Chemical Engineering Journal 474 (2023) 145534

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Chemical Engineering Journal

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

Review

Silk-based flexible electronics and smart wearable Textiles: Progress

and beyond
Tonghe Xing a, Annan He a, Zhiyu Huang a, b, Yuxin Luo a, Yu Zhang a, Mengqi Wang a,
Zhicheng Shi a, Guizhen Ke a, *, Jie Bai c, Shichao Zhao d, *, Fengxiang Chen a, *, Weilin Xu a
a
State Key Laboratory of New Textile Materials and Advanced Processing Technologies and Hubei Key Laboratory of Digital Textile Equipment, Wuhan Textile
University, Wuhan 430200, China
b
College of Textiles and Clothing, Qingdao University, Qingdao 266071, China
c
China Textile Engineering Society, Beijing 100025, China
d
State Key Laboratory of Coal Conversion Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, China

A R T I C L E I N F O A B S T R A C T

Keywords: Flexible electronics and smart wearable textiles have been widely used in healthcare monitoring, flexible sensing,
Silk thermal management, protective clothing, energy storage, and conversion devices owing to their light weight,
Smart wearable devices user-friendliness, and high-throughput performance. Silk is a traditional fiber material and is one of the most
Smart textiles
promising candidates for flexible electronics and smart wearable textiles owing to its excellent mechanical
Textile electronics
properties, outstanding wearing comfort, good biocompatibility, and biodegradability. Silk can be integrated
with flexible electrons into textiles or developed into advanced materials such as conductive fibers, membranes,
hydrogels, and scaffolds for smart wearable devices, including actuators, sensors, electronic skin, self-generating
devices, energy storage devices, microneedles, and radiation-cooling smart textiles. In this work, we review the
spinning formation, unique hierarchical and chemical structures, and fundamental properties of silk fibers.
Subsequently, the preparation methods, working mechanisms, and applications of silk materials in various
flexible electronics and smart wearable textiles are reviewed. Finally, the persistent challenges and prospects of
silk-based flexible electronics and smart wearable textiles are discussed.

1. Introduction robots, and other fields [4,5]. Textiles are the most widely used mate­
rials in daily life. They possess qualities such as comfort, breathability,
In the 1960s, Massachusetts Institute of Technology’s Media Lab softness, and flexibility to conform to the body shape. Therefore, textiles
(MITML) pioneered wearable technology, which combines material, can be considered secondary skin for humans [6,7]. Textiles are ideal
information, and electronic technologies to gather, process, and provide platforms for flexible electronics. The integration of flexible electronics
feedback on data relevant to the human body [1]. Traditional wearables, into wearable textiles provides individualized intelligent functionality
such as capacitors and sensors, use rigid materials that are incom­ to meet the requirements of diverse environments and users [8], and has
pressible and stretched, which inevitably restricts body movements significantly advanced the development and application of intelligent
during use. Therefore, such wearables are unsuitable for human motion wearable devices.
detection and the monitoring of physiological information. Flexible Silk is a traditional fiber material that has been widely used in the
electronics have ushered in an era of all-round development with the textile industry for thousands of years because of its excellent mechan­
arrival of artificial intelligence and the Internet of Things (IoT) [2,3]. ical properties, comfort, attractive luster, moisture absorption, and
Flexible electronics comprise electronic components made of organic or permeability. Currently, silk is one of the most promising candidates for
inorganic materials on flexible or malleable substrates. Owing to their flexible electronics and smart wearable textiles [9,10]. Many advanced
stretchability, light weight, user friendliness, high level of adaptability, silk-based materials, such as conductive fibers [11], membranes [12],
and other advantages, they are widely used in human motion detection, hydrogels [13], and scaffolds [14], have been developed by optimizing
personalized medical care, human–computer interactions, intelligent spinning methods, forming hierarchical structures, functionalizing

* Corresponding authors.
E-mail addresses: [email protected] (G. Ke), [email protected] (S. Zhao), [email protected] (F. Chen).

https://doi.org/10.1016/j.cej.2023.145534
Received 24 June 2023; Received in revised form 11 August 2023; Accepted 18 August 2023
Available online 22 August 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

mesoscopic materials, and modifying fiber surface [15,16]. Advanced continues to develop. However, existing electronic devices often have a
silk materials typically have conductive, antibacterial, and sensing short service life, resulting in the generation of large amounts of waste
properties. Because silk is soft and easy to process, it has been used in electronics and subsequent environmental pollution and resource loss.
flexible electronic materials, including actuators [17], sensors [18], Because silk is a biomaterial with excellent biodegradability, it can be
electronic skin [19], energy generation [20], storage devices [21], and combined with flexible electronics to prepare smart wearable devices
skin microneedles with controlled-release drugs [22–25]. In addition, that alleviate the environmental pressure caused by discarded electronic
silk can be used as an important material for the preparation of intelli­ devices and meet the requirements of sustainable development [27].
gent wearable devices and textiles, such as radiation-cooling clothing, The development history of silk-based wearable products and smart
owing to its excellent thermal and wet comfort, and high infrared textiles in recent years is shown in Fig. 1a, and the research progress of
emissivity [26]. Because of its outstanding comprehensive properties, intelligent wearable devices and silk-based intelligent wearable devices
silk has been widely applied in intelligent wearable and flexible is shown in Fig. 1b,c. This paper provides a comprehensive overview of
electronics. recent developments and applications of silk in the field of smart
Furthermore, there is a growing demand for flexible electronics and wearables. The research progress in the application of silk-based wear­
smart wearable textiles as the global population grows and technology able materials is discussed in detail, including actuators, sensors,

Fig. 1. (a) Development chart of silk application in the field of smart wearable and smart clothing. (b) Research progress of intelligent wearable devices in recent
years. (c) Research progress of silk-based intelligent wearable devices in recent years. The number of publications and citations was collected from the Web of Science
between 2010 and 2023).

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electronic skin, spontaneous electric devices, energy storage devices, 6.2) [28]. As the pH and water content gradually decrease, the fiber
microneedles, and radiation-cooling smart textiles. Finally, this review becomes thinner and finally flows into the spinning duct. The spinning
summarizes the future directions of silk in the field of smart wearable duct is composed of three organs: a common duct, a silk-pressing part,
devices. and a spinneret. The two fibers secreted from the anterior gland
converge after further stretching and shearing and are then extruded
2. Formation, structure, and properties of silk from the spinneret. In this process, the pH is reduced to 4.8 [35], the
water content of the silk protein solution is further reduced, its con­
2.1. The formation of silk centration increases to 30 wt%, and the silk protein molecules form a
small number of sheet structures [36]. The silkworm wraps the silk
Silk is a protein fiber with excellent mechanical properties. The layer-by-layer by figure-8 winding to form a cocoon. These cocoons are
structure and properties of silk are influenced by the spinning process. converted into raw silk by mixing, peeling, selection, cooking, reeling,
Therefore, understanding the relationship between the silk structure and re-reeling, finishing, and other processes [37].
its properties requires an understanding of the spinning process used by
silkworms. This information contributes to the enhancement of both
natural and recycled silk properties. 2.2. Structure and properties of silk
The spinning system of silkworms consists of two parts: a silk gland
and a spinning duct. The silk gland consists of a pair of glands that Owing to the unique spinning process of silk, it shows a sheath–core
secrete liquid silk protein and comprises three silk gland organs structure with two pieces of SF as the core and sericin as the sheath. The
(Fig. 2a–c): the posterior silk gland (PSG), middle silk gland (MSG), and cross-section of the silk shows a flat elliptical or triangular shape. Silk is
anterior silk gland (ASG) [28,29]. Silk fibroin (SF) is produced in the comprised of approximately 75% and approximately 25% sericin pro­
PSG (pH ~ 8). At this point, the conformation of the SF is mainly a tein. The SF core of silk has excellent mechanical properties and is the
random curl or helix shape [30]. Under intracavitary pressure, the SF is main silk protein used by people. Sericin is a soluble protein that acts as
continually driven forward to the MSG (pH ~ 7), where it is wrapped in an adhesive on the SF core to maintain the integrity of the silk structure
sericin secreted by the MSG and then securely integrated into the [38–40]. In the textile field, a large amount of sericin is removed from
micellar form [31,32]. In this process, metal ions (such as Ca2+ and K+) the surface of the silk fibers during a reeling process to aid weaving and
are exchanged between the SF and MSG cells to adjust their concen­ improve wearing comfort. SF is the most widely used silk protein in
tration, and the concentration of the silk protein increases from 12 to 15 wearable devices. SF has a hierarchical structure that is classified into
to 25 wt% [33,34]. The SF continues to move to the slender ASG (pH ~ five levels: amino acid sequence (first structure), sheet and helix (second
structure), crystallite (third structure), crystal network (nanofibrils;

Fig. 2. The formation and hierarchical structure of Silk. (a) the spinning organ of mulberry silk. Reproduced with permission [66]. Copyright 2017 Springer Nature.
(b)spinning duct. Reproduced with permission [67]. Copyright 2013 WILEY-VCH. (c) schematic drawings of silk and silk glands. Reproduced with permission [68].
Copyright 2022 Springer Nature. The cocoon has two symmetrical silk glands. Each silk gland is divided into ASG, MSG and PSG. ASG is the processing cavity of silk
protein liquid, MSG is responsible for the production of sericin, and PSG is responsible for the production of silk protein. (d) The five-level hierarchical structure of
silk. Reproduced with permission [41]. Copyright 2019 WILEY-VCH. A polypeptide chain with a primary structure consisting of amino acids. The secondary structure
is a β-sheet and a-helix composed of polypeptide chains through hydrogen bonds. The tertiary structure is β-crystal formed by β-sheet stack. The four-stage structure is
a crystal network composed of numerous β-crystals, and one crystal network can form an independent nanofibril. The five-stage structure is a nanofiber network
composed of numerous nanofibril.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

