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R. Xiong et al.
/ Materials Science and Engineering R 125 (2018) 1–41 1

Materials Science and Engineering R 125 (2018) 1–41
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2 R. Xiong et al. / Materials Science and Engineering R 125 (2018) 1–41
scaffolds for nanoparticle assembly. Through the chemical or most popular wet-chemistry approaches include layer-by-layer
physical linking of DNA to cargo, nanocomposite bio-metallic (LbL) assembly, one-pot assembly approaches such as vacuum
structures can be formed whereby DNA templates can guide, assisted filtration and cast-drying, wet-spinning and electro-
reduce, and position metal ions or metallic cluster. A wide variety spinning, freeze drying, and various micropatterning approaches
of cargo materials have been directed by polynucleotides including [52,144–147].
small molecules [130–132], metal nanoparticles [133–135],
vesicles [136], quantum dots [137], and simultaneous loading 1.1. LbL assembly
with multiplexed cargo has been demonstrated [133].
Metal nanoparticles can be integrated into DNA strands to LbL assembly is a popular strategy for preparing multilayered
enhance composite rigidity, and to serve as a template around thin membranes and coatings with pre-programmed composition,
which DNA is organized [21]. DNA-nanoparticle assemblies have controlled adhesion, gas barrier, and adaptable abilities [148]. This
shown increased geometric complexity with extension to long- technique allows the precise control of thickness, distribution, and
range ordered local organization [138,139], eventually leading to content of biocomponents at a single molecular layer level by
controlled superlattice architectures with different symmetries alternating deposition of the complementary components on
(Fig. 5). These complex architectures are controlled by DNA-linker various substrates via tunable interfacial interactions such as
mix to create nanoparticle short-range order [140] or nanoparticle hydrogen bonding, electrostatic interactions and hydrophobic-
geometry. Surrounding biological matrix can assist in building hydrophobic interactions [149,150].
embedded nanoparticle superlattices [141] and controlling ther- The LbL technique also affords wide diversity in the selection of
mal annealing can lead to single-crystal nanoparticle lattice substrate materials and specific deposition techniques (Fig. 6a).
formation [142]. Various bionanocomponents can be assembled on diverse sub-
strates such as flat wafers, glass, flexible films, fibers, particles, and
1. Processing of bionanocomposites textiles via spin-coating, spray-coating, and immersive/dip-coat-
ing [150]. After LbL deposition, as-prepared layered bionanocom-
Unlike synthetic thermoplastics that can be melt-extruded into posite films with desired composition can be further annealed and
properly shaped bulk material parts, biopolymers are prepared via released from the substrate in a free-standing state by selective
solution processing because their thermal degradation temper- dissolution of the sacrificial substrate or pull-off of the films for
atures are close to or lower than their glass-transition temperature further investigation, post-processing, or transfer for further
(Tg) [143]. In the past decade, solution assembly techniques were applications.
developed to shape biopolymeric materials into various macro- Recently, CNC microcages with a “haystack” shell morphology
scopic forms, including membranes, microcapsules, fibers, aero- were fabricated by assembling negatively charged CNCs on cationic
gels, patterned microstructures, and stretchable structures. These polyetherimide (PEI) modified surface of silica microspheres
fabrication approaches are highly dependent on the physicochem- (Fig. 6b) [151]. After the removal of the silica core, the resilient
ical properties of the biomaterials solutions, such as interactions cage-like microcapsules show an open nanofibrillated network of
between building blocks, concentration, and viscosity. To date, the CNCs with tunable large and open pores. It has been observed that
Fig. 7. (a) Vacuum assisted filtration approach for preparing silk/graphene oxide films, reproduced from [157] with permission. Copyright 2015 American Chemical Society;
(b) the illustration of cast-drying technique for preparing PVA/CNF/MTM films, reproduced from [159] with permission. Copyright 2014 American Chemical Society.
R. Xiong et al. / Materials Science and Engineering R 125 (2018) 1–41 3
CNC microcapsules have large pore sizes up to 100 nm that allow thick laminated structures. It also gives an opportunity to obtain
for the fast transport of large nanoparticles (30–100 nm). Notably, well-defined and stratified films with precisely designed laminat-
the loading and unloading behavior of nanoparticles can also be ed morphology, structure, and composition at the nanoscale scale.
regulated by controlling the pH. Aside from CNCs, other related Bionanocomposites fabricated by these approaches afford a high
biopolymers had been used to prepare the LbL microcapsules with degree of materials compatibility, uniformity, and enhanced
tunable porosity from single-component silks [152], modified silk physical properties [157,158], Compared to the traditional LbL
ionomers [153], and chitosan [154]. assembly, one-pot directed assembly is more efficient because it is
LbL assembly is also widely used for the fabrication of thin simpler, faster, and affords assembly of nanoscale-level dispersions
organized bionanocomposite membranes with thicknesses as low resulting in significantly improved nanocomposite properties and
as a few nanometers [155]. To this end, Hu et al. [156] fabricated relatively thick microscopic paper with large dimensions but lacks
novel freestanding robust bionanocomposites with thickness of precise control of local composition and morphology.
50 nm fabricated by spin-assisted LbL assembly from silk fibroin One-pot directed assembly can be classified into two specific
and GO sheets (Fig. 6c). These silk-based nanomembranes show methods: vacuum assisted filtration and cast drying (Fig. 7). Both
remarkable mechanical strength with elastic modulus of 140 GPa methods require uniform premixing of the biopolymer solution
and strength of above 300 MPa due to their highly uniform and nanofiller dispersion [157,159]. Subsequently, the colloidal
nanostructure achieved by the LbL technique and complementary mixture in the vacuum assisted filtration case is passed through
interfacial interactions. Moreover, Xie et al. demonstrate that LbL commercial nanofilters with pores whose size is smaller than
assemblies of GO sheets and silk possess outstanding specific nanofillers to allow the solvent to flow through while withholding
penetration energy, significantly higher than that of Kevlar fabrics these nanofillers from aggregation with bound biopolymers as the
and close to that of conventional multilayer graphene structures topmost layer.
[155]. In the cast-drying technique, the colloidal mixture is placed into
clean containers such as Petri dishes or deposited on a clean
1.2. One-pot directed assembly (vacuum assisted filtration and cast- substrates by various coating techniques such as bar coating and
drying) spraying to obtain solid films after complete solvent removal. For
example, layered bionanocomposite films with layered morpholo-
One-pot directed assembly overcomes major obstacles, such as gy can be readily fabricated by using biopolymer-GO mixture or
high cost and long fabrication time, for developing large scale and
Fig. 8. (a) Fiber spinning of CNC/PVOH composite fibers; (b) the stress-strain curves of CNC/PVOH fibers; (C) the SEM of CNC/PVOH fiber and the 2D WAXS data in inset,
reproduced from [168] with permission. Copyringht 2016 American Chemical Society.
biopolymer-MTM co-dispersion via both vacuum assisted filtration surrounding small molecular solvents are removed by sublimation,
and cast drying [157,159,160]. avoiding the capillary force-induced collapse of the nanopores that
usually happen in conventional air drying. Freeze-drying is widely
1.3. Fiber-spinning techniques adopted to prepare various bionanocomposite aerogels, including
those based upon cellulose [113], chitin [171], chitosan [172],
Spinning techniques are conventional methods for fabrication starch [173], alginate [174], and silk [175].
of bionanocomposite fibers, which can be categorized into two Notably, the macroscopic shape adopted by nanocomposite
types, wet spinning and electrospinning [161–163]. Wet spinning aerogels is basically the same as the original solution container.
has the advantage of large-scale production of biopolymer Thus, different product shapes can be obtained readily via
microfibers and bundles of microfibers (Fig. 8). templating by a container shape. The microscopic morphology
In contrast, the electrospinning approach has the capability of of aerogels such as the pore size and distribution as well as shape
producing extremely fine nanofibers in the form of non-woven and orientation can also be controlled during the freeze-drying
mats which are ready for further processing [164–167]. Notably, 1D process. The most well-known example is the ice-template
nanostructures of reinforcing components can be aligned along the approach that can form nanostructures by regulating the growth
fiber axis due to high-speed sheering forces during the spinning of ice crystal in the nanocomposites [176].
process. For example, Mao et al. [177] reported that a novel silk fibroin–
For example, Lee et al. [168] fabricated ultra-strong and stiff chitosan aerogel with controllable open-pore and oriented porous
CNC/poly(vinyl alcohol) (PVOH) nanocomposite fibers via wet structures can be constructed using the ice template technique.
spinning gels of CNC and PVOH, followed by hot-drawing (Fig. 8). It This as-prepared aerogel showed predefined microfluidic channels
was observed that adding of CNC components not only provide the that could promote the mass transport, facilitating uniform cell
direct reinforcement, but also increase the alignment and distribution and growth. Recently, Yu et al. demonstrated the use of
crystallinity of PVOH. This synergistic effect resulted in remarkable ice-template technique in the fabrication of the artificial nacre
mechanical enhancement with strength and stiffness reaching (Fig. 9) [178]. In this study, they biomineralized aragonite platelet
880 MPa and 30 GPa, respectively. within the uniform chitosan layered nanochannels that were
Recently, uniaxially aligned cellulose nanofibers reinforced by constructed by the ice-template. Then, silk molecules penetrated
CNCs were fabricated via electrospinning [169]. CNCs were finely the free space available within inner nanocomposite volume to
dispersed into the cellulose fiber matrix with preferred orientation mimic the overall composition, morphology, and internal organi-
along the fiber axes. Such mutual orientation of components zation of natural nacre to achieve comparable or higher ultimate
resulted in significant enhancement of the mechanical perfor- strength and fracture toughness.
mance of cellulose nanofibers while improving their thermal
stability. Additionally, these nanofibers show potential for use as
scaffold materials for tissue engineering. Not only are they non- 1.5. Micropatterned bionanocomposites
cytotoxic, but they also exhibit a strong role in directing cellular
organization. Micropatterned bionanocomposites with 2D or 3D organized
morphologies show interesting global physical properties and
1.4. Freeze-drying peculiar localized distribution of components with mediating
stresses, deformations, foldability, and electrical conductivities.
Freeze-drying, also known as lyophilization, is a dehydration Carefully designed micropatterns open a path to consider adaptive
process that works by first freezing bionanocomposites in solution behavior such as self-folding, self-rolling, and actuation. The
or hydrogel [170]. Freeze-drying preserves the morphology of strategies that were developed to pattern bionanocomposites
nanocomposites in the wet state to prepare highly porous, ultra- mainly exploited well-known techniques such as mask based
lightweight bionanocomposite aerogels. In this approach, the patterning, inkjet printing, and 3D/4D printing.
Fig. 9. The fabrication of the synthetic nacre via ice template technique followed by mineralization, infiltration and hot-press; (b) the image of as-prepared synthetic nacre;
(c) the SEM image of cross-section of the synthetic nacre. Scale bar: 1 cm for b; 3 mm for c, reproduced from [178] with permission. Copyright 2016 American Association for
the Advancement of Science.
4.5.1. Masks based micropatterns In an example of recent developments of this approach to

Traditional mask based pattern techniques can be applied to bionanocomposites, an electrochemical microstamping technique
various solid surfaces by using a pre-patterned stamp pressed into was exploited for fabrication of micropatterned GO/silk biopaper
a softened polymer to emboss the pattern into the substrate with high electrical conductivity on select areas at ambient
[179,180]. The stamp or mask must first be fabricated using conditions without damaging the silk matrix in order to prepare
methods such as optical cutting, electron beam or focused ion highly conductive paper-like materials and corresponding sensors
beam lithography, which enable parallel fabrication of predeter- [158]. In this research, selective electrochemical reduction
mined structures multiple times and at large areas. These patterning with micron resolution was conducted with only
techniques are based upon soft lithographic techniques that have selected regions being electrically conductive. To obtain higher
been developed extensively in elastomeric materials in works resolution, well-defined 2D microstructures were prepared by
pioneered by Whitesides et al. [181,182] This original approach has screen printing or by photolithography for masking the region of
been extended by applying different types of microstamps, reduction [191].
sequential applications of microstamps, nanoimprinting
approaches, micromolding, and capillary transfer lithography 4.5.2. Inkjet printing
[183–185]. Inkjet printing is a direct printing technique for various liquid
Developments in the patterning of silk- and nanocellulose- “inks” with low-cost, high efficiency, good reproduction and easy-
based materials offer a good starting point in the patterning of operation. In this technique, a jet of a solution breaks up into
similar nanocomposites. For instance, Omenetto et al. demonstrate droplets, which are deposited onto a surface, and form a pattern
that silk films could be employed in the transfer of micron-scale when the solvent evaporates [192]. The resolution of the final
patterned features similar to replica molding with PDMS stamps pattern depends on the size of the droplets, the viscosity of the ink,
[186]. Uncured silk-coated substrates have also been shown to be and the interaction between inks and substrates. Inkjet printing
able to pick up patterns via hot embossing at 100 ○C or water- has recently been extended to various biopolymer materials,
mediated nanoimprinting at room temperatures [187]. Parker et al. including silk [193], chitosan [194], and chitin nanocrystals [195].
generated patterned fibronectin into so-called nanofabrics by These bio-inks can be printed onto target substrates with little or
depositing a fibronectin-containing slurry onto the surface of a no reduction of bioactivities to create DNA, protein and cell
PDMS stamp with parallel 30-mm pitch channels [188]. These patterns [196,197]. Versatility of ink-jet printers is facilitated by
structured assemblies of bio-derived components generally have choice of size of the nozzles (10–100 um). The choice of different
critical feature dimensions of tens to hundreds of microns inks (solutions or dispersions) makes ink-jet printing a valuable
primarily limited by the resolution of mask used and spreading tool for constructing user-defined geometries of multilayer
of polymeric transfer agents [189]. Using specially designed structures with micron-scale precision and accuracy. In contrast
polymeric transfer agents and photolithography-generated master to the microcontact printing, the inkjet printing shows some
masks have led to an increase in the theoretical resolution, potential for the industrial-scale production due to its ability to
approaching tens of nanometers [190]. However, these innovations pattern across large print-scalable areas.
in achieving high-resolution soft lithography patterning are
unlikely to be translatable to bio-derived polymers and their 4.5.3. 3D printing
nanocomposites due to the current mismatch in physical and 3D printing is an emerging powerful tool for the fabrication of
chemical properties between bio-sourced materials and state-of- hierarchical 3D nanostructures by layer-by-layer printing of
the-art soft lithography patterned transfer agents [189]. dispersions and extrusion of melts. In the past decade, a growing
Fig. 10. (a) The shear-induced alignment of cellulose fibrils during direct ink writing and the anisotropic swelling effects of the as-prepared cellulose structure; (b) the
swelling behavior of flower-like cellulose structures. (scale bars, 5 mm, inset = 2.5 mm), reproduced from [207] with permission. Copyright 2016 Springer Nature.
number of studies reported 3D printing of biomaterials for constructing patterns with nanometer-level resolution
biomedical applications such as tissue engineering and regenera- (~100 nm) [181,208].
tive medicine because it is efficient, low-cost, and has good
reproducibility [198]. Various polysaccharide and protein biopol-
ymers used as bio-inks to fabricate complex 3D microstructures 4.6. Kirigami and origami structures
[199].
