K. L.; Ponzoni, A.; Güder, F. Cellulose Fibers Enable Near-
https://pubs.acs.org/10.1021/acssensors.1c00473 Zero-Cost Electrical Sensing of Water-Soluble Gases. ACS Sensors
2019, 4 (6), 1662−1669.
Notes (14) Prathapan, R.; Tabor, R. F.; Garnier, G.; Hu, J. Recent Progress
in Cellulose Nanocrystal Alignment and Its Applications. ACS Appl.
The authors declare no competing financial interest. Bio Mater. 2020, 3 (4), 1828−1844.

■ ACKNOWLEDGMENTS
The authors thank the financial support from Fundaçaõ de
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