fourth structure), and nanofibril network (fifth structure) (Fig. 2d) [41]. silk has good dielectric [61], piezoelectric [62], actuation properties
Based on their relative molecular weights, SF can be divided into [63]. Silk exhibits electrical conductivity after carbonization because of
light (L) and heavy (H) SF chains with molecular weights of 26 and 390 its unique β-sheet structure [64]. In addition, SF is easy to process into
kDa [42], respectively, based on their relative molecular weights. The various shapes according to the requirements of the application. The
ratio of the number of amino acids in the H chain (5263) to the L chain many active groups on the silk surface facilitate the development of
(2 6 6) is approximately 20:1. The amino acid groups are connected in a flexible devices prepared using functional nanomaterials [65]. The ad­
1:1 ratio by a single disulfide bond at the C-terminus to form H–L vantages of silk enable its broad use in wearable devices.
complexes [43]. Glycoprotein P25 and the H-chain complex are con­
nected via hydrophobic interactions to maintain structural integrity 3. Conductive of silk
[42]. The H chain is mainly composed of glycine, alanine, serine, and
tyrosine (8:5:2:1) [44–46]. Amino acids form peptide chains according Silk is often used as a base material in flexible electronics because of
to a certain sequence and are stably linked by hydrogen bonds between its excellent flexibility and mechanical properties. Electrical conduc­
amino and carboxyl groups. These amino acids are combined in different tivity plays an important role in maintaining normal operation in
sequences to form 12 large hydrophobic repetitive domains and 11 wearable electronic devices. Silk itself does not generate electricity, but
smaller hydrophilic non-repetitive domains of the H chain, which form silk fibers can be endowed with conductivity and used as a functional
highly ordered crystalline and amorphous regions in the SF, respectively fiber for flexible electronics [69]. Conducting silk fabrics can be used to
[38]. The hydrophobic repeating domain is the basic dipeptide unit of prepare silk-based electronic textiles for smart wearable devices based
the combination of glycine and other amino acids and is mainly on their excellent electrical conductivity and flexibility.
composed of the sequences of (-G-A-G-A-G-S-)n and (-G-A-G-A-G-Y-)n. Silk-based conductive fibers are prepared by introducing conductive
These two hexapeptides account for ~ 72% of all repeated dipeptides materials onto the surface of the silk fibers. These conductive materials
[47]. Hydrophobic repeating domains can be combined into an α-helix include reduced graphene oxide (rGO) [70], carbon nanotubes (CNTs)
or a β-sheet by hydrogen bonding. The α-helix and β-sheet are the most [71], metals [72], and conductive polymers [73]. Graphene is a single-
typical secondary structures, and there are corresponding random coil carbon atomic-layer nanomaterial with a 2D morphology that has ultra-
structures (polypeptides, unfolded proteins, and polypeptide chains) in high electron mobility, good thermal conductivity, and excellent me­
the secondary structures [41]. β-sheets form a tertiary structure in chanical properties [74]. The molecular structure of graphene is quite
β-crystallites through hydrogen bonding, hydrophobic interactions, van stable and there are no active groups on its surface, which makes it
der Waals forces, and other forces. The structural stability and crystal difficult for graphene to bind to the surface of silk fibers. Graphene oxide
orientation of β-crystallites are of great significance to the mechanical (GO) is obtained by oxidizing graphene, resulting in abundant surface
properties of the fibers [48]. β-crystallites and amorphous chains are active groups, such as carboxyl, hydroxyl, and epoxy groups [75]. GO
connected to form a fishing-net microcrystal network as the quaternary adheres to the surface of silk fibers by a combination of covalent and
structure of SF fibers. The microcrystalline network structure can be hydrogen bonds, which enhances the interaction and adhesion strength
used as a separate nanofibril structure. Nanofibrils exist in advanced silk between the GO and silk [75]. However, the binding force between GO
materials, such as fibers, silk protein hydrogels, films, and scaffolds. The and silk is still not adequate for some applications so it is necessary to
nanofibrils formed by the β-crystal network interact with each other to enhance the interaction and binding force between GO and the silk fi­
form a nanofibril network and finally form the fifth SF structure of silk bers using coupling and cross-linking agents [76,77]. Finally, the GO is
[41]. reduced to rGO to restore its stable structure and properties. Bovine
During silk formation, the content and type of amino acids, stability, serum albumin was used as an adhesive to treat silk fabric, which was
orientation, content of β-crystallites, and molecular weight of the silk then dipped into a GO solution to self-assemble a GO nanofilm on the
protein molecular chains significantly affect the mechanical properties silk surface, which was then reduced using hydrazine steam to achieve
of the fiber [49–51]. The hierarchical structure of silk provides excellent an rGO coating on the silk [70]. Silk samples with different rGO coatings
mechanical performance. Silk has a tensile strength of 0.5–1.3 GPa and were obtained by repeating this process. The square resistance of rGO-
toughness of 6–16 × 104 J/kg, which is higher than that of most natural coated fabric can reach 1.5 kΩ sq-1, and that of rGO-coated single silk
protein fibers [52]. The mechanical characteristics of silk are signifi­ fibers can reach 3595 S m− 1. The rGO-coated fabric and fibers prepared
cantly affected by its nano-fishnet structure. Molecular dynamics sim­ by this repeated coating/reduction method are expected to be used as a
ulations were used to study the effect of the density of arginine in the functional supporting matrix and conductive fabric/yarn for wearable
fishnet structure, which offers an intriguing concept for the production electronic products in the future. GO was coated on a silk fabric with RSF
of high-strength and high-toughness silk [53]. Other studies proposed as an adhesive, and a conductive silk fabric was obtained by thermal
that the mechanical properties of silk are limited by the 8-shaped reduction [76]. The α-sheet structure of the conductive silk fabric pre­
spinning mode of silkworms, which stops and starts during spinning, pared by this method was maintained, along with its good mechanical
resulting in defects in the aggregation morphology of silk protein mo­ properties. The resistivity and electrical conductivity of the conductive
lecular chains. The mechanical properties of silk were improved by silk fabric were 3.28 kΩ cm− 1 and 3.06 × 10-4 S cm− 1 respectively.
regulating its spinning mode to extrude uniform silk fibers at high speed, In addition to improving the conductive and mechanical properties
which had equivalent mechanical properties to spider silk [54]. of the silk fibers and fabrics, improved flame retardancy, ultraviolet
Silk fibers have good biocompatibility and have been used as surgical (UV) shielding, and thermal stability have been achieved to broaden the
suture materials for centuries. Silk does not produce allergic reactions, application range of conductive silk. An environmentally friendly dry-
irritation, or genotoxicity, and in vivo implantation does not cause any coating method was used to deposit a synthesized GO hydrosol on the
obvious inflammatory reactions [55,56]. Silk and regenerated SF (RSF) surface of the fabric and then reduced it in an L-ascorbic acid solution to
can be safely used on the skin for long periods, making it suitable for prepare large-area conductive silk fabrics with a low square resistance of
wearable devices. Silk also exhibits controllable degradability. Higher 0.13 kΩ sq-1 [78]. Using this method, large amounts of rGO sheets (up to
orientations and contents of α-sheet and β-crystallites in silk reduce its 19.5 wt%) can adhere well to the fabric surface and provide flame
dissolution properties [41]. The formation of α-sheets in silk can be retardancy, smoke suppression, and durability. Silk fabrics with both
regulated by steam annealing [57], methanol soaking [58], glutaralde­ conductivity and flame retardancy can be used in firefighting. Silk fab­
hyde cross-linking [59], addition of proline [60], mesoscopic hybridi­ rics coated with 3.9 wt% rGO are suitable for sensor applications in
zation [15], and other methods. In microneedle applications, the drug- flexible wearable devices.
release rate is regulated by the degradation rate of silk, which can be Electrostatic self-assembly is an important method of preparing
accurately controlled based on the needs of the application. In addition, conductive wires. In an acidic aqueous solution, GO is reduced to rGO by

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the self-assembly of GO on the silk surface, and then aniline is self- In the functional modification of silk fibers/fabrics, improving its
assembled on the silk surface. The surface resistance of the prepared mechanical properties is key to expanding its application in the wear­
conductive silk fabric was only 0.330 K cm− 1, and this method improves ables field. Although the core–sheath structure of silk fibers has excel­
the thermal stability of self-assembled conductive silk [77]. Silver and lent mechanical properties [81], the sericin sheath must be removed by
copper nanoparticles have excellent antibacterial properties, electrical a degumming step during silk processing. The application of functional
conductivity, thermal stability, and high surface area [79]; therefore, materials to the surface of silk can endow it with diverse functions while
they can be coated on the surface of the final silk as functional nano­ restoring the core–sheath structure. Chitosan (CS) was used as an
particles. GO, silver, and copper nanoparticles were coated on the sur­ interfacial connecting molecule with GO in an L-ascorbic acid solution,
face of the silk fabric with 3-glycidyloxypropyl trimethoxysilane as the into which silk was dipped and then dried to obtain rGO-coated silk (GS)
coupling agent, and then GO was reduced to rGO using a sodium sulfate (Fig. 3a) [82]. The hydrogen interfacial interaction between rGO–CS
solution. Conductive silk fabrics coated with rGO, silver, and copper and silk increased the tensile strength and toughness of the rGO-coated
nanoparticles using this technique exhibit excellent electrothermal silk by 1.9 and 2.6 times, respectively. rGO-coated silk shows high
properties, ultraviolet shielding, increased thermal stability, excellent electrical conductivity (0.37 S m− 1), high thermal and deformation
hydrophobicity, and low surface resistance [80]. The surface resistance sensitivity, and suitability for flexible electronics applications.
of a conductive silk fabric coated with copper was 3.15 kΩ sq-1, and the Conductive graphite/silk fiber (GSF) with a silk fiber core– graphite
surface resistance after washing was 6.76 kΩ sq-1, which is lower than sheath structure was prepared by a dry Meyer rod coating [83]. One end
that of the fabric without copper. These materials have potential ap­ of the silk fiber is fixed to a plate and aligned, then pressed on a graphite
plications in electronic textiles and smart clothing. sheet with a Meyer rod, which is moved along the direction of the silk

Fig. 3. Preparation of Conductive Silk and fabric. (a) The process of depositing rGO after degumming of silk. Reproduced with permission [82]. Copyright 2021
Wiley-VCH. (b) CSF and PCSF prepared by formic acid etching, (c) Light up five LED lights through CSF, (d) Thermal imaging of PCSF in microwave oven at 353 W
power. Reproduced with permission [84]. Copyright 2020 Elsevier. (e) The image of sewing silk dyed with PEDOT: PSS on cotton fabric after washing and drying, (f)
The image of silk dyed by PEDOT: PSS and connected with LED lamp, (g) Repeated bending resistance R of 32 cm long yarn with diameter (∅) 4.5(•) and 52 mm (◇)
around Teflon bar. Reproduced with permission [73]. Copyright 2017 American Chemical Society. (h)The image of strain sensor based on CSG has transparency and
excellent flexibility, (i) The strain sensor based on CSG can be applied to different parts of the body and smile can cause the corresponding resistance of the sensor
near the mouth to change. Reproduced with permission [90]. Copyright 2017 American Chemical Society (j) Preparation schematic of CNT@Silk,(k) Optical images
of rigid CNT@Silk wires made from SF solution directly coated on carbon nanotube yarns (left) and flexible CNT@Silk wires made by electrospinning on carbon
nanotube yarns (right). The image on the right shows good flexibility, (l) Use a multimeter to test the electrical conductivity of the CNT@Silk sewn on the yoga shirt
and the color change under different voltages. Reproduced with permission [91]. Copyright 2018 American Chemical Society (m) Preparation Technology of Silk
feeding AgNWs, (n) Relationship between tensile strength and elongation at break of different silk fibers, (o) Electrical conductivities (σ) of different silk fibers.
Reproduced with permission [93]. Copyright 2022 Springer Nature.