For example, a bio-ink consisting of peptide-modified biopol- Large volume top-down fabrication routines of functional
ymers and gellan gum were used to print brain-like 3D structures bionanocomposites have usually been confined to two dimensions,
that encapsulate discrete layers of primary neural cells [200]. Silk whereas three-dimensional shapes enable more complex, hierar-
based bioinks were also developed for high resolution 3D printing chical organization of molecules that is rarely achievable (e.g., see
of structures with adjustable mechanical properties for matching examples of 3D printing above). The combination of the ease of 2D
soft tissue properties [201–203]. The supramolecular hydrogels fabrication with the functionality of 3D structures has rarely been
based on hyaluronic acid modified with either adamantine or demonstrated to date. This interfacial stress emerges through the
b-cyclodextrin were used to print 3D microstructures that are combination of dissimilar materials, or through the transfer of
capable of self-healing through the spontaneous restoration of stresses along pre-defined points of contact. Whereas the
guest–host bonds between Ad and b-CD moieties [204]. processing of bulk materials either through casting or extrusion
Recently, so-named 4D printing approach has been introduced cannot generate micro- or meso-scale architecture by design,
by combining commercial 3D printing with responsive materials methods for generating high resolution 3D structures such as 3D
for smart textiles, autonomous robotics and biomedical devices printing or 3D photo-fabrication techniques are fundamentally
[205]. These architectures can change their shape responding to serial in nature, and cannot produce components fast and in
external conditions after printing initial planar structures [206]. sufficient volumes beyond prototyping or customization applica-
For example, Lewis’ group [207] reported biomimetic 4D printing tions. Thus, alternative strategies such as kirigami and origami,
of nanocellulose microstructures with well-defined features have been introduced in order to involve or generate non-planar
inspired by the shape-morphing behaviors of plants in response materials. Existing kirigami strategies are largely based on
to external humidity. These printed architectures demonstrated lithographic cutting then generating interfacial stresses to induce
localized, anisotropic swelling behavior because of the alignment self-folding in the material as was discussed above [209,210].
of nanocellulose structures along prescribed printing pathways External stresses can be applied to the pre-programmed
(Fig. 10). After immersion into water, the programmable archi- materials to induce deformations to accommodate differential
tectures automatically yield complex 3D structures as a result of interfacial stresses. The most well-known fabrication methods for
pre-programmed localized folding, with geometries resembling these purposes are origami and kirigami, traditional paper
that of plant petals. handicraft techniques [211]. For instance, Rogers’ group used
Notably, these direct-writing techniques present an inevitable lithography to generate kirigami cuts in an ultrathin silicon
drawback in terms of modest spatial pattern resolution and structure in the shape of serpentine twists, pinned to an
relatively low throughput at large scale production. For instance, elastomeric substrate at select anchor points. Compression of
the usual resolution of inkjet printing is at high micrometer-level the substrate causes the elevation of unanchored features off the
(~10–100 mm at best) because of the large drop size and clogging substrate into the z-dimension [212]. Overall, these methods
problems for narrower nozzles, and fabrication time can easily possess advantages in terms of precise nanostructure control, high
reach hours per s single structure. In contrast, the photolithogra- efficiency, large-scale production, generation of fibrous and porous
phy and nanoimprinting techniques have the capability of nanostructure as well as ultrahigh stretchability.
Fig. 11. (a) Micropatterns and mechanical performance of GO-PVA nanocomposites after kirigami photolithography, reproduced from [213] with permission, Copyright 2015
Springer Nature; (b) Structure and photographs of a slinky triboelectric nanogenerators by origami approach, reproduced from [215] with permission. Copyright 2015
American Chemical Society.
In another study, Kotov et al. [213] used top-down kirigami (alginate and carrageenan) [216,217]. As renewable biopolymers,
patterning techniques to program nanocomposite paper (Fig. 11a), polysaccharides possess many favorable characteristics such as
whereby deformation induces folding of the 2D film in the z- low toxicity, biocompatibility, stability, low cost, and availability of
dimension while preventing unpredictable local failure and largely reactive sites for chemical modification [218]. In this section, we
increasing the paper strain from 4 to 370%. Notably, the kirigami mainly focus on nanocelluloses from the viewpoint of their
technique has the capability of realizing remarkable stretchability, utilization for bionanocomposites [49]. We discuss the extraction
but this enhancement comes with a trade-off in overall strength. In of nanocellulose, processing of various nanocellulose nanocom-
Kotov’s study, for example, the ultimate stress of this paper sharply posites, and their applications in flexible devices.
dropped from 200 MPa to 0.2 MPa after introducing a folding
pattern [213]. This diminished performance should be considered 2.1. Nanocellulose components
before implementation of kirigami materials in practical applica-
tions and should be carefully considered for ultimate performance. Nanocellulose components can be isolated from original
Origami, another known paper folding technique, which also cellulosic sources by various methods, including acid hydrolysis
draws increasing research attention [214]. In contrast to destruc- and mechanical treatment [49]. Additionally, nanocellulose
tive cutting techniques, origami integrally saves the intact components can be produced by bacterial synthesis [219]. Nano-
nanostructure of materials, enabling the excellent mechanical cellulose not only inherits the intrinsic properties of cellulose
performance of the final programed products. For instance, fibers, but also possess specific features of nanoscale materials
inspired by the origami technique, Wang et al. [215] used paper caused by its high aspect ratio (up to several hundreds) and high
as the starting material to fabricate slinky- and doodlebug-shaped surface area. The elementary component of nanocellulose in wood
triboelectric nanogenerators (Fig. 11b). These origami structures is highly crystalline nanostructures with diameter of around 3 nm,
are mechanically robust to stretch, lift, and twist in order to harvest and consists of 5–6 molecular chains [49], providing individual
ambient mechanical energy from various kinds of human motions CNCs with elastic modulus as high as 150 GPa, comparable to
in wearable materials option. Kevlar fibers [220,221]. Moreover, nanocellulose possess a low
Overall, the choice of fabrication method is highly dependent coefficient of thermal expansion of 0.1 ppm/K and high optical
on the practical situation, including the interaction between transmittance (98% at 550 nm)—making these materials attractive
components, the functionality requirement, the mechanical for flexible and transparent electronic devices [222].
properties requirement, and the feasibility of different approaches The linear cellulose chains consist of repeat anhydroglucose
for different materials. For example, the fine dispersion of rings through b 1–4 glucoside linkages, which provide high
nanofillers is a crucial factor for the fabrication of high-perfor- content of surface hydroxyl groups (Fig. 12) [223]. Various
mance nanocomposites. Therefore, the one-pot processing chemical modifications of nanocellulose, such as esterification,
approaches are not suitable for many cases, while LbL assembly cationisation, carboxylation, silylation and polymer grafting have
can be a very efficient approach for bionanocomposite fabrication. been reported to date [224]. Most of the modifications explored
predominantly occur on the hydroxyl group of the sixth position,
2. Polysaccharides for bionanocomposites which acts as a primary alcohol [225,226]. These modifications can
enhance the interfacial interactions between nanocellulose
Polysaccharides, the most abundant group of biopolymers by components, improve dispersibility in different solvents and
weight, exist in various natural sources, including plants (cellulose matrices, and provide additional functionality. Fig. 12 gives a
and xylan), sea-animal shells (chitin and chitosan) and algae schematic overview of the typical modifications in the
Fig. 12. The general routes for modification of nanocellulose, reproduced from [225] with permission. Copyright 2014 Isik et al. licensed under CC BY 3.0; the bottom inset
shows the molecular structure of nanocellulose, reproduced from [226] with permission. Copyright 2014 Springer Nature.
nanocellulose production route and the surface chemistry of the other carbon sources [224]. The resulting BNC is in the form of a
final products [225,226]. pellicle that consists of a 3D cellulosic network structure with
randomly assembled ribbon shaped cellulose nanofibrils (Fig. 13c)
2.1.1. Preparation of nanocellulose [49].
Nanocellulose can be classified into three categories: CNCs,
cellulose nanofibers (CNFs) and bacterial nanocellulose (BNC) 2.1.2. Different forms of nanocellulose materials
[49,227]. The size, morphology and strength highly depend upon Nanocellulose can be processed and fabricated into various
the source and processing conditions. CNCs generally contain forms with variable mechanical properties, including robust 1D
highly crystallized nanostructures, while CNF and BNF types fibers, 2D optical transparent or iridescent paper, 3D soft and
consist of highly crystalline arrangements and perturbed location highly compressible aerogels. The most common technique to
referred to as amorphous regions, which can provide them more fabricate nanocellulose fibers is wet-spinning, which is widely
flexibility and continuity. used by industry [231]. During the spin process, various kinds of
Typically, CNCs are produced from the cellulosic fibers by acid functional nanoparticles, such as magnetic nanoparticles and
hydrolysis, where the more readily accessible amorphous regions electrical conductive nanoparticles can be added into the nano-
are cleaved to liberate rod-like crystalline cellulose sections [49]. cellulose dispersions to produce multi-functional nanocellulose
When the appropriate hydrolysis level has been reached, the acidic fibers [232].
mixture is diluted, and the residual acids and impurities are In contrast to the micron-scale size of wet-spun fiber, electro-
removed by repeated centrifugation and extensive dialysis. The spinning generates nano-scale size cellulose fibers [169]. However,
physical and chemical behavior of CNCs is strongly dependent on to fabricate nanofibers that only consist of nanocellulose
the type of acid used during processing and its concentration, the components remains a challenge. Recently, ultra-strong cellulose
hydrolysis temperature and time, in addition to a cellulosic source. fibers with strength of 600 MPa and ultimate strain up to 12% were
Typically, these CNCs prepared from wood pulp have a diameter of prepared by a hydrodynamic alignment method [233]. These
5–10 nm and length of 100–300 nm (Fig. 13a) [151]. cellulose fibers demonstrated highly ordered orientation that is
CNF is normally produced from cellulosic materials by intensive comparable to the strongest cellulose pulp fibers extracted from
mechanical treatment, including high pressure homogenization, wood (Fig. 13d). Hu’s group utilized a wet-drawing and wet-
grinding, and ultrasonic treatment [228,229]. To make the twisting process to assemble BNC hydrogel into long BNC fibers
preparation more efficient, Isogai et al. utilized 2,2,6,6-tetrame- [227]. This technique not only retains the interconnected network,
thylpiperidine-1-oxylradical (TEMPO) mediated oxidation to but also allows the highly uniform alignment of nanofibers. These
introduce carboxylate groups into cellulosic materials for breaking as-prepared fibers show a good combination of high tensile
the strong hydrogen bonding of the cellulose nanofibers [230]. strength (826 MPa) and Young’s modulus (about 66 GPa).
Using this method, individualized cellulose nanofibers with 3– Interestingly, CNCs is capable of self-assembling into a left-
4 nm in diameter and a few microns in length can be produced handed chiral nematic liquid crystalline (LC) phase when the
with conjugated straight segments of several hundred nm in dispersion concentration is above a critical value [234]. This
length (Fig. 13b). Excepting isolating from cell walls in plants, assembly is due to the CNC’s right-handed twist along the nanorod
nanocellulose can also be synthesized by several bacterial species axis [226]. Recently, the right-handed twist of individual CNCs
(e.g. Acetobacter G. xylinus) with low-molecular weight sugars or from different origins was observed by cryo-electron tomography
Fig. 13. AFM images of cellulose nanocrystals (a) and cellulose nanofibers (b); (c) SEM image of bacterial cellulose, reproduced from [227] with permission. Copyright 2017
John Wiley & Sons; (d) SEM image of oriented cellulose nanofibers based microfiber (inset: 2D XRD pattern), reproduced from [233] with permission. Copyright 2014
Hakansson et al. licensed under CC BY 4.0; (e) photo and optical microscopic image of iridescent cellulose nanocrystal film, reproduced from [235] with permission. Copyright
2014 American Chemical Society; (f) transparent cellulose nanofibers nanopaper, reproduced from [238] with permission. Copyright 2009 American Chemical Society; (g)
photo of large-area bacterial cellulose hydrogel, reproduced from [246] with permission. Copyright 2016 American Chemical Society; (h) weight-light and anisotropic aerogel
nanocellulose aerogel, reproduced from [249] with permission. Copyright 2012 Springer Nature.
microscopy, scanning electron microscopy, and atomic force specific bacteria can produce nanocellulose hydrogels directly
microscopy [17]. These LC structures can be preserved (frozen) from low-molecular weight sugar (Fig. 13g) [246]. Compared with
in solid films to provide a brightly iridescent structural color the CNF and CNC hydrogels, bacterial nanocellulose hydrogels
(Fig. 13e) [235]. This structural color is controlled by the helical show many advantages, including facile processing, large-scale
structure as determined by the inter-distance (pitch, P) between production, and mechanical robustness. However, their optical
adjacent layers, and the observing angel (u). These terms follow the transmittance is much lower than TEMPO oxide-nanocellulose
rule l = 2npsinu, where n is the refractive index of the cellulose hydrogels because of their larger diameter.
film, and u is the reflection angel with respect to the film surface Cellulose aerogels are flexible and robust porous ultralight
[235]. Additionally, helical nanostructures in CNC films can be used material with a typical porosity of 98% and density of ca.
as chiral templates for inorganic nanoparticles for flexible photonic 0.03 g cm—3, and are formed when water-content in a hydrogel
materials [236]. is replaced with air via freeze-drying [247]. The porosity, pore size,
Nanocellulose papers are usually prepared by vacuum assisted and pore orientation of aerogels can be regulated via controllable
filtration of a nanocellulose dispersion [237]. The optical trans- drying. For instance, in the ice templating approach, when the
mittance of nanocellulose papers is highly dependant on nano- hydrogel is exposed to a controllable temperature gradient,
cellulose size and orientation. For CNF papers with randomly unidirectional ice crystals will form in the hydrogel and the
distributed nanocellulose nanostructures, transmittance largely nanocellulose will be concentrated between ice crystals. After
increases with decreasing the diameter of nanocrystals. When the removal of ice crystals by freeze drying, the anisotropic cellulose
diameter is significantly smaller than the light wavelength, the aerogels can be prepared and the microstructure with different
nanopaper exhibits transmittance of 90% at 550 nm due to the dimensions can be achieved by adjusting freezing kinetics [248].
remarkably low light scattering (Fig. 13f) [238]. Additionally, the For example, cellulose aerogels with honeycomb structures were
mechanical properties of paper are highly sensitive to the diameter fabricated by a unidirectional freeze-drying approach (Fig. 13h).
of nanocellulose [239]. Nanopapers made up of ultrafine CNFs can Even after adding other components such as GO sheets, the aerogel
overcome the conflict between strength and toughness in can still maintain a uniform anisotropic morphology and open
conventional materials. When the average diameter of nano- microchannels [249].