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fiber to coat it with the graphite sheet. The resistance of the GSF changes surface. The manufactured conductive silk had a resistivity of 1.47 Ω
with the external loading pressure, making this material suitable for use cm− 1, high temperature sensitivity (-0.47%/K), and retains its
in strain sensors. flexibility.
Multi-walled CNTs can be coated onto silk surfaces using a control­ Functional silk fibers, such as conductive fibers, are prepared by
lable etching strategy. For example, multi-walled CNTs were mixed with loading functional materials onto the silk surfaces. However, these
hexafluoroisopropanol and then coated onto degummed silk fibers [71]. functional coatings are directly exposed to the environment, making
Hexafluoroisopropanol controllably etches the surface of silk fibers, them vulnerable to changes in light, temperature, and humidity, which
realizing strong binding between the CNTs and silk fibers while main­ can affect the conductivity stability. Furthermore, these functional
taining the main structure and excellent mechanical properties of the coatings can peel off after friction, washing, or other processes. This not
silk. Silk fabrics coated with CNTs not only have excellent electrical only impacts the performance of functionalized silk, but also poses
conductivity, but also water and solvent resistance, and heat retention. A safety hazards to human health (i.e., reduces its biocompatibility), thus
formic acid solution was used to etch a silk surface to prepare a one- limiting its wearable applications.
sided multi-walled CNT silk fabric (CSF) (Fig. 3b) with a conductivity In addition to the strategy of applying conductive functional mate­
of 468 Ω cm− 1 [84]. The slightly soluble silk protein on the silk surface rials on the surface of silk to give the silk conductive function, it is also
improves the bonding strength between the CNTs and silk and has good possible to give the silk conductive function by carbonizing the silk, silk-
durability. The resulting CSF had unique unilateral loading character­ coated carbon nanotubes strategy, and feeding the cocoon with
istics, where their resistance changes with deformation, enabling this conductive nanomaterials. Carbonized silk georgette (CSG) (Fig. 3h) was
material to be used as a sensor for detecting human motion. During prepared by carbonizing silk georgette (a commercial light tulle fabric
deposition, a patterned template can be used to prepare patterned composed of high-twist warp and weft yarns) [90]. The carbonized silk
conductive CNT silk fabric (PCSF), which is suitable for a wide range of shows excellent electrical conductivity, and the CSG retains its high-
electronic products such as electronic switches and calculators. In twist woven structure. This material demonstrates excellent sensing
addition, the PCSF exhibited Weibo-assisted heating, where the function and can detect smiling, speaking, and other movements of the
patterned part exhibited a significant temperature increase with human body (Fig. 3i). RSF is obtained by spinning after dissolving the
increasing microwave power (Fig. 3c, d). However, hexa­ silk, but its mechanical properties are poor, and further processing is
fluoroisopropanol and formic acid cause irritation and corrosion, and required. RSF can be prepared into silk nanofiber films by electro­
silk treated with these chemicals may pose a potential risk to human spinning, and conductive silk-covered CNT yarns (CNT@Silk) (Fig. 3j,k)
health [85,86]. These controllable etching strategies improve the with excellent mechanical properties were prepared by the in situ
adhesion of functional nanomaterials to silk surfaces, but safer solvents winding of silk nanofiber films on rotating CNT yarns [91]. CNT@Silk
are required for this process. has excellent electrical conductivity (3.1 × 104 S m− 1) and mechanical
Electroless plating is a simple method for integrating polymers and properties (16 cN/tex). The outer silk nanofiber film provides good
metallic materials. Supercritical CO2 technology was used to enhance insulation and biocompatibility and is safe for contact with the human
the characteristics of electroless plating and embedded palladium body. In addition, CNT@Silk exhibits electrochromism, whereby it
organic metal complexes into a silk matrix in the catalytic step without changes color in response to the applied voltage (Fig. 3l), which is
destroying the silk structure [72]. Then, a smooth and dense Pt layer was beneficial for smart clothing applications. By feeding conductive mate­
formed during the metallization step. The use of supercritical CO2 re­ rials such as CNTs, graphite, and metal to silkworms, the silk is doped
duces the metallization time and improves reliability. The Pt-coated silk with conductive materials during the silk formation process, resulting in
fabric prepared using this method exhibited excellent wear and corro­ conductive silk fibers with improved mechanical properties. When the
sion resistance and the lowest resistance of 50 mΩ under optimal con­ silkworm is fed CNTs and graphene, the nanocarbon affects the
ditions, indicating their applicability for use in wearable devices. conformation transformation of SF from the irregular crimped/α-helix to
Photocatalytic TiO2 and a conductive Ni–P metallized layer were coated β-sheet form, which may help improve the elongation and toughness-at-
on the surface of the silk fabric using supercritical CO2–enhanced elec­ break of the silk. The introduction of CNTs and graphene results in a
troless plating [87]. The prepared silk fabric had excellent electrical graphitized silk structure that becomes conducting after heat treatment
conductivity, wear and corrosion resistance, and photocatalytic activity [92]. Feeding silver nanowires (AgNWs) to silkworms increased the
and was demonstrated as a functional wearable conductive textile. The content of random crimp/α-helix in the fiber and improved the orien­
supercritical CO2–enhanced electroless plating method can deposit a tation of microcrystals (Fig. 3m). The tensile strength, elongation at
conductive metal layer on the silk surface, but the electrical conductivity break, tensile modulus, and toughness of the silk fibers after AgNW
of the layer may decline during use. In addition, the high technical and feeding increased by 37.2%, 37.6%, 68.3%, and 69.8%, respectively
equipment requirements of this method are limitations for industrial (Fig. 3n). The electrical and thermal conductivity increased by 246.4%
applications. and 32.1%, respectively (Fig. 3o) [93]. The prepared conductive silk
Conductive silk with wear and washing resistance can be prepared by showed great potential for use in smart wearables. Conductive silk can
coating the silk with conductive polymers, such as poly(3,4- be produced by carbonization or feeding silkworms conductive nano­
ethylenedioxythiophene) (PEDOT) and polyelectrolyte poly(styr­ particles. The original properties of the silk are degraded by carbon­
enesulfonate) (PSS). PEDOT:PSS was applied to dye silk to prepare a ization, which limits the application of carbonized silk. The effects of the
conductive yarn (Fig. 3e,f) with wear resistance and washing resistance size and physical and chemical properties of the nanoparticles on the
[73]. This dyeing process can produce yarns up to 40 m in length. The modified silk and its biological distribution and metabolic processes in
yarn maintained an overall electrical conductivity of 14 S cm− 1 after vivo are not clear. The performance of functionalized silk produced by
subsequent sewing, bending, and other processes (Fig. 3g). To further feeding silkworms with nanomaterials may vary, which could poten­
improve the electrical conductivity of silk, 5% ethylene glycol was tially impact subsequent processing.
added to the conductive polymer PEDOT:PSS and the silk yarn was The wear comfort, durability, and flexibility of conductive silk ma­
passed through a dyeing bath twice to increase the amount of PEDOT: terials are crucial for the development of smart wearable devices. Direct
PSS to obtain a conductive yarn with a conductivity of 70 S cm− 1[88]. coating, impregnation coating, electrostatic self-assembly, chemical
Following the introduction of MnO2 to the silk surface, flexible etching, chemical plating, and other methods of loading conductive
conductive silk fibers were prepared by the in-situ chemical polymeri­ functional materials onto the silk surface endow the silk with conductive
zation of PEDOT [89]. MnO2 oxidizes PEDOT monomers to form living functionality. However, these preparation methods make it difficult to
intermediates on the silk fiber surface for further polymerization. This maintain the original silk properties, which may be a limitation for
resulted in a higher amount of PEDOT: PSS being deposited on the silk wearable applications. The lack of reactive groups in carbon-based

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conductive materials makes it difficult for them to adhere firmly to the breathability and moisture permeability of the silk. The strategy of
silk surface. Thick carbon-based coatings are required to increase the coating silk with CNTs necessitates the dissolution and spinning of the
conductivity of silk, which may affect its flexibility. In addition, most silk; however, this process leads to a decrease in its mechanical prop­
surface-coating methods degrade the breathability and moisture erties and consequently limits its applicability. The conductive silk
permeability of silk, which makes the conductive silk less comfortable to prepared by feeding conductive functional materials to silkworms has
wear than traditional silk. Moreover, silk-based wearable devices must good air permeability, moisture permeability, washing resistance, fric­
be suitable for repeated long-time use, and the functional coatings on the tion resistance and excellent mechanical properties. However, their
silk surface may suffer from conductivity loss or even circuit breakage conductivity is difficult to control, which limits their applications in
due to exposure to friction and washing during use. Flexible conductive wearable devices. In the textile industry, fabrics are often treated with
polymer-coated silk has better washing and friction resistance compared finishing agents in the after-finish stage to enhance their appearance and
to rGO-coated silk. However, the quality of the polymer coating can be hand feel, as well as to impart antibacterial, water-repellent, moisture-
affected by various factors, such as the polymer concentration, and wicking, and other functionalities [94]. Future work includes the opti­
polymerization temperature and time. Non-optimal processing factors mization of the preparation process, and the development of new
can lead to a nonuniform distribution of the polymer coating, which in functional materials and technological methods to improve the con­
turn affects the conductivity and tensile strength of the coated silk. ductivity of silk while maintaining its comfort and abrasion resistance.
Consequently, balancing the trade-offs between the comfort, mechanical
properties, durability, and electrical conductivity of conductive silk is 4. Silk-based smart devices
exceptionally challenging.
Other methods for preparing conductive silk, such as carbonization, 4.1. Silk-based actuators
silk-coated CNTs, and the incorporation of conductive functional ma­
terials, also have limitations. Although carbonized silk has excellent Actuators convert various types of energy into mechanical energy via
electrical conductivity, it is brittle and susceptible to breakage. environmental changes [95]. The internal structure of silk fibers is
Carbonized silk is often combined with polydimethylsiloxane (PDMS) to composed of hydrophilic and hydrophobic domains. The amorphous
enhance its mechanical properties [90], but this can adversely affect the region and α-helix in the hydrophilic domain easily combine with water

Fig. 4. Silk-based actuator. (a) The schematic diagram of the fabrication process of the thread composed of oriented silk nanofibers prepared by directional elec­
trospinning, (b) A picture of the rotation of silk in the wet/dry process, (c) It demonstrates the opening and closing of silk-based cloth under the condition of human
body moving and sweating. Reproduced with permission [98]. Copyright 2019 Springer Nature. (d) Schematic diagram of microfluidic chip, MRSF (microfluidic
spinning regenerated silk fiber) protein actuator and its structure. Reproduced with permission [102]. Copyright 2022 Elsevier. (e) Schematic diagram of SF driver
with fast water reaction and its trigger circuit under humidity control. Reproduced with permission [103]. Copyright 2021 American Chemical Society. Antagonistic
driving characteristics exhibited by SF films exposed to (f) water vapor and (g) ethanol vapor, and corresponding (h)mechanistic diagrams. Reproduced with
permission [104]. Copyright 2022 American Chemical Society.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

molecules through hydrogen bonds, and the silk can absorb up to 40 per comfort requirements. Because of its good flexibility, excellent me­
cent of water in atmospheric conditions. When water molecules enter chanical properties, and easy processability, silk can be prepared as a
hydrophilic domains, the hydrogen bonds are destroyed as the structure matrix material and support for sensors during the daily activities of the
and volume of the fibers change; thus, the fibers exhibit humidity- user. Because silk protein is biocompatible and biodegradable, silk-
induced changes [96,97]. The reversible expansion and contraction of based flexible sensors can be used in direct contact with the skin. The
silk during moisture cycling makes it suitable for use as an actuator in excellent biodegradability of silk also promotes the green recovery of
intelligent textiles, artificial muscles, soft robots, and other fields. sensors and the sustainable development of flexible electronic equip­
Highly oriented silk nanofibers were prepared using electrospinning ment [105].
and humidity-sensitive silk-based actuators were prepared by a twisting Flexible sensors need to sense subtle changes in the environment
treatment (Fig. 4a,b) [98]. After moisture absorption, the gap between around the human body (e.g., pressure, deformation, temperature, hu­
the nanofibers reduces as they rotate in response to elastic capillary midity), as well as signals related to human physiology, and transmit
forces in front of the highly oriented nanofibers. This process was data quickly (usually as electrical signals). Conductive silk can be used
reversible and the fiber rotates in the opposite direction during drying. directly as a flexible electronic material or sewn into fabric as an elec­
This silk-based actuator was demonstrated as a dynamic switch for smart tronic textile to transmit information. The resistance and capacitance of
textiles (Fig. 4c). Spider silk exhibits super-shrinkage behavior; the fiber conductive silk and its derived materials (and the corresponding elec­
length significantly reduces in a wet environment, and the shrinkage trical signal) change in response to subtle changes in specific environ­
stress can reach 22% of its fracture strength [99,100]. Although natural mental factors to accurately and quickly transmit information about the
silk has no super-shrinkage ability, super-shrinking RSF was obtained by body function of the user [106,107]. According to the response of the
the mesoscopic regulation of the silk structure [15]. Some studies have sensor to different environmental factors, sensors are divided into
shown that the super-contraction of RSF is related to the random coil, pressure sensors, strain sensors, temperature sensors, humidity sensors,
the phase of the secondary structure (random and hydration random biosensors, and electrophysiological sensors.
coils), and the ordered β-sheet phase (β-sheet a and β-sheet b) [101]. A flexible pressure sensor can detect external pressure on the human
Microfluidic shearing technology was used to dehydrate and shear silk body, convert certain behaviors into electrical signals, and monitor
proteins and control the fibril orientation and diameter of microfluidic- human health and exercise. SF has been dissolved to prepare various
spun RSF [102]. In addition, the folding shape and deformation mode advanced materials, such as hydrogels. Composite hydrogels have been
can be easily programmed by orienting the hydrophobic substrate prepared by combining hydrophilic polymers with silk protein. Silk-
(Fig. 4d). The prepared silk exhibited an initial super-contraction effect based hydrogels containing electrolytes and conductive polymers have
in a wet environment and an organic solvent, with a response time of outstanding flexibility and electrical conductivity and have been used to
only 4 s. The material has excellent stability and repeatability over 250 prepare pressure sensors [108,109]. A ternary hydrogel system
moisture absorption cycles and is widely used in bioengineering, soft composed of SF, acrylamide, and acrylic acid via one-pot thermal
robots, and intelligent textiles. Silk can also be used to prepare SF film- polymerization [110]. With the addition of SF, the water retention of the
based actuators. SF-based films actuated with a reversible drive were hydrogel was improved and its mechanical properties increased by 59%.
obtained by silk fibers degumming, silk fibers dissolving, RSF solution The prepared silk-based hydrogel can be attached directly to the skin
pouring, and annealing [103]. The interactions between the water vapor and exhibits good self-healing abilities and high adhesion (75.17 N
and SF chains in the hydrophilic domain of the SF film cause a stress m− 1), thereby avoiding signal loss related to poor adhesion. Silk-based
gradient over the film thickness that drives the mechanical motion hydrogels have broad potential in the field of intelligent wearables.
(Fig. 4e). The RSF-based thin-film actuator has a fast response and Such hydrogels have been used as resistive pressure sensors to detect
actuating performance, and high durability (no significant decrease in various human movements, and adhered to the skin on a person’s neck
the performance over 1000 cycles). These actuators have applications in to detect the vibration of the voice and monitor the health of vocal cords.
intelligent clothing layers and crawling robots. In addition, the RSF films For example, silk-based aerogels were prepared via chemical grafting
actuated in ethanol vapor exhibited reversible antagonistic actuation and free-radical polymerization [111]. Compared with hydrogels, the
characteristics against water and ethanol vapor [104]. When the RSF stomatal structure of aerogels is more stable and less affected by ambient
films were operated in a water vapor environment, they bent upward humidity, and their electrical conductivity is more stable [112]. The
(Fig. 4f), whereas in ethanol vapor, they bent downwards (Fig. 4g). addition of polyethylene glycol as a plasticizer for SF chains improved
When ethanol vapor interacts with one side of the silk protein mem­ the flexibility of a silk-based aerogel and enhanced the deposition and
brane, it facilitates the desorption of water molecules, resulting in dry­ aggregation of pyrrole cations on the SF surface to guide the formation
ing and contraction of that side of the film (Fig. 4h). As a result, the silk of polypyrrole. The prepared silk-based aerogel had a high sensitivity,
protein membrane tends to bend downwards. By harnessing this unique responsivity to external pressure, high cycling stability, and durability,
characteristic of the RSF films, it is possible to produce a single-layer and was used as a highly sensitive pressure sensor for intelligent wear­
reversible multivapor-responsive material. These materials can be ables. MXenes are a new class of 2D nanomaterials with excellent
used as sandwich components in experimental garments and biomedical electrical conductivities. Their structural constituents can be easily
materials. controlled to obtain different properties and they are highly useful for
Silk-based actuators are mostly used in smart wearable devices, such sensor applications [113]. SF was used as a bridging agent to assemble
as smart fabrics or interlayers of smart textiles. Silk materials are Ti3C2Tx MXene nanosheets into a continuous corrugated layered
intolerant to UV radiation, making them prone to yellowing and brit­ macrostructure (Fig. 5a) and prepared silk-based MXene composite films
tleness under sunlight, which degrades their mechanical properties. The (SF@MXene) [114]. The addition of MXene nanosheets results in com­
silk-based smart fabric exposes the skin to sunlight after shrinkage and posite films with excellent mechanical properties and electrical con­
deformation, and the UV rays in the sunlight may damage the skin. ductivities. SF@MXene showed good flexibility and a low elastic
Therefore, the preparation of silk-based actuators with both UV resis­ modulus, with a very low detection limit of 9.8 Pa, a high detection
tance and deformation ability is an important direction for future sensitivity of 25.5 kPa− 1, and the potential for reuse over at least 3500
development. cycles. As pressure sensors, SF@MXene can detect subtle changes in
human activity, such as changes in the human voice and wrist pulses
4.2. Silk-based sensor (Fig. 5b). Silk substrates endow the silk-based composite film with good
biocompatibility for skin contact.
Sensors are important components of intelligent wearable devices. Flexible strain sensors can detect body motions, such as joint and
Flexible sensors have been developed to satisfy human movement and muscle movements. Hydrogels are rich in water and soft in texture,

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

Fig. 5. Silk-based sensor. (a) Schematic diagram of molecular structure of SF@MXene biological composite membrane. (b) The application of SF@MXene biological
composite membrane as a pressure sensor in the field of human wearability. Reproduced with permission [114]. Copyright 2020 Elsevier. (c) A flexible temperature
sensor was fabricated by silk protein lithography. Reproduced with permission [122]. Copyright 2020 American Chemical Society. (d) An explanation of the theory of
absorption and desorption of water molecules in inherent and modified SF molecular chains. Reproduced with permission [124]. Copyright 2019 Elsevier. (e)
Schematic illustration of the formation of the PEN membrane, (f) Schematic illustration of the working electrode in our biosensors, and (f) Amplification of the PEN
membrane. Reproduced with permission [128]. Copyright 2021 Wiley-VCH. (h) Schematic illustration of the fabrication procedure of the Ppy@AM-SF/CNC elec­
trodes. Reproduced with permission [130]. Copyright 2021 Elsevier. (i) The schematic diagram of the silk fiber film and the interdigital electrode that make up the
AFMS, as well as the schematic diagram of the pressure sensing, temperature sensing and humidity sensing principles of AFMS. Reproduced with permission [132].
Copyright 2022 Springer Nature.

similar to human tissue, with excellent biocompatibility and good shape electrical conductivity, and SF and tannic acid improve the mechanical
retention with human skin [115]. Hydrogel strain sensors with excellent and antibacterial properties of the hydrogel [119,120]. The prepared
mechanical properties have been prepared by adding silk protein as an conductive hydrogel exhibited outstanding tensile properties (strain
enhancer. A conductive hydrogel was prepared by blending polyvinyl greater than 1000%) and a wide strain sensing range (greater
alcohol (PVA), borax, SF, and tannic acid [116]. PVA allows borax to than650%). The hydrogel was demonstrated as a strain sensor attached
easily form a reversible borate bond, which allows the hydrogel to self- to the skin to detect human body movements, such as finger joint
heal [117,118]. The addition of borax provides the hydrogel with movement, smiling, swallowing, and breathing. Furthermore, a small

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

amount of silk nanofiber film and graphite carbon nitride nanosheets nanocomposite membrane (Fig. 5e,f,g) [128]. SF nanofibrils maintain
were used to reinforce PVA, resulting in a hydrogel with improved enzyme activity and are immobilized in PEN using glutaraldehyde. Pt
tensile strength and toughness [121]. Using water and ethylene glycol as nanoparticles have a high catalytic activity for enzymes, and partial rGO
solvent systems, the prepared hydrogel demonstrated excellent anti- with abundant hydroxyl and carboxyl groups can immobilize the PEN
freezing ability (stable use at − 18 ℃). Adding Al3+ to the water and membrane and prevent its detachment. The assembled glucose and
ethylene glycol solvent systems resulted in organic hydrogels with lactate sensors exhibited high sensitivity, good cycling reproducibility,
excellent electrical conductivity and antibacterial properties. Sandwich- and long-term stability for up to 25 and 23.6 h, respectively.
type flexible strain sensors based on this hydrogel can quickly respond to Electrophysiological sensors can detect the electric potential of the
changes in human motion, have a large linear sensing range (0–100%), human heart, brain, blood vessels, muscles, and other tissues and organs
and were stable for use over 1000 cycles. Owing to its excellent anti­ and detect the biological signals of the human body in real time [129].
bacterial and antifreeze properties, these materials have enormous po­ Electrophysiological sensors need to be in close contact with the skin,
tential for use in flexible sensors. which requires that they are biocompatible, flexible, and conformal to
Flexible temperature sensors are used to monitor the body temper­ the skin. Considering the reasons for long-term wear, electrophysio­
ature in real-time and provide feedback on human health status over logical sensors require good air and moisture permeability. Electro­
time. A conductive ink containing PEDOT:PSS conductive polymers and physiological sensors must be designed to be as thin as possible to
sericin was used to produce micropatterned cross-electrodes on a flex­ monitor changes in the target metric quickly and accurately [27]. Pol­
ible photoactive SF substrate to prepare silk-based temperature sensors ypyrrole (Ppy) was coated on an acid-modified silk (AM-SF)/cellulose
(Fig. 5c) [122]. The sensor electrode has a temperature-sensitive layer nanocrystal (CNC) film to provide electrical conductivity and Ca-
composed of photoactive sericin and rGO and is protected by a passiv­ modified SF was used as the adhesive layer to prepare a dry epidermal
ation layer prepared by cross-linking photosensitive SF and a polyimide electrode (Ppy@AM-SF/CNC) with excellent mechanical properties and
solution. The SF-based temperature sensors are flexible and biodegrad­ biodegradability (Fig. 5h) [130]. The Ca ions in the SF adhesive layer
able, with a high sensitivity of − 0.99% ℃-1 in the temperature range of capture water molecules in the atmosphere, placing the electrode in
20–50 ℃. Each layer of the sensor is covalently bonded, and the close conformal contact with the skin, thus reducing its impedance. The
temperature-sensitive layer is loaded to avoid interference from hu­ electrode monitors electrocardiography (ECG) and electromyography
midity and improve the monitoring stability. This technology has signals from the human body. Ppy@AM-SF/CNC can be removed from
considerable potential for further development in personalized medical the skin using water without damaging the skin; however, its wearing
monitoring and wearable devices. comfort and sweat resistance were shown to be poor. Furthermore, a
Flexible humidity sensors can monitor human breathing by detecting silk-based electrode with high thermal and humidity comfort, and skin
the changes in the humidity near the mouth and nose during breathing, conformability was demonstrated [131]. A silk-based electrode material
allowing health information and movement status to be monitored was prepared by doping PEDOT:PSS into a glycerol-plasticized silk fiber
[123]. A capacitive humidity sensor based on an SF dielectric film using felt. Under sweating conditions, the silk-based electrode plasticized with
a low-cost and simple patterning method for AgNW interdigital elec­ glycerol showed low evaporation resistance (~23 Pa m2 W− 1,) and high-
trodes [124]. After methanol immersion and annealing, the β-sheet area water vapor permeability (117 g m-2h− 1). The glycerol-plasticized SF
of the SF film increased. Unbound water can escape quickly, the local electrodes produced high-quality ECG signals and have the potential to
humidity decreases, and a faster capacitive response (Fig. 5d) can be be sewn in textiles to monitor muscle potential signals during human
produced. The capacitive humidity sensor can identify the respiratory activity.
rate and intensity of a person based on the breath, covered the breathing Single-function sensing in silk-based wearable sensor devices is often
rate up to 4 Hz. The capacitive sensor prepared using this method also insufficient to fully reflect human health and movement. An all-fber
exhibited excellent flexibility and stable mechanical and electrical multifunctional sensorsensor (AFMS) based on human motion-sensing
properties during bending. This portable humidity sensor has a good and physiological data can assist in detecting body performance more
application potential for future wearable devices. A self-powered elec­ intelligently and at multiple levels. AFMS were fabricated with a double-
trochemical humidity sensor was developed based on the effect of hu­ layer structure composed of a silk fiber film and a AgNW electrode using
midity on metal–air batteries [125]. Metal–air batteries use graphite electrospinning and spraying technology [132]. Owing to the all-fiber
paper and aluminum foil as the cathode and anode layers, respectively, structure and dielectric properties of the silk fiber film, these sensors
SF and lithium bromide with good water absorption as the gel, and GO can realize multifunctional sensing of pressure, humidity, and temper­
flakes rich in hydrophilic functional groups as the electrolyte. The ature (Fig. 5i). The porosity of the silk fiber films good air permeability
excellent water absorption of the electrolyte gel layer has an evident and flexibility to the sensor during the detection of human breathing,
effect on the redox reaction during battery discharge. The ionic mobility joint movement, skin temperature, etc.
of the electrolyte determines the short-circuit current of the battery. By Although silk has many advantages in sensor development, some
measuring the current, the changes in humidity and breathing of a challenges remain. To date, researchers have mostly focused on silk to
person can be monitored. The gel electrolyte sensing layer with excellent improve the detection performance of single-signal sensors, which
moisture absorption ability resulted in a self-powered electrochemical cannot achieve simultaneous multimodal detection without noise
humidity sensor with high sensitivity (0.09 μA/S/1%), fast response interference [133,134]. Moreover, most silk-based sensors require pro­
(1.05 s), and fast recovery (0.80 s). These sensors have excellent po­ longed human contact, which significantly affects their portability and
tential for applications in the fields of convenient wearables and per­ comfort. Therefore, future research on silk-based sensors should focus
sonal health management. on improving their simultaneous multimodal detection, comfort,
Biosensors can detect normal metabolic fluids (such as sweat, tears, portability, and compatibility with other electronic devices.
blood, urine, and saliva) [126], and extract relevant data to analyze
human health. Sweat is secreted by the exocrine glands of human skin in 4.3. Silk-based energy generator
most areas of the body. Sweat is quite abundant, easily detected, and
contains numerous health-related biomarkers (ions, hormones, proteins, Smart wearable electronic equipment requires a lightweight, soft,
glucose, lactate, and alcohol) [127]. Silk provides suitable thermal and stretchable, stable, and sufficient energy supply, whereas traditional
wet comfort and biocompatibility for use in biological fluid sensors. A battery equipment (such as Li-ion batteries) are heavy and uncomfort­
glucose and lactate sensor was developed by combining a silk-based able for long-term use in a wearable device [135,136]. To provide en­
porous enzyme nanofiber (PEN) membrane consisting of SF nanofibrils ergy for wearable electronic devices, an energy conversion device can
and enzymes with an ultrathin Pt nanoparticle/graphene convert mechanical energy and body heat into electrical energy via