cellulose decreases to 11 nm, both the strength and toughness of
the nanopaper increase by two orders of magnitude [239]. These 2.2. Current and emerging applications of nanocellulose materials
results suggest that smaller nanocellulose diameters can lead to
stronger and tougher nanopapers with superior properties. Due to the good biocompatibility, biomedical applications of
Additionally, it has been demonstrated that CNFs ultrathin films nanocellulose materials are widely reported and well-reviewed
can be fabricated via spray-assisted LbL assembly, where CNFs are recently, including tissue scaffolding [250] and drug delivery
uni-directionally aligned along the spray direction as controlled by applications [251]. Additionally, nanocellulose materials possess
the deposition conditions [240]. In another recent study, spin- abundant functional groups and ultrahigh surface area, making
assisted LbL assembly was exploited for formation of mechanically them attractive materials for waste water treatment, such as
robust CNFs/silk ultrathin films with high modulus of 30 GPa and removing metal ions [127], removing organic pollutants [252], and
strength of 260 MPa, having a peculiar “shish kebab” CNFs/silk separating oil/water phases [253]. The approaches for these
nanostructures [241]. These nanoporous films allow ultrafast applications are well established and several reviews summarize
water transport combined with high rejection rate for various recent progress [254–256]. Therefore, here we mainly focus on the
organic molecules and capturing heavy metal ions. emerging applications for structural nanocomposite materials,
Cellulose hydrogels are physically or chemically cross-linked 3D health monitoring, energy harvest and storage, and optical and
networks that contain up to 90 wt% water [242]. They can be electronic bioenabled devices.
fabricated in a variety of forms including slabs, membranes, beads, Compared with other biopolymer components widely exploited
and microspheres. Regenerated cellulose hydrogel is prepared for bionanocomposites, such as proteins and DNA, nanocellulose
from the cellulose solution via a sol-gel process and mainly consists demonstrates the critical advantages in overall mechanical
of amorphous cellulose, which is much weaker than the native performance, chemical and thermal stability, robust functionali-
crystalline nanocellulose. In contrast, the nanocellulose hydrogels ties, easy availability, and modest cost, and easy processing, which
are prepared from the nanocellulose dispersion by gelation [243]. are extremely important for their applications. For example, the
The gelation involves physical entanglements, noncovalent inter- strength of nanocellulose paper is higher than 200 MPa [257],
actions (hydrogen bonding, ionic interaction, and van der Waal which is several times higher than comparable protein films
forces) and covalent crosslinking. Cellulose nanofibers prepared by (below 100 MPa for regenerated silks)[258]. Moreover, from a
TEMPO method will gel spontaneously when the concentration nanomanufacturing viewpoint, unlike many other biological
exceeds 1 wt% [230], while the CNC dispersion has to have a several solutions and dispersions [259], nanocellulose dispersions show
times higher concentration to form the hydrogel due to the high excellent shelf-life over many years and can be processed within
aspect ratio of CNF, enabling the more efficient physical harsh conditions, such as different and extreme pHs, intensive
entanglement. sonication, and stirring.
Adding other crosslinkers can significantly decrease the
requirement for the minimum nanocellulose concentration to 2.2.1. Structural applications
form hydrogel, and the mechanical properties also can be largely In the emerging applications, the nanocellulose nanocompo-
enhanced. For example, metal ions were explored to induce the sites should satisfy very diverse and strict mechanical require-
gelation of nanocellulose because of the presence of negatively ments. For example, bioelectronic devices applied on human skin
charged carboxyl and sulfate groups [244,245]. Freestanding or embedded in some tissues (such as brains, teeth and eyes)
transparent carboxylated CNF hydrogel can be prepared by using require mechanical compatibility (similar compliance and
divalent or trivalent cations (Ca2+, Zn2+, Cu2+, Al3+, and Fe3+) as strength), conformability to biological surface and high tolerance
crosslinkers to form interconnected porous nanofibril networks by body. All three are necessary to ensure bioelectronic devices’
[244]. The storage moduli of these hydrogels are strongly long lasting functionality and integrity. Various parts of the human
dependent on valency of the metal ions and can vary within a body possess very diverse mechanical properties with the elastic
wide range from 3 KPa to 31 KPa. Notably, several culturing- modulus ranging from 1 KPa for the prostaglandin to 80 GPa for
teeth, which represents a significant challenge for matching with nanocomposite for sensitive e-skin [246]. Also, conventional
existing bionanocomposite implants [260–263]. To integrate compressive sponges such as polyurethane (PU) foams can be
bioelectronic devices into humans for detection or therapy used a compressible template to support these functional
purposes these mechanical properties must be closely matched. biopolymers for fabricating highly sensitive pressure sensors
For instance, remarkable properties of human skin include its [266].
exceptional flexibility, foldability, and stretchability (up to 30% of In another example, robust flexible bionanocomposites can be
elongation). These unique properties enable skin to accommodate fabricated through LbL assembly of flexible GO sheets with stiff
body movements and protect inner organs and bones against CNCs component (Fig. 14) [267]. In this case, the flexible GO sheets
external impacts [264]. Besides, skin has excellent sensing tightly wrap the cross-junctions of the dense interlocked CNCs.
functionality that not only can detect the tiny vibrations in the Thus, reorientation, displacement and pulling-out of the confined
external environment such as a gentle breeze and insects’ CNCs components absorb massive energy during deformation,
movement, but also reveal the biological changes in our body resulting in high mechanical performance with elastic modulus as
such as the body temperature variation and sweat constituent high as 170 GPa and strength up to 650 MPa, both being close to the
variation. To create artificial nanomaterial designs that match record values achieved.
these unique properties, it will require the electronic skin (e-skin) Wen et al. reported the fabrication of ultrastrong nano-
materials that has matching strength, stiffness, toughness, and composite films via evaporation-induced assembly of GO sheets
flexibility to that of skin on the human body. Natural polymers and small amount of CNCs components [268]. These films
possess wide mechanical variation, depending on their molecular demonstrate a good combination of mechanical performance
structure, degree of polymerization, and constituent chemical and electrical conductivity, such as 765 MPa and 15.6 MJ m—3 for
components which can be instrumental in solving this issue. strength and toughness, respectively, and 1105 S/cm for conduc-
Moreover, combining biological components with other func- tivity. Mittal et al. utilized the engineered spider silk to crosslink
tional synthetic components is one conventional approach for the cellulose nanofiber for constructing ultrastrong fibers with the
constructing variable mechanical properties and facilitate added elastic modulus of ~ 55 GPa, strength at break of ~ 1 GPa, and
functionality to the resulting materials. Notably, the most widely toughness of 55~ MJ m—3 [269].
used strategy is the incorporation of stretchable or compressive Controllable porosity and wide pore size distribution play an
components to provide the biomaterials high extensibility and important role for the mechanical and transport properties of
compressibility. For example, bionanocomposites composed of a nanocellulose-based bionanocomposites. Among manufacturing
rubbery polymer matrix and rigid CNCs demonstrate a reversible approaches, the unidirectional freeze-drying route or 3D printing
change with tunability within a wide range of the elastic moduli allow for the fabrication of unique materials with controllable
when exposed to environments that can mediate CNC interactions mechanical performance [199,249]. Strong and highly anisotropic
[265]. Functional biopolymers can be embedded into an elasto- aerogels can be constructed through ice-template freeze-casting
meric synthetic matrix to construct soft and highly stretchable suspensions of cellulose nanofibers, GO and sepiolite nanorods,
Fig. 14. (a) The CNCs/GO nanocomposites fabricated by spin-assisted LbL assembly; (b) the mechanical performance of CNCs/GO nanocomposites with other materials; (c) the
TEM image of cross-section of nanocomposites. Reproduced from [267] with permission. Copyright 2015 John Wiley & Sons.
which show excellent combustion resistance and low thermal particles, high specific surface area, and flexibility [222]. In a recent
conductivity of 15 mW/m/K [270]. Even at 30 ○C and 85% relative study, Singamaneni et al. [275] reported a novel BNC film-based
humidity, the foams retained their shape and more than half of SERS nanocomposites that combined BNCs and gold nanorods.
their initial compressive strength. Notably, individual CNCs Gold nanorods were uniformly and densely absorbed on the BNC
demonstrate excellent mechanical properties, and their use is surface across entire substrate, enabling the large SERS enhance-
regarded as a promising alternative for use in bulletproof armor ment and the detection of 1 nM rhodamine (R6G) and bacteria.
[271]. However, it is difficult for CNCs to retain their properties In addition, 3D plasmonic aerogels were fabricated by
when these nanoscale components are combined with synthetic integrating metal nanorods with highly porous BNC/silk aerogels
components into bulk materials. Overall, the mechanical perfor- (Fig. 15a) [175]. Unlike the relatively low SERS activity of 2D
mance of nanocellulose microfibers is still lower than composites substrate, the 3D aerogel demonstrated much higher sensitivity,
fabricated from commercial structural fibers from Kevlar and ultra- which allows detection of 10 fM of R6G. Additionally, these
high molecular weight polyethylene (UHMWPE) materials [233]. bioplasmonic aerogels showed other functionalities, including
Finally, the small-scale production and high cost of nano- the highly efficient solar steam generation through photothermal
cellulose components are bottlenecks for commercial structural heating.
applications even if the raw source availability is abundant that Plasmonic nanostructures for SERS can be formed in situ inside
limits their applicability in large-scale massive structural appli- of nanocellulose materials by the reduction of noble metal salts.
cations. Nanocellulose materials currently have no advantages For instance, by simply boiling HAuCl4 infused BNC hydrogel in
over natural wood materials in traditional building applications in sodium citrate solutions, Au nanoparticles of~60 nm in diameter
terms of both supply and price, although they are superior in terms can be uniformly formed throughout the BNC matrix [276]. The
of mechanical performance in specifically crafted nanomaterials resulting composite hydrogel is densely loaded with Au nano-
with controlled assembly of nanocomponents. Therefore, the particles and shows two broadened tunable localized surface
application of nanocellulose materials in the massive structural plasmon resonance (LSPR) peaks that indicates extensive con-
applications remain a grand challenge that needs more efforts to trolled interparticle coupling [276]. The highly porous morphology
address. plays an important role in enabling ensembles of plasmonic
nanoparticles that existing suspension-based SERS systems are not
2.2.2. Optical applications capable of functioning in [277]. For example, BNC hydrogels have
Nanocellulose-based optical devices include light and colori- been demonstrated to show excellent SERS signal reproducibility
metric monitoring of the biophysical, chemical and biological for the detection of environmental contaminants in low pH
changes with Raman, fluorescence, and UV–vis spectroscopies. For environment [276–279]. Conventional nanoparticle suspensions
instance, surface enhanced Raman Scattering (SERS) has the will likely uncontrollably flocculate under such conditions, and
capability of non-destructive and single-molecule sensitive common paper based substrate is unlikely to maintain its original
detection of analytes with noble metal nanostructures as active 3D structure.
substrates [272–274]. Compared to traditional glass and plastic Because of the ubiquitous presence of hydroxyl groups on BNC
film SERS substrates, nanocellulose substrates show many nanofibers, well dispersed Au nanocrystals sparsely populated
advantages, including strong interfacial interaction with nano- along nanocellulose fibers can be synthesized without the need for
Fig. 15. (a) Preparation of bacterial cellulose based plasmonic biofoam, reproduced from [174] with permission. Copyright 2016 American Chemical Society; (b) photo of
transparent and photoluminescent foldable nanocellulose/quantum dot nanopaper, reproduced from [291] with permission. Copyright 2015 American Chemical Society; (c)
photo and SEM of CNC based responsive photonic hydrogels, reproduced from [293] with permission Copyright 2013 John Wiley & Sons; (d) the preparation of near-IR-
sensitive upconverting nanostructured photonic cellulose films, reproduced from [294] with permission. Copyright 2016 John Wiley & Sons; (e) the scheme of chiral
plasmonic films nanostructure by co-assembly of CNC and gold nanorods, reproduced from [296] with permission. Copyright 2014 American Chemical Society.
external reductants [280,281]. The density and size of these Au network cannot be re-dissolved. Coupled with CNF’s low Raman
nanocrystals can be controlled by varying reaction time. Interest- background, the method results in highly sensitive (pM) detection
ingly, these BNC hydrogels form a unique multilayered 3D limit for R6B and dopamine with excellent reproducibility [283].
structure with relatively dense ultrathin layers separated by Moreover, nanoparticle loaded nanocellulose materials can also
regular spacing of several microns [282]. Another important aspect be used as a disposable colorimetric sensing platform. Plasmonic
of such hydrogels is that upon dehydration, the nanofibers shrink nanopapers produced via in situ synthesis of Ag and Au nano-
and tighten the interlock with each other, the interlayer distance particles in BNC platforms have been demonstrated to display
also decreases. This self-induced deformation is extremely sensitivity to specific types of chemicals [275]. For example, thiol
advantageous for SERS detection, as the porous structure of compounds such as methimazole can act as a molecular linker and
swelled hydrogel ensure the maximum adsorption of analyte promote Ag nanoparticles in the BNC platform to aggregate,
molecule onto Au nanoparticle surface, while the subsequent inducing plasmon coupling and color redshift. A similar chemical
drying creates strong coupling between the plasmonic nano- induced aggregation and color changes can be observed when Au
particles to form active SERS hotspots that greatly enhances the nanoparticle-BNC materials are exposed to thiourea, cyanide and
Raman signal of molecules trapped on the nanoparticle surface iodine. The chemical etching effect will cause the Ag nanoparticles
[282]. to shrink, resulting in detectable blue shift.