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

frictional, piezoelectric, and thermoelectric principles, but the device biocompatibility and high transparency, and can easily lose electrons,
must be flexible and stretchable [137]. Silk has both triboelectric and making them ideal materials for use in friction generators [140]. In
piezoelectric properties and can be used in triboelectric nanogenerators 2016, SF films were used in friction generators for the first time (Fig. 6a
(TENG) and piezoelectric nanogenerators (PENG). Silk is frequently and b) [141]. The SF film was highly transparent, with a visible trans­
used in thermoelectric generators (TEG) because of its aforementioned mittance above 90%, and was developed to dissolve in aqueous solu­
benefits. tions. The friction generator based on the SF film showed a strong ability
In 2012, the first friction generator was reported [138], which was to lose electrons, with a high and stable output performance. However,
able to collect during human activities, thus independently powering in this method, an oxygen plasma process is required to increase the
tiny wearable electronic devices [139]. SF films have good roughness of the SF film, which is a complex process not suited for large-

Fig. 6. Silk-based energy generator. (a) Photograph of the silk-based triboelectric generator (TEG) and (b) schematic structure of silk-based TEG. Reproduced with
permission [141]. Copyright 2016 Elsevier. (c) Optical image of the arch shaped testing TENG and the schematic view of the working mode. Reproduced with
permission [145]. Copyright 2020 American Chemical Society. (d) Schematic diagram of the structure of the CSPCF-TENG and the output voltage of the CSPCF-TENG
located in various parts of the automotive system when the driver touches it. Reproduced with permission [144]. Copyright 2021 Elsevier. (e) Working principal
diagram of all-fiber hybrid piezoelectric-enhanced triboelectric nanogenerator. Reproduced with permission [153]. Copyright 2018 Elsevier. (f) Preparation process
diagram of SF-substrate SWCNT/P3HT thermoelectric generators. Reproduced with permission [156]. Copyright 2023 American Chemical Society.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

scale manufacturing. To overcome this, a TENG was prepared using an formed by PVDF during electrospinning has strong piezoelectric prop­
SF film as the triboelectric layer, which was sprayed onto a polyethylene erties; therefore, the composite can be used as a piezoelectric material
terephthalate (PET)/indium tin oxide (ITO) substrate (Fig. 6c) [142]. (Fig. 6e). The two forms of energy collection resulted in a PENG with
The voltage and power density of the prepared TENG reached 213.9 V strong output performance (power density of 310 μW cm− 2 and a
and 68.0 mW/m− 2, respectively. The spraying method is suitable for voltage of 500 V). This fiber-based nanogenerator can be integrated into
mass production and has promising future prospects. A printed SF-based clothing. In addition, the device can recognize gestures to interpret
TENG was developed by micropatterning a graphite surface by screen human movements and has the potential for use in wearable anti-fall
printing, and a thin SF layer was coated onto the surface to form the alarm devices.
interdigital electrode of the generator [143]. This process further Because the ambient temperature changes periodically, the temper­
improved the output performance of the TENG toward commercializa­ ature difference between the environment and human skin can be used
tion, with optimal voltage and power density values of 666 V and 412 to drive TEG devices. According to the Seebeck effect, a higher tem­
μW cm− 2, respectively. In addition, it was reported for the first time that perature difference produces a higher TEG power [154,155]. An all-
SF can selectively absorb water molecules from the air in different states solution process was used to prepare a silk-based wearable TEG by
(gaseous and liquid). Thus, this TENG also provides respiratory moni­ spraying patterned PEDOT:PSS/AgNWs electrodes and single-walled
toring functionality and great application potential in intelligent wear­ carbon nanotube/poly(3-hexylthiophene) (SWCNT/P3HT) thermoelec­
able devices. tric nanocomposites, followed by casting the SF substrates (Fig. 6f)
Silk has also been used to prepare composite friction nanopowders. [156]. Continuous and repeated spraying/vacuum processes enabled the
Dudem et al. prepared a friction nanogenerator using crystalline silk RSF-substrated SWCNT/P3HT films to exhibit an optimized power factor
microparticles (SMPs) extracted from discarded silkworm cocoons, PVA of 204 ± 4.6 μW m − 1 K− 2 at 50 ◦ C, an electrical conductivity of 1170
and polytetrafluoroethylene (PETF) material extracted from discarded ± 52.8 S cm− 1, and a Seebeck coefficient of 41.8 ± 0.9 μV K− 1. Since
PETF [144]. Crystalline SMP loaded PVA composite film (CSPCF) was well-dispersed SWCNT/P3HT nanocomposites are obtained through π −
used as a substrate material for the friction nanogenerator, a thin Au π interactions between conjugated backbones, the performance of the
layer was coated on its surface to make it act as a positive friction RSF-substrated SWCNT/P3HT films is approximately 1.5 times better
electric material, PETF extracted from waste PETF was used as a friction than that of the glass-substrated device. The silk-based TEG, designed to
electric negative electrode, and an Al foil was introduced on its surface be worn on the forearm, generated a maximum output voltage of 6.1 mV
as a counter electrode (Fig. 6d). The device was packaged with silicone when subjected to a temperature gradient of 8 ◦ C and maintained a
rubber to avoid the influence of water molecules in the external envi­ consistently low internal resistance, even after repeated bending.
ronment and obtain stable electrical performance. The maximum output A low output power is an important issue in the use of silk-based
voltage and power density of the device reached 280 V and 14.4 W m− 2, TENGs for wearable applications. Methods such as plasma etching and
respectively, and stable performance over more than 10,000 cycles was grafting chemical groups onto the friction layer can improve the electron
demonstrated. Furthermore, a flexible fiber TENG was prepared by affinity and increase the energy-harvesting efficiency of silk-based
combining silk with CNTs via electrospinning and electrospraying TENGs. Silk and most biomaterials readily lose electrons, resulting in
[145]. In this process, the liquid solution is directly converted into a thin a positive charge. To achieve a higher output performance, silk-based
fibrous film. The prepared TENG was soft and durable and exhibited a TENGs require the addition of non-biodegradable materials [157], but
distinct layered structure. The TENG generation capacity reached 317.4 this reduces their recyclability. Although different materials are used to
μW cm− 2 in response to tapping it with fingers. improve the performance of silk-based TENGs, the energy-harvesting
Silk also exhibits an excellent piezoelectric effect and can be used in efficiency of silk-based TENGs is still low. Various strategies have
PENG devices. In 1939, Harvey observed the piezoelectric effect in silk been proposed to overcome this, such as the development of circuit
and showed that it was electronegative through a friction experiment designs incorporating charge pumps or charge excitation types, as well
between silk fragments and a steel ball [146]. The piezoelectric prop­ as circuit management switches [158]. The output power of silk-based
erties of silk were quantitatively analyzed by Fukada in 1956 [147]. The TENGs for powering sensors and other devices can be unstable after
piezoelectric coefficient of silk was measured for the first time and prolonged use because the effects of temperature and humidity in the
shown to be similar to that of quartz crystal (~2 pC N− 1) [148,149]. The environment degrade the performance of the silk-based substrates.
piezoelectric properties of silk can be improved by enhancing its crys­ Therefore, it is necessary to optimize the existing silk-based materials
tallinity and orientation [150]. Recently, it was shown that the molec­ and develop more robust materials to meet the needs of various
ular chains of SF films prepared by electrospinning can be polarized applications.
easily and exhibit a high degree of orientation [151]. An output voltage Compared to silk-based TENGs, silk-based PENGs are more stable
of 8 V, power density of 5 μW cm− 2, dynamic pressure sensitivity of 0.15 during operation and more versatile in their use in regions of the body.
V kPa− 1, and energy conversion efficiency of 21% were obtained from Although silk has excellent piezoelectric properties, it is still difficult to
the SF films, which are considered suitable for use as a PENG to provide use it alone to achieve stable functionality in medium–high-power
energy to low-power electronic devices. However, the output perfor­ electronic devices. The output performance of silk-based PENGs can be
mance of silk-based piezoelectric sensors is low, making it difficult to improved by modulating the hierarchical structure of silk, introducing
provide sufficient energy to a large number of wearable devices. active substances, or compounding it with other materials with high-
Furthermore, ZnO nanoparticles were synthesized using a direct pre­ voltage electrical properties [159]. In addition, when people sleep at
cipitation method and mixed with a silk protein solution to prepare night, silk-based TENGs and PENGs do not work properly and do not
composite films by spin coating [152]. A PENG was prepared based on provide real-time feedback on the physical health of the person. Because
the piezoelectric properties of the composite film, which exhibited a silk-based PENGs have only been reported in the last few years,
maximum output voltage of 25 V and a maximum output power density improved devices with high output power and improved comfort and
of 6.67 mW cm− 3. durability are expected in the future.
The human body can produce different forms of mechanical energy Because silk-based TEGs harvest energy through the temperature
during different activities, so combining friction and piezoelectric difference between the human body and the environment, the energy
nanogenerators can maximize the use of human body movements for conversion process is not affected by human activities or rest. However,
power generation. Electrospun SF and polyvinylidene fluoride (PVDF) silk-based TEGs are less efficient at converting energy in comfortable
nanofibers were used to prepare conductive fabrics for a wearable temperature ranges. N-type flexible thermoelectric materials currently
triboelectric PENG based on textiles [153]. Silk has good triboelectric used in silk-based TEGs are unstable in air and the required thickness
properties owing to its excellent electron loss ability, and the phase and size of the active material affect the output performance and

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

wearability of the device [160]. Therefore, the development and selec­ carbonization to confer conductive properties and applied as an elec­
tion of flexible thermoelectric materials should be a research focus of trode material in energy-storage devices to enhance their performance
future studies. [161,162]. Silk can be used in energy-storage devices in the form of fi­
Silk-based TEGs harvest energy through the temperature difference bers, fabrics, or RSF materials [163,164]. According to current research,
between the human body and the environment, so the energy conversion silk-based energy-storage devices can be classified into three categories:
process of silk-based thermoelectric generators is not affected by peo­ flexible batteries, supercapacitors, and flexible battery–supercapacitor
ple’s activities or rest. However, silk-based TEGs are less efficient at hybrid (BSH) devices. The energy and power densities are two important
converting energy in the temperature range where people are comfort­ metrics for energy-storage devices. Silk-based flexible batteries are
able. The n-type flexible TE materials currently used for silk-based TEGs characterized by a high capacity and low power density, similar to other
are unstable in the air environment. The thickness and size of flexible TE battery materials. Silk-based supercapacitors have high power densities,
materials affect the output performance and wearing comfort of silk- fast charge/discharge rates, and long cycle lives. However, they gener­
based TEGs [160]. Therefore, the development and selection of flex­ ally exhibit lower energy densities than flexible batteries. Silk-based
ible TE materials is the focus of future research on silk-based TEGs. BSH devices are designed to combine the high capacity density of bat­
tery materials with the high power density of capacitor materials in a
single device [165,166].
4.4. Silk-based energy storage devices The performance of a flexible battery is correlated with the rate of
the electrochemical reactions occurring within the battery. For example,
With the rapid development of wearable devices, the demand for Zn–air batteries are mainly affected by the kinetics of the oxygen
flexible energy-storage devices is growing. Silk has been modified by

Fig. 7. Silk-based energy storage devices. (a) Schematic structure of flexible Zn-air battery. Reproduced with permission [167]. Copyright 2019 American Chemical
Society. (b) Schematics of the structure of the quasi-solid-state Ag-Zn batteries with self-healable SF-gel electrolyte. Reproduced with permission [169]. Copyright
2023 Elsevier. (c) Flexible micro supercapacitors are fabricated by lithography. Conductive ink rotates the coating on the SF substrate and develops it with water after
UV exposure. It also shows that the device is flexible and independent and can be placed on the surface of the skin as a folded or flat structure. Reproduced with
permission [179]. Copyright 2021 Elsevier. (d) Schematic cross-section of MnO2-5/AC (activated carbon) @SSY (stainless-steel yarn)//AC@SSY asymmetric fiber
supercapacitors. Reproduced with permission [180]. Copyright 2021 Elsevier. (e) Preparation process diagram and Structure Diagram of Silk-Based Battery-
Supercapacitor. Reproduced with permission [181]. Copyright 2020 Elsevier.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

reduction reaction/oxygen evolution reaction (ORR/OER) at the air (such as –OH and –NH2) [177,178], which can be used as stabilizers and
cathode. The ORR/OER reaction rate can be increased by adding an dispersants for metal droplets. Recently, a conductive ink based on
electrocatalyst. Silk protein membranes have a larger specific surface EGaIn and silk fibroin (EGaIn/SF) was developed (Fig. 7c) [179].
area than silk fibers, thereby providing more active sites. Mixing the silk Conductive patterns were prepared on flexible substrates by screen
protein solution with Ketjen black (KB) carbon, drying, and heat treat­ printing. The coordination and complexation between SF and EGaIn
ment produced a defect-rich porous nitrogen-doped nanocarbon elec­ stabilize the EGaIn/SF and its conductivity can be restored using gravity
trocatalyst (SilkNC/KB) [167]. Silk NC/KB demonstrated remarkable deposition, evaporation induction, and mechanical sintering. In addi­
ORR catalytic activity. The flexible Zn–air batteries exhibited an tion, cross-finger electrodes with a graphene 3D array structure were
impressive ultimate current density of 6.34 mA cm− 2 and a Tafel slope of obtained on the EGaIn layer by adjusting the screen meshes and pre­
68 mV dec-1 (Fig. 7a). Moreover, its outstanding stability was demon­ cisely printing graphene ink. The prepared micro-supercapacitor had
strated by a minimal loss of only 30 mV in half-wave potential after good flexibility, cycling stability, and an areal capacitance of 35.72 mF
subjecting it to 50,000 cycles of accelerated durability testing, along cm− 2 at a current density of 25 μA cm− 2. Therefore, this technology has
with a mere 10% decline in limiting current density. great development potential for flexible wearable electronic products in
Owing to the growing demand for flexible batteries in various en­ the future. Silk is suitable as a packaging material for supercapacitors
vironments and advancements in the preparation technology for smart considering its many aforementioned benefits. For example, 1D fiber
wearable electronic devices, flexible energy batteries with multifunc­ supercapacitors were prepared using an optical fiber anode (cathode)
tional capabilities have been developed. These batteries exhibit de­ comprising stainless-steel yarn current collectors coated with MnO and
gradability, shape control, and self-healing. The good degradability and activated carbon (only activated carbon), along with a silk composite
biocompatibility of silk, along with the abundant active groups on the film (silk protein and polyurethane) on two parallel optical fiber elec­
surface of its protein chains, make it a suitable functional material for trodes (Fig. 7d) [180]. The electrical performance of the fiber super­
use in flexible batteries. The key component of a flexible degradable capacitor encapsulated in the silk composite film was 28% higher than
battery is the solid or gel electrolyte. A formable yarn-like zinc-ion that of an equivalent device packaged in plastic. A fiber supercapacitor
battery (ZIB) consisting of a smart humidity-sensitive plasticized with a diameter of only 1 mm showed good potential as an energy-
gelatin-silk protein (GSF) electrolyte film and a dual-yarn electrode storage device for wearable devices as it had good flexibility and
structure was prepared [168]. The responsiveness of the GSF electrolyte wearability, and its capacitance retention was maintained at 97.1% over
film to water vapor allows convenient modification of the shape of the 1000 bending cycles.
battery to suit the working environment and user requirements. The ZIB- Batteries have high energy densities, and supercapacitors have good
assembled transient flexible battery device exhibits a significant specific power density. By combining battery-type and capacitor-type elec­
capacity of 311.7 mA h g− 1 and demonstrates excellent cycling stability trodes, the advantages of both can be combined to develop new BSH
with 94.6% capacity retention after 100 cycles. Furthermore, the yarn devices. A flexible high-performance BSH device based on a Ni4.5Co4.5-
ZIB devices showcase remarkable shape plasticity, retaining up to 82.5% selenide nanowire/Ni-plated cotton (NPCC) cathode, silk fabric sepa­
of their capacity after 80 bends. These batteries also display good rator, and Fe3C/carbon fiber anode was developed (Fig. 7e) [181]. The
biodegradability, completely degrading within 45 days through enzy­ Ni-plated cotton cloth was first prepared by a simple chemical plating
matic digestion. method, onto which Ni–Co–Se nanowires were grown as a cathode
Gels are commonly used as self-healing materials that dynamically material (battery-type metal electrode). The carbon fibers were verti­
repair themselves via the formation of numerous internal hydrogen, cally immersed in a solution containing ferric chloride and subjected to
ionic, and covalent bonds. A flexible Ag–Zn battery with a self-healing heating, drying, and annealing to obtain Fe3C/carbon fiber anodes
silk protein-based hydrogel (SF-gel) as the electrolyte (Fig. 7b) [169]. (capacitive carbon electrodes). Silk fabrics have been used as diaphragm
This self-healing silk protein-based hydrogel consisted of SF and poly­ materials owing to their excellent electrical insulation properties, suit­
acrylamide, which formed a semi-interacting network structure. The able pore sizes and porosities, and good electrolyte wettability. More­
amide-bonded molecular chains of polyacrylamide (PAM) and SF mo­ over, an asymmetric packaging strategy was employed to enhance the
lecular polypeptides within the polymer matrix readily form abundant voltage and energy density of a BSH device. The silk-based BSH device
hydrogen bonds, thereby providing the self-healing capability of the SF- exhibited an impressive maximum energy density of 47.4 Wh kg− 1 at a
gel electrolyte. The final battery exhibited an average capacity of 100 power density of 1.5 kW kg− 1. Furthermore, it demonstrated remarkable
mAh/g at 0.5 A/g and retained 85.7% of its capacity after 800 cycles. cycling stability, retaining 80.0% of the initial capacitance after 4000
Flexible supercapacitors are new portable energy-storage devices cycles. This strategy provides an efficient and simple method for pre­
that are widely used in smart wearable devices because they are soft and paring high-performance wearable BSH devices.
stretchable and exhibit high power densities, fast charging and dis­ In recent years, silk-based energy-storage devices for smart wear­
charging rates, long cycle lives, and low environmental impact ables have made rapid progress. However, some problems remain to be
[170–172]. Silk and its regenerated materials can be used as function­ solved. In the wearables field, good comfort performance and excellent
ally active encapsulation materials in flexible supercapacitors. A simple flexibility are essential; however, it is difficult to prepare flexible elec­
method for fabricating 2D planar flexible supercapacitors was reported trode materials with excellent mechanical and electrochemical proper­
based on co-doped rGO and SF composite films [173]. Through a co- ties. Carbon materials are highly flexible, conductive, lightweight, and
doping strategy, the introduced Co nanoparticles modify the electronic chemically stable, and have great advantages in both supercapacitors
structure of graphene, thereby improving the pore affinity of the ionic- and battery materials. Silk materials have a hierarchical structure,
liquid electrolyte, reducing the resistance of the electrode, and contain abundant nitrogen, and can be transformed into N-doped carbon
improving the electrochemical performance of the electrode. The SF nanomaterials with hierarchical pore structures that are suitable for use
solution was prepared by adding an ionic liquid (EMIm+BF_4) and in future energy-storage devices [162,182].
dripping it onto Co-doped GO paper to prepare Co-doped GO/SF com­ Batteries and supercapacitors cannot simultaneously achieve high
posites. The resulting supercapacitor exhibited a high weight capaci­ energy or power densities. Although BSH devices have been developed,
tance of 104F g− 1, and a capacitance retention rate of 89% over 10,000 their energy density is still lower than that of batteries. Moreover, the
cycles, indicating good chemical stability. Liquid metals are ideal can­ preparation of BSH devices is more complicated, and the devices are
didates for flexible electronics because of their high electronic conduc­ large. Therefore, it is also necessary to develop new technologies and
tivity and excellent self-healing performance [174]. SF has been shown flexible materials to improve the energy and power densities of silk-
to exhibit metal-ion adsorption and tunable gelation in recent studies based energy-storage devices. In addition, the preparation method of
[175,176]. The amino-acid residues of SF have numerous polar groups flexible energy storage devices also affects the energy storage

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

performance to a certain extent, while energy storage devices with 1D drug delivery through the skin over an extended period and can be
fiber shapes, 2D film shapes and 3D structures can be adapted to loaded with a range of drugs (vaccines, insulin, hormones, enzymes,
different environments. For smart and wearable energy-storage devices, contraceptives, antibiotics, and anticancer drugs) for painless delivery,
fiber-shaped batteries and supercapacitors have the advantages of high thereby improving patient compliance and cure rates [188–191].
flexibility and small volume and are expected to contribute significantly Silk-based microneedles have great advantages for transdermal drug
in the future of this field. delivery owing to their biocompatibility and controllable drug release.
Based on the mode of drug release, silk-based microneedles are classified
into solid microneedles, coated microneedles, dissolved microneedles,
4.5. Silk-based microneedles phase-change microneedles, and biodegradable microneedles
[188,192]. Long-term contact between the microneedle and the skin
Microneedles can easily penetrate human skin for humoral infor­ also contributes to wound healing. Flexible electronics can also be in­
mation detection, drug delivery, and skin repair [183–185]. Because silk tegrated into microneedles to prepare smart silk-based microneedles for
has excellent biocompatibility, controllable degradability, excellent human wearable diagnostic and therapeutic bonding systems.
mechanical properties, soft and easy processing (can be processed using PDMS is typically used as a template for the preparation of silk-based
water), and enables a long drug-storage time, it is widely used in microneedles, and the corresponding microneedles are prepared by
microneedle substrates, needles, and other medical applications injecting silk proteins into the template. The aspect ratio of the PDMS
[60,186,187]. Silk-based microneedles can accurately achieve stable