Nanocellulose materials are also exploited as a pre-formed Nanocellulose components can be used as templates to
substrate to direct the drying of Au nanoparticle suspensions to construct advanced chiral plasmonic nanostructures [285–287].
facilely fabricate high performance SERS platforms. In this Recently, both electron tomography and AFM studies have shown
approach, a sessile drop of concentrated CNF solution can dry that individual CNC rods are twisted along their axial in the right-
on a glass substrate to form a uniform CNF network [283]. This hand direction [17]. These unique molecular structures can be
network then acts as a pre-structured host to direct the local flow utilized to assemble plasmonic nanocrystals that align along the
of Au nanoparticle suspensions to form a widened “coffee ring” twisted nanocrystals. Resulting nanostructures display chiral
aggregation. Unlike the narrow “coffee-rings” formed by direct plasmonic properties at the single nanocrystal level. The actual
deposition of Au nanoparticle suspensions, which can be easily application of this principle is, however, more intricate. In practice,
disturbed by subsequent casting of analyte solutions [284]. The cationic spherical Au nanoparticle can be assembled on sulfate
CNF-AuNP nanocomposites are extremely stable, because CNF ester surface groups [285,286]. The chiral optical properties of the
Fig. 16. (a) Photographs and SEM images of neat CNC and CNC/PEG composite films; (b) Photograph and transmission spectra showing the reversible color change of CNC-2/
PEG (80/20) composite film in (a) under different relative humidity, reproduced from [300] with permission. Copyright 2017 John Wiley & Sons. (c) Color changes of MPC films
soaked in EtOH/H2O mixtures of different ratios; (d) Pressure induced color change of MPC film. Reproduced from [301] with permission. Copyright 2014 John Wiley & Sons.
assembled structures are closely related to the size of the Additionally, chiral nematic structures formed by CNCs have
nanoparticle. If the nanoparticles are too large compared to the garnered attention as either an LC template or as a host for
diameter of CNCs (= 7 nm), the size mismatch will prevent the developing active optical materials, if CNC components are
nanoparticles to follow the chiral twist of the CNC, yielding achiral combined with other nanoparticles (gold, silver, and rare earth)
structures. When nanoparticles of 8.5 nm diameter are used, chiral [226]. For example, flexible photonic nanocellulose films were
structures (30–60 nm in lateral dimension and 200–500 nm in fabricated by helicoidal co-assembly of CNCs with NaYF4:Yb,Er
length) displaying strong circular dichroism (CD) signals can be hexagonal nanorods [294]. These films showed not only upcon-
obtained [287]. version with near-IR light, but also retained tunable photonic chiral
Quantum dots, highly fluorescent semiconductor nanocrystals, activity (Fig. 15d). This approach has been extensively used for the
have drawn increasing attention due to their prospective alignment of Au nanorods of different sizes and aspect ratios. Au
applications in optical materials, biosensors, biomedical imaging, nanorods co-dispersed in nematic phase show orientation of Au
marker development, and anticounterfeiting [288]. Various types nanorods with the increase in CNC concentration [295]. The
of quantum dots were incorporated onto the nanocellulose resulting film showed a distinct polarization-dependent extinction
surfaces to fabricate transparent, smooth, and fluorescent nano- profile with the longitudinal and transverse mode of Au nanorods
paper materials. For example, carbon quantum dots that are low separately excited. Au nanorods co-dispersed in chiral CNC phase
toxic, nanosized, luminescent, and easy to functionalize, can be follow the orientation of CNCs in each layer and are arranged into a
covalently attached to cellulose nanofibers via covalent coupling helical configuration (Fig. 15e) [295,296].
[289,290]. Water-soluble ZnSe quantum dots modified by positive The structural color of CNCs in liquid crystal phases can be
charged polymer were added to the cellulose nanopaper surface by selectively modified by changing the spacing between each CNC
vacuum assisted filtration [291]. As shown in Fig. 15b, the as- layer. This can be achieved by the co-assembly of CNC with another
prepared nanopaper shows high optical transmittance and high compatible component such as various hydrophilic polymers
intensity photoluminescent performance. [297–299]. For example, CNC can be self-assembled with poly
CNC films demonstrate iridescent structure color due to their (ethylene glycol) (PEG) into uniform interlayered helical structure
long-range chiral nematic ordering, which showed great potential while retaining its chiral nematic phase [300]. The pitch size of the
for bio-optical devices, such as displays and biosensors [292]. multilayered structure can be controlled by the relative ratio of the
When exposed to various external environments, the pitch of two components, producing different structural iridescence
helical structures will change, leading to the variation of structural (Fig. 16a). Depending on the polymer component incorporated,
color of CNC films. It was reported that a responsive nanocomposite films like this can have many interesting properties. For
composite hydrogel can be prepared by assembly of CNCs with instance, since PEG has high affinity towards water molecules,
various hydrogel materials (Fig. 15c) [293]. These new chiral CNC/PEG composite films will have different water absorbing
hydrogels demonstrated tunable colors, respond to various stimuli, capabilities depending on the relative loading of PEG. More
including pH and solvent and temperature, resulting in the importantly, the infiltration of water causes the PEG layer to swell
variation of pitch. and changes the pitch size, hence color, of the cholesteric structure,
yielding stimuli responsive color changes (Fig. 16b) [300].
Fig. 17. (a) Comparison of transparent cellulose nanopaper and regular paper, reproduced from [305] with permission. Copyright 2009 John Wiley & Sons; (b) photo of a CNF
decal transfer with conductive traces conforming to an epidermal surface, reproduced from [315] with permission. Copyright 2014 John Wiley & Sons; (c) photo of organic
solar cell fabricated on CNC substrate, reproduced from [317] with permission. Copyright 2013 Zhou et al. licensed under CC BY 4.0; Photo and optical microscopy image of
transparent nanopaper-based organic light-emitting diode array (d), reproduced from [321] with permission. Copyright 2013 John Wiley & Sons, and gallium arsenide
microwave devices (e), reproduced from [29] with permission. Copyright 2015 Jung et. al licensed under CC BY 4.0.
The polymer can also act as a co-template for the construction of traditional flexible substrates for electronics including plastic film
mesoporous photonic cellulose (MPC) films. In one example of this and regular paper, cellulose nanopaper demonstrates unique
set up, CNC and urea–formaldehyde (UF) precursor are first co- advantages for these applications. Their excellent mechanical
assembled into a chiral nematic structure, the interlacing UF is properties ensure the stability of devices even after numerous
then cured into a resin. A subsequent KOH etching step removes bending and folding, while the high optical transmittance facilitates
the polymer network and produces a porous structure of CNC with transparency of flexible devices (Fig. 17a) [305]. Moreover,
preserved nematic order [301]. Apparently, the structural color of nanocellulose papers possess much lower coefficient of thermal
MPC film is highly sensitive toward the chemical nature of the expansion (CTE) < 8.5 ppm/K than plastic (CTE,~ 50 ppm/K) [306].
solvent. By simply varying the mixture ratio of EtOH/H 2O, the Their smooth surface with low roughness and high degradation
difference in induced swelling can shift the transmission peak from temperature allows the fabrication of high resolution electronic
430 nm (pure EtOH) to 840 nm (pure H 2O) (Fig. 15c). Due to its patterns even at high temperature environment. In the past years,
porous structure, the application of different pressure on MPC various electronic devices were integrated on these substrates,
films in the macroscopic level can be directly transferred to the including solar cells, transistors, organic light-emitting diodes
change in pitch size, making the film piezochromatic [301]. The (OLED), antennae, and touchscreens [307–310].
color change is completely reversible, suggesting potential Conductive circuits can be integrated on various substrates by
applications in facile color based pressure sensing. writing, printing, and vapor deposition (CVD). In the previous
decade, regular cellulose papers were widely used as substrates for
2.2.3. Electronic biodevices patterning various conductive components such as graphene [311],
Flexible wearable electronic devices are in a high demand for CNT [312], silver nanoparticles [313] and conductive polymers
various sensing and monitoring applications [302–304]. Although [314]. However, the emergence of transparent cellulose nanopaper
nanocellulose materials are not electrically conductive, they can materials can facilitate the fabrication of flexible and transparent
play the role in the electronic devices either as non-active (e.g., conductive circuits with high resolution. Recently, novel conformal
supporting substrates) or active components after adding conduc- electronic decals based on a CNF and pullulan bi-layer structure
tive additives. were reported [315]. In the approach, the circuit board on CNF layer
can be fabricated on targeted surfaces with complicated topogra-
2.2.3.1. Nanocellulose as flexible and transparent substrates for phy such as human skin or flowers (Fig. 17b). Additionally, these
electronic devices. Flexible substrates play an important role in transparent conductive materials can be deposited on the nano-
the flexible electronics as a major component, which determines the papers to prepare highly electrical conductive substrates for the
mechanical, optical, and portable robustness. Compared with electronic integration.
Fig. 18. (a) Nanocellulose based ionic diode, reproduced from [325] with permission. Copyright 2012 American Chemical Society; (b) scheme of preparation of CNC aerogel
based supercapacitors, reproduced from [326] with permission.Copyright 2015 John Wiley & Sons ; (c) the scheme of the formation of proposed core–shell PPy coated CNC.
PVP was adsorbed onto the CNC surface prior to the polymerization to promote the homogeneous growth of PPy shell and the responding TEM images, reproduced from [327]
with permission. Copyright 2014 Royal Society of Chemistry; (d) scheme of LbL assembly of the CNF aerogel based energy storage materials, reproduced from [328] with
permission. Copyright 2013 John Wiley & Sons.
The solution processing of bionanocomposites allows solar cells In another study, Wu et al. [327] used poly(N-vinylpyrrolidone)
to be constructed on large-area substrates [316]. For instance, (PVP) coated CNCs as templates to in-situ polymerize polypyrrole
Kippelen et al. reported that polymer solar cells can be fabricated (PPy). These PPy uniformly coated CNCs surface to form a well-
on optically transparent CNC substrates, which showed good defined core–shell structure. As shown in Fig. 18c, the size of the
rectification in the dark and good conversion efficiency (Fig. 17c) PPy modified CNC significantly increased and no aggregation was
[317]. Notably, these solar cells on the CNC substrate will observed. These highly uniform PPy-CNC nanostructures exhibit
disintegrate when exposed to water at room temperature. largely enhanced electrochemical performance with an outstand-
On the other hand, CNF-based nanopapers have better ing conductivity of 36.9 S/cm, specific capacitance of 323 F/g and
flexibility than the rigid CNC paper [318]. Recently, foldable solar excellent cycling stability.
cells were fabricated by integrating organic cell components on the In an alternating approach, Hamedi et al. [328] explored LbL
transparent conductive nanopaper substrates [319]. The conduc- assembly of poly(3,4-ethylenedioxythiophene):poly(styrenesulfo-
tivity of the transparent nanopaper from CNFs and silver nano- nate) (PEDOT:PSS) and sodium poly[2-(3-Thienyl)ethoxy-4-butyl-
wires almost unchanged after repeated multiple foldings. sulfonate] (ADS2000P), and single-wall CNTs (SWCNTs) on the
Moreover, solar cells integrated on the nanopaper exhibited a chemically crosslinked cellulose nanofiber aerogel surface to
power conversion efficiency of 3.2%, comparable with ITO glass- fabricate charge storage devices (Fig. 18d). Benefiting from the
based solar cells. high porosity close to 99%, supercapacitors fabricated from these
Flexible organic field-effect transistors with high transparency aerogels show excellent specific capacitance values up to 400 F/g,
fabricated on nanopapers demonstrated outstanding transmit- exceeding the best reported CNT based supercapacitors. In another
tance and flexibility [320]. Flexible CNTs were introduced on the recent work, the authors used the same method to fabricate
nanopaper as a gate component. The good compatibility between compressible interdigitated thin-film supercapacitors and batter-
polymer and cellulose nanopaper allows only a 10% decrease in ies by using nanocellulose materials as templates [329].
mobility when experiencing bending or folding, while maintaining
high optical transmittance. In another study, Fujisaki et al. [321]
successfully fabricated large-area organic transistor array on a 2.3. Other polysaccharides: brief introduction
nanopaper by lithographic and solution-based processes (Fig. 17d).
These flexible transistors benefited from the ultra-smooth surface 2.3.1. Chitin and chitosan
of nanopaper and exhibited a high hole mobility of up to 1 cm2/V/s. Chitin is the second most abundant biopolymer produced by
Zhu et al. [322] manufactured OLED devices on transparent nature after cellulose, and can be found in marine crustaceans,
nanopaper, which exhibits very little difference in terms of — JV shrimp and crabs. Chitins are known to be cellulose analogues with
curve before and after bending. Jung et al. [29] reported large-area a (1,4)-b-N-acetyl glycosaminoglycan-repeating structure (Fig. 1)
gallium arsenide microwave devices deposited on nanopaper (Fig. [330]. Naturally occurring chitin shows highly ordered crystalline
17e). These devices demonstrated comparable performance to their microfibrils for constructing these structural components in the
rigid counterparts, and can be biodegraded by fungi. Other exoskeleton of arthropods or in the cell walls of fungi and yeast to
electronic devices such as touch screens, touch sensors and provide structural integrity and protection [331]. To obtain pure
antennae can also be efficiently constructed on the nanopapers colorless chitin, natural chitin sources are treated by acid and
[310,323,324]. alkaline in order to remove the calcium carbonate and soluble
protein components, respectively. A decolorization step further
2.2.3.2. Nanocellulose as active components in the electronic removes residual pigments. Chitin is basically insoluble in
devices. To function as active components in electronic devices, common solvents such as water and organic solvents due to the
nanocellulose materials should be modified to obtain acceptable hydrogen bonded structures similarly to nanocellulose.
electrical conductivity. These modifications involve surface Ionic liquids and NaOH/urea were found to be good solvents for
grafting, in-situ growth, post-coating, and blending of both cellulose and chitin [332,333], and thus can be used to
conductive components such as conductive polymers, carbon- based prepare various chitin materials, including fibers, films and
materials and metal nanoparticle. For example, Zhang et al. aerogels. By partial deacetylation under alkaline conditions,
[325] used a two-step (oxidation and sulfonation) method to chitosan can be obtained, which is the most important chitin
produce negatively charged cellulose nanofibers, while positively derivative. The NH2 groups on the chitosan backbones provide
charged cellulose nanofibers were prepared by grafting quaternary positive charges, enabling the good solubility of chitosan in the
ammonia salt. These two types of cellulose nanofibers were slightly acidic water. Additionally, these positive charges also
successfully integrated into a new biopolymer based ionic diode provide the possibility for the interfacial strength enhancement
device, where cations and anions can selectively transport under through the strong electrostatic interactions. Notably, native chitin
positive and negative bias due to the different charged cellulose nanofibers can also be obtained from natural sources by simple
nanofibers (Fig. 18a). mechanical treatment after the removal of proteins and mineral,
Various conductive materials were incorporated with nano- such as grinding [334], ultrasonication [335] and high pressure
cellulose to construct a wide range of electronic devices form homogenization [336].
supercapacitors to biosensors. Yang et al. [326] demonstrated that The elementary chitin nanofibers might have a diameter of 3–
CNC aerogel can act as a universal support for various conductive 4 nm [335], although the majority of these nanofibers have a
components to fabricate flexible light-weight supercapacitors with diameter of 10–100 nm [334,337,338]. Besides, chitin nanocrystals
high performance. The combination of two kinds of CNC with can be prepared by acid hydrolysis of amorphous domains of
NHNH2 and — —CHO functionalities will induce the gelation of CNCs semicrystalline chitin. Chitin nanofibers also possess excellent
by chemical bonding (Fig. 18b). During the gelation, polypyrrole mechanical performance and their film are highly transparent,
nanofibers (PPy-NF), (B) polypyrrole-coated CNTs (PPy-CNT), and ultra-smooth, and electrically insulating. For example, Jin et al.
(C) spherical manganese dioxide nanoparticles (MnO2-NP) can be [339] demonstrated the chitin nanofiber paper prepared from
incorporated into this system. After the freeze-drying, these hybrid squid-pen can be used as transparent flexible substrate for OLED.
aerogels can be used as supercapacitors and show excellent Hosseini et al. [340] reported a flexible and transparent resistive
capacitance retention at high charge–discharge rates due to their switching memory chips based on chitosan films, which is
high porosity and uniform 3D morphology. biodegradable and decomposable when exposing to water.
2.3.2. Alginates common tertiary structures: fibrous, globular, membrane, and

Alginate is an anionic biopolymer typically extracted from disordered. Disordered and globular proteins tend to function as
brown seaweed by alkali treatment, and widely used in the enzymes or catalysts. Membrane proteins facilitate transport of
biomedical applications because of its good biocompatibility, low- species between extracellular matrices and carriers.
cost and easy-processing [341]. It is a linear copolymer with blocks Fibrous proteins offer reinforcement and elasticity to tissue and
of (1–4)-linked b-D-mannuronate (M) and a-L-guluronate (G) bone. In human skin, collagen fibers confer toughness and
residues, covalently linked together in different sequences, and its flexibility [348]. Fibrous proteins derive their strength from a
chemical structures highly depends on the natural sources (Fig. 1) hierarchical micro/nano morphologies [259]. This mix of strength,
[342]. Alginate is a water soluble biopolymer, which can be biocompatibility, and facile processing have made fibrous proteins
crosslinked by the divalent cations such as Ca2+ for preparing the a common additive in biocomposites for a range of applications
hydrogel because of the presence of abundant carboxyl groups in from actuating soft materials and flexible electronics to drug laden
the molecular chains [343]. scaffolds. Silk materials have been thoroughly studied with respect
The compliance that matches the extracellular matrices of to each attribute, so this example will be the focus in following
living tissues enables applications in wound healing, drug delivery, discussion of respective bionanocomposites.
and tissue engineering. For example, alginate hydrogels can
preserve a stable, moist environment for wound tissue healing 3.1. Overview of silk: source and structure
to minimize infection risk [344]. Some active agents or anti-
bacterial drugs can also be incorporated into the hydrogel to Natural silk is a fibrous protein expressed by many arthropods
further facilitate the wound healing [345]. Alginate can act as a bio- including spiders, silkworms as well as flies and silverfish. Each
surfactant for dispersing various nanoparticles, such as graphene arthropod produces silk with different amino acid structure and
and 2D transition metal dichalcogenides, for providing them different propensity for beta sheet, helical, and amorphous
enhanced biocompatibility and interfacial strength with other structures (Fig. 19a and b) [349–352]. The spider’s major
matrices. For example, Zong et al. [346] reported that sodium ampullated spidroin functions as a high modulus dragline
alginate can high efficiently exfoliate and disperse the tungsten preventing insect prey from falling. It consists of mostly glycine
disulfide (WS2) nanoplates to obtain stable dispersions. Then, and alanine residues. The alanine portions stack to form b-sheet
tough and strong bionanocomposites can be fabricated from this crystals while glycine introduces amorphous structure and
dispersion, which demonstrated good multi-responsive response conformation. Fibers from the minor ampullate consist of non-
to humidity and light. Kovalenko et al. demonstrated that the repetitive, conserve C and N termini peptides dominated by glycine
combination of Si nanopowder with alginates can result in a stable and alanine dominant non-repetitive central sequence [353]. This
anode possessing reversible capacity eight times higher than that structure confers the fiber tensile strength and extensibility
of conventional graphitic anodes [347]. needed to wrap and preserve prey.
Factors such as the source, arthropod’s diet, and living
3. Proteins for bionanocomposites environment also effect silk properties. Commercial silks used
in textiles is produced by Bombyx mori, or mulberry silkworms,
Primary configurational protein structures or protein sequences then extracted and wound into fibers. When Nicodemo enriched
usually fold and interweave to form secondary structures with the leaves with specific amino acids like valine and threonine prior
ordered components such as beta sheet, turns, and helices, as well to silkworm consumption, silkworm mortality and cocoon weight
as amorphous coils [48]. Further assembly yields one of four was relatively unchanged [354]. However, the silk produced by
Fig. 19. Key hierarchical structural features of Bombyx mori silkworm cocoon silk (a), reproduced from [349,352] with permission. Copyright 2013 John Wiley & Sons,
Copyright. Copyright 2003 Springer Nature; and spider silk (b), reproduced from [48] with permission. Copyringht 2010 Springer Nature.
silkworms on the amino acid enriched diets had higher tensile amorphous sections (Fig. 19b) [48]. The hierarchical, semi-
strength than those fed untreated Mulberry leaves [355]. Similarly, crystalline fibers exhibit non-linear stress-strain behavior as their
feeding the silkworms spray dyed leaves produces silk cocoons of ordered structure unfolds in response to strain. In the Nephila
the same color. Some groups have even engineered graphene and clavipes orb weaving spider, the semi-crystalline structure is
nanoparticle containing silks by feeding the silkworms leaves formed by ordered poly(alanine) stretches mixed with beta-turns,
coated in the desired filler or active agent [74]. and amorphous spacers. GPGQQ subsections create beta-turns
Within the arthropods, silk production is impacted by while GGX sections, where X is glutamine (Q), tyrosine (Y), and
physiology, spinning speed, and cytology. Environmental con- leucine (L), form 310-helices. The b-turn which form spirals and
ditions would conceivably affect the organism’s health and thus helical sections are not as common in silks from other species,
physiology. Spiders tend to move faster under high temperatures allow spiders to make more flexible silks for applications where
and spin silk faster. Increased reel speeds then lead to fibers with toughness is less needed than in dragline silk. The spider silk fibers
higher tensile strength and narrower diameters [356]. Upon are usually obtained by direct extraction from a spider, drawing
extrusion, spider silk fiber dimensions and strength were from their spinneret, or expression from E. coli.
influenced by temperature [351]. Additionally, humidity can also Silks have three common polymorphs: coiled silk I, b-sheet
alter silk properties by facilitating rearrangement under high crystalline silk II, and helical silk III [358,363,364]. Glandular silk
humidity and locking in the initial extruded conformation via has secondary structure of silk I. This is characteristic of silk ex vivo
dehydration [356]. solution state. Mechanical stress like stretching or shear as well as
Although, many insects produce silk, Bombyx mori and Nephila heating cause a transformation to silk II polymorph. The shear and
clavipes are the easiest to obtain and extract silk [350,357]. Spiders pulling endured during spinning from the silk gland cause this
have six silk glands, two each at their anterior, median, and shift. Solvents and buffers can be used for the same effect [365].
posterior. At these silk glands, the aqueous dope resides as a liquid The silk II b-sheets exhibit strong inter and intramolecular
crystalline solution prior to fiber forming during extrusion. Spiders hydrogen bonding and van der Waals interactions. This polymorph
produce tubuliform silk as a protective coating for egg sacs, is largely insoluble and requires treatment with chaotropic agents
aciniform silk to wrap prey and egg sacs, course flagelliform fibers for processing. The abundance of inter and intramolecular bonding
to capture prey on orb webs, piniform to anchor non-silk surfaces, in the silk II polymorph contributes strength and stability under
minor ampullate to coat as a non-sticky web scaffolding, and major heat.
ampullate to act as a safety line. Though, Bombyx mori cocoon and Nephila clavipes dragline silk
Silk from the Bombyx mori starts in the same state as an aqueous boast high toughness and extensibility, spider major ampullate
suspension of proteins and ions silkworm glands [349–351]. The spidroin is the strongest and most extensible silk available with
silkworm forces this suspension out through a spigot in a figure tensile modulus comparable to Kevlar and greater strength to
eight to form the many layers of its cocoon (Fig. 19a). This cocoon density ratio than steel [366,367]. Major ampullated spidroin is
insulates the silkworm from temperature and humidity fluctua- often harvested from spider glands then rinsed copiously to
tions, protects it from ultraviolet rays, bacterial and fungal threats remove the gummy outer layer. Artificial spider silks are available
as well as predators. A closer look at the cocoons shows silkworm but expensive and usually are not comparable to the natural
silk derives tensile strength from its semi-crystalline structure, products.
imperviousness from densely layered cocoon microstructure, and Bombyx mori silk production is a centuries old industry that
resistance to radiation to protein based coatings on the fibers. produces millions of pounds of silk per year [368]. Though inferior
Silkworm fibers are 10–25 um in diameter and consist of two to major ampullated spidroin, silkworm silk is still one of the
fibroins bound by hydrophilic gumming proteins and sericins strongest natural fibers available that makes silkworm silk the
which comprise 25–30% of silk cocoon mass [358]. The fibroin most commonly used silk in research and the most economical
reduces to many fibroin fibrils of silk molecules of glycine (43%), choice for composite-based devices. Thus, further discussion of silk
alanine (30%), and serine (12%) [359]. The fiber structure resembles structure, properties and processing will focus predominantly on
a hydrophobic co-polymer with alternating 390 kDa heavy chain the more abundant Bombyx mori silk. Although spider and
and 25 kDa light chain sections joined by one disulfide bond with silkworm silks differ compositionally, their higher order structure,
each comprising an equal proportion of the fiber [360]. The heavy properties, and processes are similar with some major differences
chain forms the crystalline fiber regimes with aliphatic amino to be noted.
acids glycine and alanine assembled into a series of hexapeptides:
GAGAGX or GAGXGA, where X is alanine (A), serine (S), valine (V), 3.2. Processing of silk: extract, chemical and non-chemical
tyrosine (Y), and threonine (Thr). GAA or GAGS cap the subdomains manipulation
(Fig. 19a) [349].
Aliphatic amino acids make up this section, rendering it Processing can affect silk structure and ultimately the silk
hydrophobic. Poly(alanine) in major ampullate spidroin, the properties. Fundamental studies have been conducted on untreat-
hydrophobic GAGAGX portion, produces anti-parallel b-sheet ed silk fibers to establish current understanding of the natural
crystals. Non-repetitive peptides intersperse up to 12 domains of fibers. However, for composites, the silk protein is typically
the hexapeptides [361]. Eleven non-repetitive light chains link 12 extracted and treated to facilitate aqueous processing [350]. First,
heavy chain domains. The light chain has 25 amino acid sequence, silk cocoons are boiled in an alkaline solution to extract the sericin
consisting of proline, charged residues lysine and arginine, and proteins. Cutting the cocoons or delaminating them prior to sericin
tryptophan. Charged residues lend the domain hydrophilicity, extraction can expedite this process. Sericins break down, and the
while proline introduces turns that wind its mix of helices, beta degummed silk is washed copiously to remove degraded sericin
sheets, and turns into an amorphous globular linkage between and residual alkaline salts. Without degumming, sericin would
crystalline domains [361]. Single cysteines form disulfide linkages induce silk aggregation in solution. This process also reduces silk
between the heavy and light domains. molecular weight and can be used to produce silk of specified
Spider silk fibers consist of a fibroin encased in gumming molecular weights.
protein [362]. Each fibroin is a several micrometers wide bundle of Degummed silk fibroin can be spun into fibers and ropes, cast as
fibrils where hydrophobic sections of the protein primary structure a non-woven, or further treated for aqueous dissolution. The first
have assembled into nanocrystals nestled between neighboring two processes are more common industrially and limited in
materials research and design. Aqueous dissolution, also known as processing mechanical properties. Silk assembly is primarily
reconstitution, opens silk to a wide array of fabrication methods; controlled by shear stresses and water loss during processing,
thus, aqueous dissolution is a preliminary step for developing most which causes assembly of rod-like structures and branched linear
silk containing devices. structures of native and reconstituted silk fibroin, respectively
From the solution state, silk can be electrospun to form mats, [372]. In addition to shear and water loss, silk fibroin structure may
lyophilized to form porous sponges, noncovalently crosslinked to be tuned by chemical modification, solvent and water annealing in
make gels, or cast into films. Silk reconstitution begins with order to alter hydrogen bonding and ion pairing [373,374]. By
dissolving silk in 9.3 M LiBr solution then dialysis against water. manipulating b-sheet content, silk fibroin toughness and strain at
LiBr is a chaotropic salt used to disrupt inter and intramolecular break can be tuned over a wide range of values. For instance, it has
hydrogen bonds inherent to the silk II structure of degummed silk been shown that exposure to alcohols, particularly methanol,
[369]. Other lithium based salts and chaotropic salt/solvent blends induces a rapid conformational transition from amorphous
work as well, however, silk is most soluble in LiBr. However, like random coils to crystallization as b-sheets thus increasing strength
degumming, treatment with chaotropic salts has adverse effects. but reducing ultimate strain [365].
Disrupting silk-silk hydrogen bonds shifts the structure from silk II Water as a solvent may also induce a conformational shift from
to silk I, a weaker polymorph and less stable. To this end, Koebley random coils to helices and b-sheets [375]. At temperatures below
et al. reported that the dissolution process damages binding sites 60 ○C, the random coil content decreases and leads to an increase in
that enable native silk to assemble into 1D fibers upon shearing helices and b-sheets secondary structures. At higher temperatures
while reconstituted silk cannot [370]. b-sheets become the dominant structure (Fig. 20a). In this method,
There are a few viable alternatives to these noxious processes. water molecules effectively plasticize silk fibroin to increase local
For silk harvested from silkworm glands, copious washes with chain mobility while thermal mobility provides energy necessary
deionized water will remove sericin and produce an aqueous silk to transition from random coils to crystalline b-sheets. Initial
slurry, requiring no noxious agents to achieve an aqueous silk studies implementing this method saw silk crystallization of 60%,
suspension [370,371]. Unfortunately, this method is only viable for the maximum achievable with silk fibroin.
fundamental studies and interaction studies, not for large-scale Genetic engineering affords greater control of silk-based
composites. For cocoon silk, ionic liquids used to solvate cellulose biomaterial properties [376,377]. These methods tend to be
were employed to dissolve silk prior to and after sericin removal. 1- truncated silk-like structures primarily used for fundamental
butyl-3-methylimidazolium (BMIM) based ionic liquids success- adhesion and cell encapsulation studies. Drachuk et al. created cell
fully reverted the silk II–silk I, disrupting protein-protein hydrogen and drug capsules using alternating layers of silk modified with
bonds [369]. BMIM with bromide counter ion did this while lysine and glutamate (Fig. 20b) [378]. The lysine and glutamate
dissolving sericin, showing that BMIM Br could be used to bypass functionalities have opposite charges whose electrostatic attrac-
the alkaline salt and chaotropic agent treatments for degumming tion allow for LbL membrane assembly. Silk-like peptides modified
and reconstitution, respectively [369]. either with poly-lysine and poly-glutamate are used to create drug
Furthermore, methods have been established to tune silk delivery vehicles. Addition of charged amino acids and much more
primary and tertiary structure in attempt to partially recover pre- is possible with silk fibroin thanks to the hydroxyl groups on
Fig. 20. (a) The effect of thermal vapor annealing on silk crystallinity, reproduced from [375] with permission. Copyright 2011 American Chemical Society; (b) Silk ionomer
electrostatic interactions on silk microcapsule fabrication, reproduced from [378] with permission. Copyright 2015 American Chemical Society.
threonine, serine, glutamic acid, aspartic acid, and tyrosine When biomaterials remain in the body, degradation occurs and
residues. However, less than 4% of silk residues contain hydroxyl the degradation products become a kind of debris that set off
groups. adverse reactions. There are many ongoing investigations into
Silk is amphiphilic and contains many sites for hydrogen understanding this immunologic response and how this response
bonding, van der Waals interactions, and electrostatic interactions is affected by the size and morphology of degradation products.