Fig. 8. Application of Silk in the Field of Microneedle. (a) digital light processing 3D printing scheme using SF ink; using anti-aliasing technology to produce
microneedles with smooth edges. Reproduced with permission [194]. Copyright 2020 Elsevier. (b) A kind of enhanced silk microneedle with double layer structure.
Reproduced with permission [59]. Copyright 2021 American Chemical Society. (c) The schematic diagram of the design of the microneedle patch with active liner
and the process of quickly separating the microneedle patch from the backing paper by smearing the microneedle patch on the skin by generating a large number of
air bubbles. Reproduced with permission [198]. Copyright 2022 Elsevier. (d) Glucose-dependent equilibrium of phenylboronic acid derivatives, (e) Schematic di­
agram of controllable insulin release from skin layer caused by blood sugar changes in human body. Reproduced with permission [200]. Copyright 2019 American
Chemical Society. (f) Schematic diagram of electrochemical biosensor microneedle based on SF/D-sorbitol [201]. Copyright 2020 Royal Society of Chemistry. (g)
Schematic diagram of multi-functional silk-based microneedle structure. Reproduced with permission [203]. Copyright 2020 Wiley-VCH.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

template has been controlled by a thermal stretching method to manu­ (Fig. 8e). This silk-based intelligent microneedle is expected to provide
facture high-aspect-ratio silk-based microneedles in large quantities insulin on demand over an extended period.
[58]. Methanol can induce the formation of β-sheets in SF structures Because silk-based microneedles can stably and safely contact bio­
[193]. Therefore, immersing silk-based microneedles in a methanol so­ markers in the subcutaneous tissue for a long time, they have great
lution can change their mechanical properties and regulate the drug- advantages in the field of biosensors. A convenient wearable biological
delivery rate. In 2021, Shin et al. first proposed a digital light- diagnostic device was prepared by combining flexible electronics with
processing 3D printing technology to prepare silk-based microneedles silk-based microneedles. Human health factors can be accurately
(Fig. 8a) [194]. The solution was solidified by mixing the riboflavin assessed based on the biomarker contents. An electrochemical biosensor
photoinitiator and SF solution, and SF microneedles with high hardness microneedle was developed based on a silk/sorbitol composite material
were obtained after dehydration and shrinkage treatment. Riboflavin for the base and needles, with platinum and silver wires attached as the
can induce the free radicals of SF to form double tyrosine bonds during working, counter, and reference electrodes (Fig. 8f) [201]. Glucose ox­
photo-crosslinking, and the shape of the silk-based microneedle can be idase was integrated into the needle to catalyze the oxidation of glucose
precisely controlled by controlling the optical image [195]. to H2O2, which is transported to the Pt electrode. A current proportional
Silk-based solid microneedles produce large pores for delivering to the initial glucose concentration is obtained by detecting the H2O2
drugs to the surface of the skin, thereby facilitating drug absorption. In concentration of the anode on the surface of the Pt working electrode,
addition, these microneedles can be used in photodynamic tumor ther­ and the blood glucose concentration can be monitored in real time. After
apy. After silk-based solid microneedle pretreatment, the skin exhibits 24 h of monitoring, the initial reaction rate reduced by less than 7%. In
improved absorption of porphyrin and other photosensitizers, which addition, the microneedle sensing device can be stored for a long time;
then combine with visible light to produce highly cytotoxic reactive the response decreased by 23.1% after 35 days of storage at 37 ℃.
oxygen species that cause tumor cell death [196]. Silk-based micro­ Because the silk-based microneedle is conformal with the skin and re­
needles are coated with the desired drug, which is released into the leases drugs in a controlled manner, it can also be used for skin repair.
subcutaneous tissue with the swelling or degradation of the silk. A The strong adhesion of the microneedle to the skin is key to skin repair.
double-layer microneedle with enhanced mechanical properties was Inspired by the insertion of a swollen beak of an internal parasite, a
prepared via the mesoscopic hybridization of silk (Fig. 8b) [59]. The bilayer hydrogel phase-change microneedle was developed based on an
crosslinking of silk with glutaraldehyde, followed by annealing pro­ expandable mussel protein as a shell and a non-expandable SF core
moted the formation of silk-protein molecular networks, from which the [202]. The outer layer of mussel protein exhibited good adhesion to the
first layer of silk-based microneedles with excellent mechanical prop­ skin and wet tissue. The local expansion of the microneedles results in
erties was prepared. Then, the drug and low-crystallinity SF were mixed interlocking with tissues, and the adhesion derived from mussel adhe­
on the first layer of silk-based microneedles to prepare silk-based coated sive protein (MPA) can capture bioactive cells and growth factors
microneedles with a double-layer structure, which have great applica­ secreted during cell proliferation to help wound healing. This double-
tion potential in vaccine delivery, cosmetology, and antibacterial ap­ layer microneedle can also deliver anti-inflammatory drugs to the
plications. Silk-based dissolving microneedles encapsulate the drug in a target tissue, thus exhibiting great advantages for skin trauma and in­
soluble or degradable matrix. When the silk-based microneedle is ternal wound repair. Recently, a multi-functional silk-based micro­
inserted into the skin, the drug is released quickly with the dissolution of needle was developed for biochemical sensing, movement monitoring,
the matrix and base when they come into contact with body fluids [197]. and wound healing [203]. The microneedle is based on silk proteins and
Silk-based biodegradable microneedles are prepared by mixing drugs integrates an inverse opal photonic crystal (IOPC) structure, a micro­
with silk proteins, and the drug is released slowly upon degradation of fluidic channel, and a microcircuit for sensing (Fig. 8g). The IOPC
the microneedle. After the silk-based microneedle is inserted into the structure significantly increased the specific surface area of the tip,
skin, the needle separates from the base and remains in the skin to slowly which improved the drug-loading capacity of the microneedles and the
degrade and release the drug. Such microneedles were prepared using sensitivity to the biomarkers via the optical properties of the IOPC. The
polyacrylic acid/NaHCO3 as the base for silk-based microneedles [198]. microneedle system uses an N-isopropylacrylamide hydrogel with a
After pressing the microneedle into the skin for 1 min, contact with body phase transition temperature of 37 ℃ as an intelligent drug delivery
fluid stimulates the HCO3 in the base to produce CO2, thereby realizing system. When the temperature increases to 37 ℃, the hydrogel contracts
patch separation (Fig. 8c). The microneedle was loaded with growth and releases the encapsulated drug. When the body fluid flows through
hormones for drug release over 7 days, and the separated microneedle the microfluidic channel, the wound inflammatory biomarkers IL and
was completely degraded within 21 days. Silk-based phase-change CRP in the body fluid bind to specific antibodies and fluorescent marker
microneedles can release drugs into a matrix via the swelling of the silk antibodies in the detection area, and the detected area is identified to
and other polymers as they absorb tissue fluid. SF/polyethylene glycol diagnose the skin wound. After microneedle treatment, the skin wound
and acrylate (PEDGA)/sucrose polymer microneedles were developed, showed good collagen deposition and a large amount of granulation
with SF as a scaffold and PEDGA and sucrose as the matrix, which can tissue growth. The surface skin treated with drug-loaded microneedles
trigger rapid drug release; with the dissolution of sucrose, PEDGA ac­ recovered quickly, demonstrating good wound-healing ability. In addi­
celerates swelling to achieve subsequent drug release [199]. However, tion, the microcircuit on the microneedle surface can detect the move­
controlled-release microneedles cannot achieve drug release in response ments of the fingers, wrists, and elbows. Therefore, this system has great
to stimuli, such as diabetic blood glucose levels. To realize intelligent potential for personal health management.
drug delivery, an intelligent SF microneedle composed of a semi- The excellent control of the biodegradability and biocompatibility of
interpenetrating network hydrogel prepared from SF and phenylboric silk make it the foremost candidate material for microneedle prepara­
acid/acrylamide was developed [200]. The silk-based microneedle tion, highlighting its tremendous potential and research value in the
consisted of two hydrogel layers. The needle area was composed of a future advancement of smart wearable microneedles. The controllability
semi-interpenetrating network of hydrogels containing SF and boric of the silk degradability is key to precise drug release, and the degra­
acid. Phenylboric acid can reversibly bind to glucose in an aqueous so­ dation and drug-release times of silk-based microneedles can be
lution (Fig. 8d). The microneedle base layer was composed of an SF controlled by modifying the silk structure. However, owing to differ­
hydrogel, which provided the necessary mechanical properties. The ences in patient constitutions and the influence of human activities,
outer layer of the skin has a local lack of water, and boric acid combines which may accelerate or delay drug release from silk-based micro­
with water at high sugar levels to increase the hydrophilicity of the skin needles, especially in chronically ill patients, an unsuitable drug-release
layer, thus releasing insulin. When the blood sugar drops, an internal time could harm the patient. The combination of silk-based micro­
hydrated phase is formed, preventing the release of preloaded insulin needles with flexible electronic components allows for real-time health

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

monitoring, precise drug release based on feedback from collected nanofiber films are transparent and self-healing. Currently, silk-based e-
physiological information, and self-diagnosis and therapy. skins mainly comprise electrically conducting RSF materials as the
functional layer or nanofibrous membranes and hydrogels as the base
5. Silk-based electronic skin material.
A transparent carbide filament nanofiber film was combined with an
Skin is the largest organ in the body and serves as a physical barrier unstructured PDMS film to prepare a highly sensitive pressure-sensing e-
between the body and the outside world. The skin responds to changes in skin with a unique interconnected N-doped nanofiber structure [207].
the external environment and internal information from the human The e-skin exhibited excellent electrical properties, extremely high
body and transmits signals accordingly. The skin also protects the in­ sensitivity (34.47 KPa− 1), ultra-low pressure detection limit (0.8 Pa),
ternal organs and is the first immune barrier of the body [204,205]. fast response time of 16.7 ms, and stability over 10,000 cycles. E-skins
Flexible electronic skin (e-skin) inspired by human skin has been applied can be attached to human skin to detect human physiological signals.
to the surface of the skin, and exhibited a sensory function similar to that However, they currently cannot compete with human skin, which can
of human skin, thereby realizing the monitoring and diagnosis of human simultaneously detect friction, pressure, temperature, humidity, and
movement and health [128,206]. The e-skin must be conformal and other stimuli. Therefore, future e-skins should achieve multi-responsive
biologically compatible with human skin and have appropriate softness, sensing functions to comprehensively detect physiological information.
stretchability, and be comfortable to wear. Silk proteins show great Conductive carbon nanofibers with a graphite structure were transferred
potential for use in e-skin because of their inherent biocompatibility and to flexible polymer films using an elastic seal strategy (PET for tem­
outstanding mechanical properties. The primary purpose of the e-skin is perature sensing and PDMS for strain sensing) to prepare silk nanofiber
sensing [206]. carbon-fiber membranes (Fig. 9a) [208]. The temperature-sensitive
Silk-based e-skins simultaneously exhibit functionalities such as resistive layer and strain-sensing fiber-fracture layer were combined to
sensing, self-powering, and energy storage. The conductive functional­ prepare a dual-functional e-skin that successfully detected and distin­
ization of silk greatly expands the application of silk-based materials in guished the spatial distribution of exhalation, finger compression,
portable wearable devices. Although silk fibers, yarns, and fabrics temperature, and pressure, and improved the detection of physiological
exhibit excellent breathability and moisture permeability, they are not information.
in close contact with the skin and do not self-heal. Silk hydrogels and silk Humidity sensors can also be used to monitor human respiration and