[48,349,350,361]. Hydrophobic species will adhere to silk surfaces. The degradation rate of reconstituted silk depends on secondary
Ionic interactions with silk fibroin are similarly mediated. For and supramolecular structure. For example, silk fibers degrade
instance, Yin et al. created laminated silk-GO composites to faster than fibroin. Wang et al. [392] reported the degradation of
capitalize on these interactions between polar silk moieties and 3D silk scaffolds implanted in rat models within three weeks with
GO’s hydroxyl and epoxide groups. In doing so, they achieved a 6% complete disappearance after one year. The study showed that silk
increase tensile modulus and three-fold increase in elasticity over is both biodegradable and resorbable, meaning that silk will break
contemporary silk-GO composites [379]. The complementary into smaller components that can be carried by fluid transfer and
multi-domain interfacial interactions facilitated stress transfer filtrated or metabolized by the body.
through the composite. The silk crystalline formation fostered via Silk’s ease of modification also allows one to engineer its
silk-GO hydrogen bonds provided added reinforcement. degradation path and kinetics. And the same means used to control
Despite the existence of many modification methods, the degradation can be used to tune mechanical properties. In nature,
performance characteristics of raw silk remains elusive. While silk produced by the same organism can have vastly different uses
many methods exist for silk crystallization, few methods allow and performance characteristics. This differentiation derives from
exact control over degree of crystallinity or directionality of changes in inter- and intra-molecular interactions which define
crystallites [380]. However, these methods grant control over their supramolecular structure. These differences are enacted via
reconstituted silk fibroin structure and interfacial interactions that changes in composition, ionic gradients, drawing speed, and drying
define mechanical and active performance. This control matched conditions of released silk [48]. Likewise, silk-based composite
with degummed silk’s biocompatibility make silk readily applica- mechanical properties can be tuned via chemical and non-
ble to a variety of design challenges. chemical modification of silk microstructure.
One common problem for reconstituted silk fibroin is poor
3.3. Applications of silk nanocomposites control over crystal confinement and composition. Methanol-
annealing, shearing, heating, and many more methods can
Numerous studies have shown silk’s potential utilities in a host facilitate a full transition from silk I to silk II within a few minutes,
of applications including hydrogels, core-shell particles, tissue but the degree of crystallinity is difficult to control [393–395].
scaffolds, and nanocomposites [381–388]. Highly elastomeric Hydrogen bonds form quickly within silk molecules, leaving little
natural biomaterials enable the effective load transfer between time for reorientation into directions for maximized strength
reinforcing and functional nanoscale fillers through an array of [395]. Resulting silk structures have high moduli but exhibit brittle
hydrophobic, van der Waals, electrostatic, and hydrogen bonding fracture. Poor control over crystallinity also effects degradation
interactions. Generally, silk materials serve as a matrix for reactive kinetics because increased crystallinity lengthens degradation
and functional components with a variety of inorganic or carbon time. Hu et al. showed that the thermal water vapor annealing
components [389]. Optically active components lend functionality method enables better control over degree of crystallinity and
as sensing and energy storage devices while the elastomeric degradation kinetics [375]. The study provided a discrete outline of
bioderived matrix confers flexibility and biocompatibility [390]. which temperatures to use in this process to achieve specific
Silk also offers a matrix for nanofiller loading and adjustable degrees of crystallinity, degradation rate, and toughness.
mechanical, degradation, thermal, and optical properties. Similar results were achieved by introducing plasticizer
glycerol to silk films. Glycerol impede some intra- and intermo-
3.3.1. Biomedical applications lecular silk-silk interactions, while facilitating others. This results
Biological processes on the human body such as blinking, in change from silk I to disordered silk II structures, where
breathing, and renewing are highly complex processes. These heterogeneity and dispersion of beta sheets allows for retained
processes rely on controlled concentration gradients to send flexibility. Glycerol infused films exhibited comparable crystallini-
messages along a synapse, unraveling of DNA to encode production ty to water and methanol annealed silk films after removal of
of new cells, and pH and thermal control to ensure key enzymes glycerol and with ductility 21 times greater than water annealed
retain their activity. Hydration, ion concentration, pH, and samples [396].
hydrophobic interactions effect the hierarchical structure of our Di-tyrosine crosslinking is a chemical alternative to non-
body’s tool and processes needed for daily function. Biomaterials chemical modification of hydrogen bonding. Most notably
must be designed to perform to their desired functions without horseradish peroxidase facilitates tyrosine crosslinking of proteins
adversely impacting the body’s regular functions and answer some in the presence of free radicals from hydrogen peroxide. Partlow
critical questions. Does the composite match the mechanical et al. have demonstrated the utility of HRP crosslinking in tuning
properties and structure of the organelle it supports? How does the elastomeric properties of silk hydrogels that are also fully
construct impact adhesion, growth, and differentiation of cells? degradable thanks to their all-natural constituents [397]. Resulting
And, any biocomposite desired to be used in situ must be either systems have the elastic modulus up to 10 kPa and Exhibit 100%
retrievable or biodegradable. strain rarely seen in silk-based hydrogels. Even hydrogen peroxide
Fibrous proteins, particularly silks, have proven adept at alone can induce a silk I–silk II shift comparable to methanol by
meeting these design criteria. Silk suture have been employed redox driven disulfide crosslinking of cysteines on silk-elastin-like
as biocompatible sutures for centuries. Silk sutures elicited few proteins [398].
adverse reactions, and those sited have been linked sericin. When Silk has been applied to many biomaterial applications
properly degummed and sterilized, silk has proven successful in including as capsules, scaffolds, and films. Beyond meeting
short term uses with biocompatibility comparable polylactic acid fundamental design criteria, silk has broad applicability in
and collagen [391]. However, it falls short like many of its biomaterial design owed to its multifunctionality [399–401].
contemporaries in extended use applications in the body. A major Silk-like peptides can also be used to create actuating films. For
immunological trigger is debris. instance, Ye et al. constructed LbL films using alternating active silk
Fig. 21. (a) The fabrication of bimorph silk ionomer films using lithography, reproduced from [399] with permission. Copyright 2016 American Chemical Society; (b) The
effects of dip coated then crystallized silk films on strawberry preservation, reproduced from [401] with permission. Copyright Marelli et. al licensed under CC BY 4.0; (c) Silk
microneedle patches for subcutaneous delivery (d), reproduced from [405] with permission. Copyright 2011 John Wiley & Sons.
ionomer and passive crosslinked silk b-sheet layers as shown in Silk’s suitability for enzyme entrapment stems from its ease of
Fig. 21a [399]. After deprotonation, the silk ionomer layer swells, functionalization. This property, partnered with facile aqueous
and the differential stress between the swollen silk ionomer layer processing, make it possible to design many constructs with drugs
and constant volume crosslinked layer will induce film folding or other functional components loading. Just as silk capsules and
[399]. This folding effect was also achieved with silk-polymer films have been used for enzyme entrapment and release, other
composites. In another example, Romera et al. constructed more complex structures can be built using silks. Thanks to
actuating silk-polypyrrole composites [400], where the polypyr- micromolding, drug loaded silk-microcapsules have been designed
role was functionalized onto porous silk fibroin films. Upon to deliver drug innocuously from a microneedle patch (Fig. 21d)
electrical stimulation, polypyrrole releases anions and contracts as [405].
the silk layer expands.
Silk microstructure control also open paths toward preserving 3.3.2. Biodevices from silk materials
organic matter. To this end, Marelli et al. exerted control over The advantages of silk as a biomaterial carry over into its usage
crystal confinement to produce silk membranes that prevent fruit in bioelectric composites. Although, silk fibroin is not electrically
degradation [401]. They dip coated various fruits including conductive, it can be integrated into conductive biocomposites by
bananas and strawberries in aqueous silk fibroin followed by compounding with electronically active components. If for use in
water annealing for twelve hours to reach 53% beta-sheet content. vivo, degummed silk offers the benefits of low immunogenicity and
Fig. 21b shows pictures of untreated (i and iii) and treated (ii and controllable biodegradation. For use on spherical or non-uniform
iv) at time zero (i and ii) and after seven days (iii and iv). The highly surfaces, silk confers flexibility. This same flexibility partnered
crystalline protein film impeded permeation of air and preserved with engineered extensibility make it ideal for use in strain sensors
the strawberries for up to a week at room temperature. This for skin deformation. In all these areas, silk fibroin forms a
capability is being applied to preservation of enzymes and other lightweight flexible, extensible, bio-compatible matrix for loading
active biological matter. of electrically active components.
The tunability of silk makes it adept in this area where selective For example, Hu et al. created skin-mounted tactile sensors
degradation determines a drug’s effectiveness and controlled using one-pot batch processes to make large-area films. They used
permittivity ensures activity even after shipping. Silk based one-pot silk-GO mixture to lay large area, conformal bio-paper and
structures are used to stabilize enzymes like HRP and lipase used electrochemical reduction by aluminum paste to form circuits
[402,403]. More recently, silk has proven effective in stabilizing of (Fig. 22a) [5]. Moistening the metal-GO junction, either by
complex matter such as blood. Blood contains proteins, lipids, deionized water or human skin, generates an electrical potential.
peptides, enzymes, and metabolites used as biomarkers by The humidity sensing films exhibited fast activation, deactivation,
physicians. Kluge et al. used silk matrix encapsulation to preserve and recovery rates when cycled with each output of equal and
blood through elevated temperatures and freeze-thaw cycles opposite magnitude. Additionally, the output did vary according to
(Fig. 21c) [404]. These initial results can be considered as a proof of the magnitude of water molecular and bio-electrolyte ion
concept for the future of blood sample transport and preservation. presence, suggesting that this could also be used for qualitative
Fig. 22. (a) Silk-graphene oxide composite based tactile sensor, reproduced from [5] with permission. Copyright 2016 John Wiley & Sons; (b) Depicts stress and thermal
sensor with silk fibroin substrate for cardiac mapping in animal models, reproduced from [25] with permission. Copyright 2010 Springer Nature; (c) Silk based sensor for
detection of food degradation, reproduced from [28] with permission. Copyright 2012 John Wiley & Sons.
Similar techniques have been applied to for detection across the

analysis of water ionic content. Ma et al. then expedited the process
electromagnetic spectrum.
for creation of similar devices capable of operating as proximity
Optical biological sensing applications not only benefit from the
sensors with large-volume scalable screen printing [191].
previously mentioned substrate characteristics but also from silk’s
Kim et al. constructed similar devices where silk fibroin, not its
capacity for enzyme stabilization [187]. As Domachuk et al. show,
functional filler, was the most prominent component (Fig. 22b)
silk matrices can be readily loaded with optical elements using
[25]. They fabricated transparent, soluble substrates for electrode
lithography [409]. At the same time, they immobilize hemoglobin
arrays from concentrated silk fibroin. Polyimide undergoes
onto the silk film. This creates an oxygen sensor since hemoglobin
photolithography and patterned etching to form wire like planar
is an enzyme used to in the body to oxygenate blood cells. Added
electrode arrays. The high concentration silk fibroin forms a more
structural complexity in the form of microfluidic pathways
gel-like film. This partnered with the thin circuitry design rendered
demonstrate the breadth of conformations and microstructures
films that conformed to a feline brain. The devices successfully
for optical and electrical devices enabled by silk substrates and
mapped neural activity over select electrodes, however half had
matrices. Just as silk can be a passive component, it can also
poor contact with the brain and didn’t produce reliable neural
contribute optical activity. In nature, sericin affords silk cocoons
response data.
their color and protection from electromagnetic radiation. In one
This same technology has even been applied to map deforma-
instance, Muller et al. submerged silk fibroin fibers in PEDOT-S
tion of the heart as it pumps [406]. The main design modification
solution to create electrochemical transistors [410]. Integrating
was use of kirigami in creating the nanowire electrode. The wires
functionality in to silk fibroin itself rather than substrate or matrix
were cut to have curvilinear profiles, introducing added extensi-
functionalization enables the creation of optical and electrically,
bility through effectively longer interconnects. This technique
active textiles.
enhanced the composites’ ability to actively deform with the heart.
Finally, even if silk shares strengths with its fellow fibrous
The device mapped temperature, electrophysical signals, and
proteins like keratin and collagen, key differences between the
strain in animal models. Recent implementations have been used
proteinaceous components define their different properties as
ex vivo in proofs of concept for wearable device platforms. These
outlined in the following section.
include strain sensing temporary tattoos and temperature
mapping films with energy storage capability [407,408].
Silk’s lightweight and dexterity have also found use in optically 3.4. Other fibrous proteins for bionanocomposites
active devices. Tao et al. took advantage of constructs previously
discussed and exchanged electrodes and metal-GO junctions for 3.4.1. Collagen and gelatin
optical or photonic components like dyes or quantum dots [28]. Fibrous proteins have compositions, and therefore require
They printed a gold array on silk substrate. The resulting film different processing conditions and yield different performance
readily conformed to several edible samples: a banana, a slice of characteristics. Although silk has been an area of intense research
cheese, and, as shown in Fig. 22c, an egg. The devices detected focus, here we explore existing literature in three other major
bacterial contamination on solid foods as well as in a glass of milk. classes of fibrous proteins: collagen, gelatin, and keratin. Although,
Fig. 23. Schematic summarizing the sources, extraction process, and applications of collagen, gelatin, and keratin. Ocular lens is reproduced from Ref. [416]. Copyright 2011
Elsevier; Knee scaffold is reproduced from [417] with permission. Copyright 2015 Springer Nature; flexible film is reproduced from [418] with permission. Copyright 2015
Johns Wiley & Sons.
distinct materials, they share similar sources, extraction methods, Denaturation of collagen produces gelatin, a structural protein
and a broad range of applications as shown in Fig. 23. commonly encountered in the kitchen but has great utility in
Collagen is the main structural protein in human connective biomedical device design due to its high biocompatibility and
tissue and comprises 90–95% of organic bone matter and accounts ability to promote cell adhesion, differentiation and proliferation
for tensile strength in blood vessels, cartilage, bones, etc. as well as [412]. Fundamental research focuses on the same gelatin sources
fibrils and membranes in vivo [411]. Collagen’s primary structure prized in the culinary community, predominately bovine and
consists of glycine-x-y triads where x is mostly proline and y is porcine skin collagen. Of the two, porcine skin is most popular
mostly hydroxyproline. The molecule has 1000 amino acids at because it has greater crosslinking and has many glycine and
100 kDa molecular weight wound into a triple helix. Alpha chains proline groups, which result in superior modulus, as well as free
may be the same (homotimer) or different (heteotrimer), thus hydroxyl groups that enable facile hydrogen bonding with water
multiple forms of collagen exist within the animal kingdom. [413]. Other factors of consideration when using gelatin are its
When secreted into the extracellular matrix, collagen mole- sensitivity to environmental conditions like temperature, humidi-
cules align head to tail in a staggered array, bringing molecule ty, and pH. At room temperature, gelatin forms semi-crystalline
crosslinking sites into proximity. The sites link by oxidative network that is brittle when dry, so plasticizers like glycerol
amination with age. The age of collagen, i.e. degree of crosslinking, usually accompany it to inhibit interchain interactions and thereby
determines its solubility. Un-crosslinked, fresh collagen is salt- improve toughness and flexibility for use in films, fibers, and 3D
soluble. Crosslinked collagen is mostly acid soluble with high structures.
crosslinking necessitating proteolysis by pepsin. In research, type 1 Duration of denaturation and method of extraction are
collagen is the most frequently used – often harvested from rat important factors in resulting gelatin mechanical properties
tails or bovine hooves, soaked in salt, dissolved in acid, and then [412]. Thermal denaturation disassembles and truncates the
dialyzed for aqueous processing. tropocollagen structure, leaving much smaller and less ordered,
water-soluble gelatin molecules. Denaturation decreases the proliferation is limited. More research into methods to manipulate
propensity of triple helices, secondary structure, molecular weight, the mechanical and structural properties of these proteins is
and hydrophobicity, while increasing chain polydispersity. These needed.
factors affect mechanical strength and must be tailored for each
targeted application. Depending on the extraction method, 4. Polynucleotides for bionanocomposites
different gelatins may be produced. Extraction from collagen via
acidic and basic treatments yield type A and type B gelatin, 4.1. Overview of polynucleotides
respectively.
Collagen and gelatin are largely used as matrices for tissue Polynucleotides have been intensively used as components in
scaffolds [414]. Like silk they are biocompatible and lightweight. bionanocomposites because of their robust helical structure and
Their proline residues are sites for crosslinking with glycine or rich presence of available functional groups that enable strong
loading with electrically, optically, or biologically active compo- interactions with other composite components [421]. The human
nents. However, they mostly were used in scaffolds for tissue body uses polynucleotides RNA and DNA to synthesize biomole-
regeneration [414]. For flexible electronics, Moreno et al. recently cules, determine their function, and trigger cell death. Polynucleo-
asserted collagen’s utility in this field [415]. They fabricated tides also encode a wide range of genetic predispositions such as
collagen films and e-beam deposited electrodes directly on for diseases like diabetes and for environmental protection in
collagen, illustrating the hardiness of collagen compared to silk melanin production [422]. Structurally, polynucleotides are chains
whose electrodes are fabricated separately then loaded to the film. of nucleotides – RNA is a single polynucleotide, while DNA consists
Flexible film-based applications using gelatin are less prevalent, of a polynucleotide pair wound helically. Each nucleotide has a
and research suggests this may be due to its brittleness. Plasticizers nitrogenous base, a five-carbon sugar (ribose for RNA and
like polyethylene glycol help mitigate this issue as showed by deoxyribose for DNA), and at least one phosphate group. In vivo,
Ahmed et al. [415] They crosslinked gelatin and chitosan, using a the liver produces nucleotides via de novo synthesis from
plasticizer to create flexible, biodegradable packaging films. The metabolized carbohydrates and amino acids. In vitro, nucleotides
abundant presence of aromatic groups in gelatin enable it to serve are produced by modification of protective groups. And, bacterial
as an ultraviolet light barrier. Applications for gelatin and collagen gene expression is used for high throughput production.
are limited, and their implementation outside of scaffolds and While structural proteins primarily impart flexibility and
capsules are relatively recent compared to silk fibroin. However, mechanical reinforcement, polynucleotides confer functionality.
more time could see its range of utility grow to match the research Of most interest for in polynucleotides their use in assembling
and application uses of silk fibroin. bionanocomposite materials and organized structures for bio-
chemical sensing and supramolecular assembly [24,423–426].
3.4.2. Keratin components Polynucleotides allow fast, label-free detection of biochemical
As one of the most ubiquitous fibrous proteins in nature, keratin markers. For instance, Wang et al. fabricated such a system, a
enables animals to protect themselves from predators, competi- laminated composite of highly conductive chemically modified
tion, and environmental hazards. The fibrous protein does this as graphene and self-reducing sulfonic-acid doped polyaniline with
aqueous slime, flexible high strength hair follicles, whale baleen polynucleotide binding probe on the surface [423]. When DNA
and feathers as well as high toughness nails, horns, and beaks hybridizes with the analyte, this perturbs the self-reduction of
[416–418]. Like silk and collagen, keratin derives its strength and polyaniline and signals the analyte’s presence. Tran et al. used
dexterity from hierarchical structure and inter-/intra-molecular relatively the same construct, modified GO, to make an immuno-
crosslinks. Keratin polypeptide chains containing cysteine amino sensor for microRNA [187]. Similar DNA hybridization based
acids that crosslink upon oxidation and form filamentous matrices sensing platforms have been made using gold, ruthenium and
that organize into lamellar and tubular structures that form other metals as redox indicators of target hybridization with
compact, porous structures at the macroscale. Varying degrees of binding probes of various levels of specificity. Polynucleotides have
microscale organization and mesoscale compaction and porosity available hydroxyl amine moieties that allow easy silane mediated
can yield a wide variety of mechanical properties, readily tailorable surface functionalization.
for use higher performance and niche biomedical applications.
Though available from many sources, for research purposes, 4.2. Soft nanostructures: DNA origami
keratin is typically extracted from bovine hooves using the general
approach applied to collagen (Fig. 23). Raw hooves are washed Polynucleotides such as DNA have been explored extensively
with distilled water, dried and pulverized then defatted via Soxhlet for their conformation into custom geometries through directed
extraction. Further incubation and dialysis yields pure keratin. No self-assembly processes. For complex hierarchical nanostructures,
additional modification is needed for biocompatibility thanks to lithographic techniques are currently used, however, difficulty
keratin’s natural derivation and cell adhesion promoting factors inducing precisely-directed self-assembly has limited bottom-up
RGD and LVD in its sequence. scalability [427]. One way of overcoming this challenge is DNA-
Due to keratin’s high biocompatibility and high strength, mediated controlled assemblies into these well-defined architec-
keratin is used broadly in tissue scaffolding applications. However, tures which are spontaneously created will be precisely duplicated
keratin as a pure material tends to be brittle and readily degrades into composite 3D structures in large quantity.
during use, and so is often used as part of a composite to with other Sophisticated DNA nanotechnology demonstrated various
proteins or polysaccharides to add toughness and stability. Another designs including 2D and 3D crystals [428,429], nanoscale shapes
way to add toughness is through crosslinking. However, cross- [430,431], and nanoscale devices [432,433]. In this technique, pre-
linking is an expensive option that would alter keratin’s inherent designed cocktails of polynucleotide sequences can self-assemble
properties and reduce its biocompatibility [419,420]. Introducing a and fold in a self-controlled manner under controlled temperature
plasticizer like glycerol may be the simplest fix for brittleness and chemical conditions to form desired 2D and 3D nanostructures
when flexibility and aqueous permeability are most desired as in a practice known as DNA origami (Fig. 24). This DNA origami
shown by Reichl et al. [416] They used keratin films as scaffold for process leverages the highly specific hybridization between
ocular surface reconstruction. As was the case for collagen and complementary polynucleotide sequences, increasingly available
gelatin, use of keratin outside of scaffolds or matrices for cell polynucleotide sequences either synthesized or extracted (i.e. from
Fig. 24. DNA origami to creat various nanoscale structures. Reproduced from [430] with permission. Copyright 2006 Springer Nature.
the M13 phage), and increasingly powerful computation suites experiments relied on DNA as a framework to which conductive
such as caDNAno to design complex polynucleotide structures metal nanoparticles were loaded[437,438]. Recent experiments
[434]. Both predictable and programmable, DNA can serve as a have begun to pave the way towards using DNA backbones as
scaffold or frame to enable the construction of 1D–3D structures of nanowires without additional modification and biometallization.
varying complexity. For example, Jorgenson et al. successfully Initially, understanding the conductivity of DNA molecules was
induced microscale assembly of DNA into rigid L, T, and Y shapes compromised by its polyelectrolytic behavior. However, after
[425]. significant efforts, it has been demonstrated that the helical, tube-
Directed assembly can be used to enable assembly of gold and like structure of DNA could serve as a channel for long-range
silver particles as well as other optically active materials into charge transfer on long distances with both transfer of vacancies
complex superlattices to form metamaterials by using comple- and electrons demonstrated for helical DNA nanowires.
mentary interactions and spatial frame of templated DNA Building upon this, Magro et al. created a mechanism to trigger
constructs. Young et al. [435] employed similar self-assembly DNA electrical conductivity [439]. In this work, they immobilized
properties in DNA to construct silver and bimetallic gold and silver DNA using surface active maghemite nanoparticles (SAMN) and
superlattices. formed nanobioconjugates that could self-assembled into 1D–3D
Initially, the authors identified proper constructs with poten- structures. When in solution, DNA demonstrated electric conduc-
tially interesting optical activity using electrodynamic modeling, tion between electroactive solute and SAMN. The opposite was
which predicted the selected structures would exhibit epsilon- achieved with free DNA, indicating that triggering by the nano-
near zero behavior and some optically metallic response. To build particles was necessary for electrical conduction through DNA.
this structure, Young et al. relied on the helical structure of DNA to Further investigation of this phenomena at the mesoscale using 3D
orient the chirality of noble metal nanospheres to form liquid structures to form metamaterials exhibited electrical conductivity
crystal metamaterials then dried to form dense thin films. The comparable to carbon paste (0.013–0.014 S/cm) and durability as it
ultimate film exhibited a metallic glossy facade and dielectric withstood cycles of voltammetry without losing performance.
properties as predicted by electrodynamic simulations. This Though a long way from forming a device, works like this enable
approach highlights another benefit of DNA-mediated assembly broader utilization of DNA in bioelectronics and more develop-
for optical materials which is that the reliability of DNA induced ment of more sensitive biosensors. These works provide better
assembly enables achievement of results that are a near match understanding of transport behavior of DNA backbones which is
with theory and allows one to precisely nail down specific useful for DNA nanowires and DNA-templated biometallized 3D
compositions and organization with unique functions not achiev- nanocircuits.
able in trial-and-error approaches.
Just as DNA-templated nanostructures can be used to manipu- 4.3. Sensing applications of bionanocmposites
late visible light, some have used it to manipulate fluorescence.
Typically, detection of biomolecules is limited to tags with distinct One of the areas that has extensively employed polynucleotides
colors in the visible range. However, DNA enables fabrication of as a component is the field of plasmonic nanosensors for
angstrom-sized tags with tunable brightness and color, meta- colorimetric detection of specific biomolecular events. As men-
fluorophores [436]. This enables better biomolecule detection as tioned earlier, LSPR can be excited in metallic nanostructures that
well as a potential disrupter of geometric barcoding since the DNA are far smaller than the wavelength of light. The spectral feature of
assembled metafluorphores can form dynamic intensity-based the far-field radiation from these plasmonic nanoantennae are very
barcodes whose color and brightness can be tuned by specific sensitive to the resonant conditions, such as local refractive index
biomolecular triggers. changes, and coupling between individual plasmonically active
Beyond aiding in assembly of optically active nanomaterials, structures [440]. Such a peculiar property makes these structures
DNA assembly can also be used to construct complex nano- strong candidates for nanoscale molecular sensors [441]. However,
electronic “devices” by templating 2D and 3D nanocircuits. Early the electrical field decays exponentially from the surface of the
metal, meaning the effective sensing radius and coupling distance assembly [448]. Simply put, this is the fundamental underlying
of plasmonic nanostructures is in the range of tens of nanometers. principle for almost all LSPR based colorimetric apta-sensors
Thus, precise nanoscale positioning of active nanocomponents is [441,449]. The exact structural change can vary by design, common
required. types include the dissociation of particle matrices [450], particle
There is already a plethora of examples reported in the literature pairing [451], aggregation formation [452], and induced particle
with suggestions of plasmonic nanostructures of remarkable growth [453], Similar designs are also applied in photoluminescent
sophistication and versatility that have been fabricated via DNA nanosensors where paring between a fluorophore and a quencher
guided assembly [442]. These examples include homogeneous (usually an Au nanoparticle) is used [449]. More complex sensing
nanoparticle oligomers with specific geometries such as triangle, scheme utilizes the structure actuation of DNA aptamers to directly
square, and hexagon, heterogenous planet-satellite assemblies of trap molecular analyte into ~nm sized gaps between plasmonic
different nanoparticles, even linear chains of different nano- nanoparticles in order to exploit the strong electrical field between
particles with individually programmable interparticle spacing the couple nanostructure for enhanced Raman or infrared
[442]. More complex systems such as 1D–3D plasmonic crystals spectroscopy [454,455].
with programmable anisotropy, mutual positing, and lattice Of course, the application of the nanostructural actuation
constants have also been demonstrated (Fig. 25) [442,443]. behavior of polynucleotides in nano-sensing is not limited to
An obvious application of these DNA linked plasmonic nano- optically-based devices [441]. The coil transformation of DNA
structures in sensing would be to use them as detection platforms aptamers upon target binding has long been used in electrochem-
for complimentary DNA strands in the so called “plasmonic ruler” ical sensing of molecular analytes, in which the distance between a
setup with high specificity [444,445]. Specifically, pairs of Au or Ag redox center and the electrode surface is modulated by the binding
nanoparticles are linked into dimers by a flexible single strand DNA event [456]. DNA/RNA based aptamers are also frequently used in
that is complimentary to the target sequence. Once the target DNA field effect transistor based and microcantilever based nano-
is introduced, it hybridizes to the linker DNA, reducing the sensors purely for their molecular recognition capabilities
flexibility of the linker, and subsequently extends the inter-particle [457,458]. The relative small size and chemical resistance of
spacing of the dimer, causing observable color changes. One can polynucleotides compared to protein based antibodies help solve
even investigate the specifics of DNA hybridization dynamics by many engineering problems faced by these devices such as sensing
continuously monitoring the spectral change of the ruler [446]. surface regeneration and environmental tolerances.
This approach can be generalized to the detection of other
molecules via the incorporation of DNA aptamers, which are 5. Carbonized bioderived materials
specific DNA sequences that are artificially evolved to have
selective affinity towards certain molecular targets such as Carbon materials are some of most essential materials for
adenosine [447]. electronic devices and various other functional applications such
These DNA strands will preferentially bind to target molecules as catalysis, optical devices, and pollutant remediation. Specially,
upon contact, therefore disrupting the existing nanoparticle carbon nanomaterials derived from natural biopolymer are
Fig. 25. Shape changing DNA–GNP films are fabricated via LbL deposition using a PDMS gasket, reproduced from [443] with permission. Copyright 2016 Springer Nature.
drawing increasing attention due to their low-cost, renewability, carbon. Heteroatom-doped (P, N-P, B-P) three-dimensional (3D)
and ease of modification. To transform biopolymers to carbon nanostructured carbon materials are successfully fabricated by
materials, the biosource is degraded to release small molecules carbonizing bacterial cellulose pre-immersed in various aqueous
such as H2, CO2, CH4, and C2H4, while collapsing to form aromatic solutions (H3PO4, NH4H2PO4, and H3BO3/H3PO4) respectively,
residual molecules that may stack to form a lamellar phase, and exhibiting good supercapacitor performance [463]. Luo et al.
transforming into a conjugated carbon structure (graphitization) [464] reported that the nitrogen-doped (N-doped) carbon can be
[459]. prepared by the carbonization of cellulose paper under NH 3
Although these bio-derived carbon materials exhibit only environment, which showed a large surface area up to 1973 m2/g.
modest electrical conductivity, thermal conductivity, and mechan- For biopolymers containing nitrogen groups such as proteins,
ical performance due to their low degree of crystallization, they direct carbonization without any other component or treating gas
possess impressive specific surface area that can reach 3700 m2/g— change will lead to the N-doped carbon [465].
even higher than that of graphenes [460]. This high specific surface Another favorable property of carbonized biopolymer is that
area is attractive for energy storage with supercapacitor and the micro/nanostructure of biopolymer materials can be to some
lithium ion battery. Indeed, Zhu et al. reported CNC derived carbon extent replicated into the carbon materials, which will benefit
can be used as high-performance carbon anode of sodium-ion various multifunctional applications. For example, chiral nematic
batteries, which demonstrated high capacity of 340 mAh/g at mesoporous carbon can be derived from helical LC structure of CNC
current density of 100 mA/g and good stability with 12% capacity film; highly porous, flexible, lightweight and compressive carbon
loss over 400 cycles [461]. Generally, the increase of the aerogel can be derived from bacterial cellulose aerogel for water
carbonization temperature will improve the graphitic region, purification; stretchable carbon film can be fabricated from the
resulting in the higher conductivity [462]. However, the high cost commercial silk fabrics for wearable strain sensors [466,467].
of energy consumption and equipment make this approach not Active carbon with anisotropic microchannels can be derived from
very cost-efficient. natural wood [468]; carbon nanomaterials with fibrous stipes can
To solve this problem, other highly conductive carbon nano- be obtained from the natural mushroom for solar steam-
materials such as graphenes and CNT components can be added generation devices [469].
(see Section 3.1). For example, the carbonization of well-aligned
GO (GO)-CNF hybrid fibers result in highly conductive carbon 6. Conclusions, trends, and perspectives
fibers with conductivity of 649T60 S/cm, 20 times higher than
that of carbonized CNF fibers. Moreover, the addition of other In this review, we highlighted recent research progress in the
components into the biopolymer or the variation of the carbonized structural design, fabrication, and applications of nanocomposite
environment can be used to prepare various element doped materials derived from natural biopolymer components by
Fig. 26. Outlook of bionanocomposites. (a) 3D printing of bacteria for producing living cellulose bionanocomposites, reproduced from [470] with permission, Copyright 2017
Schaffner et. al licensed under CC BY 4.0. (b) Mechanically-robust nanostructure of nacre, reproduced from [472] with permission, Copyright 2010 Springer Nature. (c)
Structural color of butterfly, reproduced from [476] with permission. Copyright 2017 American Chemical Society. (d) Conductive structure in electric eel, reproduced from
[479] with permission. Copyright 2017 Springer Nature. (e) Programming DNA nanotechnology, reproduced from [481] with permission. Copyright 2017 Springer Nature.
focusing mainly on the two most popular representatives, nano- self-grown materials with fully integrated biological and synthetic
cellulose and silk fibroins. Because of their abundant functional functions.
groups, multi-leveled organized, and easily reconfigured second- Despite the aforementioned advantages of bio-derived poly-
ary structure, biopolymers can produce complementary interfaces mers for structural and functional applications, current applica-
with various synthetic components with tailored functionalities. tions of these materials usually rely heavily on the properties of
As a result, the combination of biopolymers and synthetic added synthetic components, rather than nanostructure design
components usually demonstrates advantages in structural alone. Although most isolated biocomponents are relatively
enhancement and high-performance multi-functionalities. For modest in mechanical robustness (compared with inorganic
example, controlling molecular and supramolecular organization nanofillers discussed in this review) and non-active in terms of
of biopolymers on graphene surfaces allows efficient load transfer optical and electrical applications, their hierarchical nanostruc-
at synthetic and biological interface, facilitating the construction of tures might provide unique added functionalities. However, these
flexible wearable electronic biodevices with enhanced strength abilities are rarely realized in current materials designs, let alone
and robustness. Furthermore, incorporation with other synthetic living designs close to the complex hierarchical biomachines
functional components, such as metallic nanoparticles, adds new exploited by nature. To this end, a new level of computational
physical and chemical properties of interest such as high electrical simulations of near-exact replicas of natural and synthetic
conductivity, barrier transport, catalytic ability, and optical activity components in realistic environments at multi-length and real-
for prospective applications in sensing, energy harvesting and time scales is needed for guiding design efforts. These computa-
storage, biomedicine and structural nanomaterials. tional approaches should be integrated into research efforts to
Although the last few decades have seen impressive progress in understand the complex network of interfacial interactions in
the applications of naturally derived nanocomposites, several order to initiate targeted materials design instead of trail-and-
urgent challenges need great efforts to be addressed. Nano- error approached widely exploited now [470].
cellulose, spider silk, and DNA components still lack efficient The transformation of starting materials into functional
methods of extraction, synthesis, purification, and modification products has traditionally involved bottom-up and top-down
that are low-cost, scalable, reproducible, and can generate highly processing. For instance, biocomponents in LbL nanocomposites
purified components with low polydispersity in dimensions and build together a network of weak intermolecular bonds to produce
composition. For example, current conventional synthesis meth- materials with exceptional strength and toughness; whereas
ods of nanocellulose materials, including sulfuric acid hydrolysis complex set of top-down lithographic processes can transform
and mechanical exfoliation, not only are usually inefficient and lack polymer resists (including silks and celluloses) into well-defined
dimension control, but involve high energy consumption, hazard- high-precision nanostructures. However, each approach is plagued
ous constituents, and capital-intensive manufacturing equipment. by current material and processing limitations. Bottom-up
On the other hand, spider silks demonstrate superior perfor- material designs lack defined control over micro- and nanoscale
mance and their structural properties are much higher than those structure, while top-down approaches are prohibitively expensive
known for synthetic polymer fibers, but harvesting spider silk to generate massive structures on a per-unit basis unless at large
microfibers in sizeable quantities is highly challenging because it economies of scale. Functional and hierarchical nanomaterials
must be drawn from individual spiders in small quantities. based on bio-derived polymers and complementary nanoscale
Building a large “spider factory” or other exotic approaches components present an unprecedented opportunity to circumvent
suggested seem to be a questionable technology prospective and these traditional tradeoffs between top-down and bottom-up
other alternative approaches should be invented and proven. approaches. Natural materials such as proteins and genetic
Although biopolymer costs of extraction and synthesis have going components are created with incredibly high precision, and with
down, current costs are still prohibitively high. We believe there low polydispersity. By using these bio-derived polymers as a
will be persistant gap in materials that are industrially-scalable template for use alongside highly-specific reactions (i.e. click
and can be assembled into complex architectures within the next chemistries, Diels-Alder, living polymerizations) would result in a
several years. However, some emerging advanced extraction plethora of new bioenabled nanomaterials that can be solution-
nanotechniques, such as the enzymolysis and gene engineering, scalable like bottom-up processing, while retaining the specificity
demonstrate great potential for future large-scale and “green” of top-down processing.
production. As the per weight cost of bottom-up assembled polynucleotides
Additionally, many naturally-derived polymers cannot be and polypeptides goes down, these materials can be incorporated
readily derived from its source, or suffer reduced performance en masse into a new class of active bionanocomposite whereby the
(e.g., strength) after extraction, a more interesting alternative bio-derived component no longer just plays a passive role as a
approach to address the above issue is recombinant cells within matrix or is used for structural support. Although errors may arise
the composite generating bio-derived composite components. We in the folding of bioconstructs in the composite, a large number of
believe that the incorporation of recombinant organisms into such constructs will ensure that a sufficient number in close
composites could generate living bionanocomposites whereby the proximity retain the functionality to serve the prescribed
bio-derived component is constantly fixed and recycled by biota application. Also, progress in organic chemistry is likely to yield
within the material, rather than applied one-time in generation a diverse range of polynucleotide derivatives that can perform
(Fig. 26a). [470] Examples of such systems in nature include bone various complex tasks at the molecular level, such as highly
or skin, where embedded cells fix and regenerate the material to selective molecular recognition and catalysis. Integration of these
retain the organ’s functionality after wear and damage. Living new functional units into the previously mentioned hierarchical
bionanocomposites could respond to internally programmed structures will lead to a whole new generation of bio-nano-
scripts, or external signals, and readjust strength and properties composites. This kind of nanoconstructs will be able to perform
accordingly which is next to impossible to achieve in current exceptionally sophisticated functions such as nanoscale optical
materials designs. In the very distant future one can imagine an signal processing in nanophotonic circuits, coherent light genera-
array of designed synthetic cells pre-programmed to integrate tion and conversion, high speed biocomputing, in vivo multi-
themselves into biological environment and start generating molecular monitoring, and precise cell-targeted therapeutics that
tailored biosynthetic components in order to create organized never thought possible before.
The mechanical performance of current generation of biona- the environmental humidity thus creating either highly open or
nocomposites is still unsatisfactory when compared with all- closed macroscopic shapes. The organized structural elements in
natural materials themselves in many important aspects. Although spider legs can detect the position of prey trapped on the silk web
the reported bionanocomposite materials show advantages in from a complex strain pattern. Peculiar morphology hair on
some specific properties (e.g. high modulus or strength), the global different legs of wharf roaches initiates fast water propagation
performance in terms of a combination of all aspects still is far along the legs against gravity driven by unidirectional capillary
below the best natural materials because well-developed multi- forces. However, these unique abilities are rarely replicated outside
scale structural hierarchy usually miss in man-made nano- of laboratory settings due to a lack of a critical understanding of the
materials Fig. 26b. [472] For example, even if the best bionano- structural origins behind these properties, and of how to exploit
composites with silks and nanocellulose show excellent toughness existing biological pathways toward generating these structures.
far exceeding synthetic composites, the spider silk by itself still Naturally occurring phenomena (and only few of them are
shows a much more superior toughness and strength reaching mentioned above) show that nature still is a rich source of
180 MJ m—3 and 1.5 GPa respectively [471]. The careful selection of engineering inspiration to draw upon in the design and
biocomponents and synthetic counterparts, as well as the manufacturing of next generation bionanocomposite materials.
approaches for their efficient assembly into nanocomposites, While some progress has been made toward understanding vivid
plays a crucial important role for realizing a myriad of structural bionanocomposites with tunable structural color caused by
applications. To construct highly mechanically robust materials, responsive layered structures with periodic refractive index
we foresee the combination of 1D biopolymers and 2D nanoplates variation, the intimate combination of structural and functional
as choice materials because of their synergistic reinforcement purposes observed in the natural materials is still largely
mechanisms such as sliding and re-orientation of constituent unexplored for current materials designs.
components. On the other hand, the gamut of different fabrication In previous sections of this review, we have shown the
methods should be developed and refined to be available for the seemingly infinite applications of nanocellulose and silks as
reproducible production of bionanocomposites offer advantages structural, encapsulating, and functional materials. However, in
such as the low-cost, environmentally-friendly, potential for high each case, only micron scale proofs of concept usually exist. The
volume scale-up, and ease of reproduction. same is true for DNA constructs, which mostly serve as a binder for
In terms of optical functionalities, current bionanocomposites biological sensors and structural template. Due to the highly
basically only demonstrate existing intrinsic optical properties of specific pairing of nucleobases, DNA and RNA strands can assemble
each components, such as the transparency of nanocellulose, in an efficient and predictable manner, even in complex chemical
chirality of proteins and DNA molecules, and photonics, absorp- environments. Not surprisingly, such properties are considered
tion, or light emission of nanostructures. Very few examples with extremely attractive in the field of nano-fabrication, as different
beyond optical properties have been explored. In sharp contrast, nanocomponents can be easily functionalized via conjugation
many plants and animals can generate vivid and bright structural chemistry and spontaneously assemble into desired superstruc-
colors via regulating the light scattering and reflection by “using” tures that are otherwise very difficult, if not impossible, to
the highly periodic photonic nanostructures organized in a tedious manufacture using traditionally top-down microfabrication tech-
fashion on a large spatial scale [472,473]. For example, Pollia niques Fig. 26e [477,481].
condensate fruits demonstrate a strong iridescence, caused by It is worth to note that although DNA nanotechnology is
Bragg reflection of large-scale helicoidally stacked CNC multilayers currently entering the fourth decade since its inception by Seeman
in the cell walls of the epicarp [472]. The unique changing color at [478], progress in DNA-guided assembly of such composites has
different viewing angles, a phenomenon known as iridescence, of been limited by the availability, design, and knowledge over
the butterfly wing and the metallic beetle skins are suggested to be control in DNA linker strands. Advancements in this field has only
generated by the constructive interference arising from the accelerated after key innovations such as the establishment of
complex 3D organization of porous and oriented elements robust DNA-nanoparticle systems in spherical DNA nanoparticles
Fig. 26c [474,475,476]. We believe that patterning and constructing [21], new design themes of folding bio-derived scaffold strands
bionanocomposites, using these patterning techniques we dis- [430], and ever-decreasing costs of synthetic DNA as a source
cussed in Section 4.5 (e.g. lithography and 3D printing), to mimic material for large-scale development [479]. However, while
these unique structures of plants and animals will open the route polynucleotides remain the premier polymer for the precise
toward new forms of optical materials for active biophotonics and localization of attachments and folding to form composite
lasing. structures—the barriers to source material cost is still one of the
Progress towards the integration of conductive bionanocom- major factors limiting their use as an engineering material. In the
ponents into bioelectronic materials and devices requires a short-term, we expect research interest in polynucleotide-guided
significant portion of conductive components such as carbon assembly to focus on applications that require high-precision and
nanomaterials and metal nanoparticles, usually limiting the low-scale. As the cost of polynucleotides and the cost of the design
mechanical compliance, flexibility and biocompatability. Interest- of their structures continues to decrease, we expect to see the first
ingly, some animals, like the electric eel, are able to harness the practical applications of polynucleotide-based nanocomposites in
chemical energy available inside biological systems to output some unique cases initially.
ultrahigh power with peak potential differences of 600 V and Utilization of DNA as self-assembled 3D templates opens a
currents of 1 A [476]. In their specialized electric organs, thousands route toward design of highly specific nanostructures through co-
of membranes with highly selective and actuating ion channels are and self-assembly processes such as DNA origami. But we believe
highly packed, allowing electricity generation from the ion flux that this is only the first class of bio-derived molecules that can
that is induced by the ionic gradients Fig. 26d [476]. This concept is leverage multistage folding by-design. Such pre-programmed
very attractive for the construction of soft biopower sources and folding processes will be replicated as protein origami, whereby
can be potentially realized using the LbL techniques. we expect synthetic control over protein primary sequence,
Some other reconfigurable and adaptable functionalities that assembly environment, and controlled introduction of synthetic
are a response to the mild changes in the surrounding also are co-factors and co-enzymes could create even more versatile
achievable for bionanocomposites with special structure designs. structures and machinery than what we see today accessible with
For example, the pine cones can switch their shapes responding to DNA.
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4.5.1. Masks based micropatterns In an example of recent developments of this approach to

2.3.2. Alginates common tertiary structures: ﬁbrous, globular, membrane, and

Similar techniques have been applied to for detection across the

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