Fig. 9. Application of silk in the field of E-skin. (a) Schematic diagram of the manufacturing process of the temperature–pressure combination E-skin derived from
the whole filament. Reproduced with permission [208]. Copyright 2017 American Chemical Society. (b) Schematic illustration showing the fabrication process of
(Ga/SF/Ca2+) electronic tattoos. (c) Schematic diagram of self-healing mechanism of electronic tattoos based on reversible hydrogen bond and coordination bond.
Reproduced with permission [19]. Copyright 2019 WILEY-VCH. (d) Schematic diagram of the preparation process of multi-functional silk-based hydrogel sensor with
super toughness. Reproduced with permission [212]. Copyright 2021 Elsevier. (e)Schematic diagram of SF/Ca (II) ion permeation. Reproduced with permission
[215]. Copyright 2020 WILEY-VCH. (f) Preparation and working principle of photoelectric skin (OE-skin). Reproduced with permission [219]. Copyright 2022 Wiley-
VCH. (g) Schematic and optical images of packaged hybrid PZ (piezoelectric) devices. The scale shows 1.5 cm, (h) Schematic diagram of working principle of (Hybrid
triboelectric-piezoelectric) TB-PZEG-skin in sealing device under mechanical stress. Reproduced with permission [220]. Copyright 2020 Elsevier.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

other functions. To further improve the monitoring performance, a horseradish peroxidase and Ca (II) was complexed to form a non-
curable multi-functional electronic tattoo was developed based on gra­ covalently crosslinked compound to improve the mechanical proper­
phene/SF/Ca2+ (Fig. 9b) [19]. SF was used as the substrate material, ties of the hydrogel. A dielectric elastomer layer was placed between two
and graphene sheets with excellent electrical and mechanical properties hydrogel layers to fabricate a silk-based capacitive sensor that was
were used as the conductive and sensing layers. The temperature and sensitive to pressure and deformation. The e-skin prepared using this
pressure sensing performance of the electronic tattoos originates from hydrogel had an elastic modulus of 20 kPa and a maximum strain of
the separation of adjacent graphene layers under pressure and the 900%. It exhibited responsivity to both temperature and strain and was
transition of the interfacial charges of graphene at elevated tempera­ able to monitor the movement of joints and the throat while simulta­
tures [209–211]. When the humidity increases, Ca ions expand the neously monitoring temperature.
matrix by coordinating and trapping water molecules from the air. Thus, The sensing signals produced in response to multiple environmental
the conductive path of graphene is reduced, resulting in a change in stimuli from the same conductive material may overlap and be distorted,
conductivity that can be used to monitor changes in skin humidity [29]. making it difficult to distinguish between them. To address this, an RSF-
In addition, the abundant coordination and hydrogen bonds in elec­ based hydrogel e-skin was developed based on AgNWs pressure and
tronic tattoos provide an excellent self-healing ability (Original con­ ionic temperature sensing [217]. Using cotton fabric as the substrate, a
ductivity restored within 0.3 s) (Fig. 9c), and the e-skin adhered well to microstructure was formed on the surface of the RSF hydrogel, and
human skin to monitor breathing, ECG, body temperature, and other AgNWs were embedded on the surface of the RSF. The formed AgNWs/
information. RSF hydrogel was saturated with a CaCl2 aqueous solution to introduce
Hydrogels have very good skin conformance, and silk-based hydro­ Ca (II) ions and prepare RSF/AgNWs/Ca (II) hydrogels with temperature
gels have good biocompatibility. Thus, hydrogels are ideal materials for and pressure sensitivity. Two pieces of the RSF/AgNWs/Ca (II) hydrogel
e-skin. A high-performance silk-based hydrogel e-skin was developed by were layered with the conductive layers of the AgNWs oriented toward
dissolving silk protein in a lithium bromide solution, which was then each other. Owing to the microstructure, the conductive AgNWs layer
added to PEDOT:PSS and tannic acid (Ta) (Fig. 9d) [212]. PEDOT ex­ was uneven, whereby the contact area of the conductive region (and
hibits both thermoelectric and conductive properties. Tannic acid and resulting current signal) increased under pressure. The mobility of Ca
polar groups in the hydrogel achieved strong bonding, which improved (II) ions in the hydrogel increases with increasing temperature to pro­
the toughness of the silk-based hydrogel; the free diffusion of tannic acid vide temperature sensing. The RSF/AgNWs/Ca (II) hydrogel had pres­
in the hydrogel also provided thermal resistance, moisture retention, sure and temperature sensitivities of 0.20 kPa− 1 and 1.54 %◦ C− 1,
and antibacterial properties. This silk-based hydrogel exhibited highly respectively, and was able to successfully monitor the heartbeat, upper
sensitive pressure detection in the range of − 40 to 60 ◦ C, responded to and lower jaw movements, body temperature, and temperature changes
external temperature changes from 20 to 60 ◦ C, and had a good thermal during orthodontic treatment.
sensitivity of − 2.3 ◦ C. The mechanical properties of advanced functional Although human skin cannot respond to light, owing to its high
materials such as hydrogels decline after the dissolution of silk fibers. To expansibility, e-skin can achieve light sensitivity by the addition of
overcome this, a method for hybridizing and reconstructing the hierar­ conductive materials with light responsivity. Melanin, which contains
chical structure of silk by combining wool keratin and CNTs into an photoreactive free radicals, is an ideal material for the preparation of
intermediate structure of SF via intermolecular template nucleation photoelectronic e-skin as its electrical conductivity increases upon light
[213]. This improves both the mechanical and electrical properties of irradiation [218]. Melanin was combined with SF to prepare photo­
the silk. Wool keratin is an effective molecular template for the nucle­ electric OE-skin (Fig. 9f) [219]. OE-skin is a p-type semiconductor ma­
ation and formation of SF materials; the α-helix in wool keratin mole­ terial with high conductivity of up to 6 mS cm− 1. In addition, its
cules can be formed into the hierarchical structure of SF molecules conductivity increased by 40% under green laser and ultraviolet LED
(mesoscopic hybridization), while the addition of CNTs can improve the illumination. Melanin/silk produces more free radicals in the hydration
overall electrical properties of SF. The asymmetric double-sided protein state, and g increases, which can further improve its conductivity and
material hybridized by WK and CNTs had an insulating side with enable humidity sensing. Two pieces of OE skin sandwiched between
biocompatibility and a conductive side with a resistance of 130 Ω sq-1. metal electrodes accumulated charges at the junction and exhibited
The mesoscopic hybrid strategy produced an e-skin with excellent me­ capacitive energy behavior. In addition, OE-skin has self-healing ability
chanical properties and adjustable electrical properties. Its sensitivity and shows great potential for e-skin applications. Most e-skins require
was adjustable between − 1.05 and − 6.35 kPa− 1, and the nondestructive energy to transmit the collected information. Therefore, self-powered e-
measurement range was close to 2 kPa. The e-skin was able to detect skins have been extensively studied in recent years. For example, ZnO
micro-vibrations of the human skin, such as pulse waves, so that nanorods (NRs) were added to a silk-based hydrogel to prepare friction
vascular sclerosis and real-time blood pressure conditions can be eval­ and power-generating e-skin (EG-skin) (Fig. 9g) [220]. The addition of
uated to achieve real-time health monitoring. ZnO NRs increased the piezoelectric metrics of the silk-based hydrogel
Some e-skin use ions to sense and transmit environmental informa­ by eight times. Owing to the mixed effect of friction and piezoelectricity
tion from human skin. Similar to the information transmitted by human (Fig. 9h), the EG-skin can produce a power of 1 mW cm− 2, which can
nerve cells, ion-based sensing uses the changes in ion mobility in the activate devices such as LEDs, oximeters, and stopwatches. In addition,
matrix in response to environmental changes to produce a more sensi­ finger movements were monitored. Furthermore, hollow Ag nanofibers
tive e-skin that better simulates the information collection of real human were deposited on silk membranes to prepare friction electrodes [221].
skin [214]. Temperature-sensitive e-skin was prepared using silk as the The mesoscopic functionalization of silk proteins by the addition of
raw material and Ca (II) as the conductive ion (Fig. 9e) [215]. Ca (II) glycerol and polyurethane greatly enhances the elasticity of silk-protein
chelates and stabilizes the silk structure, captures water molecules from membranes. The hollow silver nanofibers exhibited good air perme­
the atmosphere, and reduces the freezing point of water, thus improving ability, while the silk substrate provided excellent stretchability,
the moisturizing ability and temperature application range of ionic e- biocompatibility, and biodegradability. The maximum power density of
skin (-30–80 ℃). Silk-based ionic e-skin is also transparent and has self- the self-powered e-skin was 0.8 W m− 2. This type of e-skin also has the
healing capability. The prepared e-skin was able to monitor temperature function of tactile sensing and can be used as a switch to control the IoT.
changes in human skin, but because the electrical conductivity of Ca (II) In the wearables field, e-skin is a very important device and repre­
is insensitive to deformation, it cannot be used as a pressure or strain sents an application of the IoT and artificial intelligence (Such as robots)
sensor. To overcome this limitation, RSF was cross-linked with horse­ in the wearable field. With the continual progress in science and tech­
radish peroxidase and combined with CaCl2 to prepare a silk-based nology, society’s focus on health and its demand for intelligent equip­
hydrogel [216]. The covalently crosslinked compound formed by ment have increased. The functionality, safety, and comfort of e-skins

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

are constantly being improved. The biocompatibility of silk and its transmission of information from in situ signals [222]. However, the
excellent performance in many electronic devices provide a huge systematization of silk-based e-skin is challenging because of the poor
development space for e-skin. compatibility between different units in the system and size limitations.
The future development of silk-based e-skins includes three main In addition, owing to the need for prolonged wear, silk-based e-skins
directions: multifunctionality, systematization, and high efficiency. Like must be efficient in processing the large amount of physiological infor­
real skin, silk-based e-skin is expected to enable the sensing of multiple mation continuously generated by the body. The development of intel­
types of environmental information and provide multifunctionality, ligent algorithms to process the data collected by silk-based e-skin and
including good comfort, self-healing capability, long detection time, and intelligently filter out important information would improve the effi­
excellent durability. Therefore, silk-based e-skins need to avoid inter­ ciency of data acquisition and transmission. These improvements are
ference between different physiological signals, quickly and accurately expected to drive the efficient development of silk-based e-skins.
process and transmit physiological information from the body, and
monitor and diagnose the health condition of the human body in real 6. Silk-based smart wearable textile
time. The systemization of silk-based e-skin requires it to harvest its own
energy and independently perform the acquisition, processing, and Silk fibers/yarns and fabrics offer a multitude of advantages, such as

Fig. 10. Silk-based smart wearable textile. (a) Schematic diagram of twisting muscle of two-ply torque balance silk, (b)The sleeves of smart clothing shrink in a
humid environment, A continuous photograph restored to its original length in dry air. Reproduced with permission [225]. Copyright 2019 WILEY-VCH. (c) The
schematic diagram of the layered interface in the thermochromic silk fiber and the color change of the patterned thermochromic silk sewn in the fabric when the
temperature changes. Reproduced with permission [227]. Copyright 2021 Springer Nature. (d) The working principle of a CT-TEG based on silk. Reproduced with
permission [233]. Copyright 2017 Springer Nature. (e) Schematic diagram of MRC circuits using ubiquitous wire OSCs to power electronic textiles. Reproduced with
permission [236]. Copyright 2021 Elsevier. (f) Preparation of carbonized silk fabric@Mxene flexible 2D Planar Capacitor. Reproduced with permission [241].
Copyright 2017 Elsevier. (g) Schematic illustration of fabrication process of the C@Si@G composite. Reproduced with permission [242]. Copyright 2021 Elsevier.

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

a low density/weight, softness, deformability, breathability, and mois­ analyze the health of the human body by detecting various fluids,
ture permeability, making them ideal materials for preparing smart including sweat droplets secreted by the skin and saliva produced during
wearable textiles. Silk fibers/yarns and fabrics can be functionalized and breathing.
modified to obtain various properties, such as conductivity, antibacte­ Silk fabrics are used as the flexible substrates or frictional electrical
rial capabilities, UV shielding, water resistance, and friction resistance. layers for the preparation of smart wearable energy-harvesting textiles.
These functionalized silk materials can be used to develop wearable A corrugated textile-based triboelectric generator (CT-TG) with a woven
textiles with actuating, sensing, energy-harvesting, and energy-storing fabric made of silk at the top and a knitted fabric made of silicone rubber
functions [223]. In addition, smart wearable textiles exhibit superior at the bottom, with narrow air gaps between the layers, which had an
durability compared with other silk-based flexible electronics. The overall corrugated structure [233]. The CT-TG generates considerable
weave structure of textiles helps minimize the strain on the yarns within energy by pressing, rubbing, and stretching (Fig. 10d). During the
the fabric during extensive deformation. Consequently, fabric-based stretching and releasing motions, the CT-TG exhibited a maximum
textiles offer significantly longer cycling lifetimes than film-based flex­ output performance of 28.13 V and 2.71 μA. This impressive perfor­
ible electronics. Smart wearable textiles also allow for a high degree of mance highlights its potential applications in wearable energy-
stretching, double curvature bending, and in-plane shear simulta­ harvesting textiles. However, fabric-based wearable triboelectric gen­
neously. Therefore, smart wearable textiles provide better wearing erators tend to be characterized by a lack of abrasion and stain resis­
comfort and withstand the deformation caused by human activities tance, and repetitive washing may degrade their electrical performance.
[224]. To address this problem, a highly abrasion-resistant and machine-
When silk fibers reach their maximum water-absorption capacity, washable fabric-based TENG was prepared using a liquid-phase fluori­
they undergo significant changes in their physical dimensions; the vol­ nation technique with a homemade urethane perfluorooctyl silane
ume of the silk fibers increases by ~ 34% and the diameter expands by (NHCOO-PFOTS) [234]. The F atom has strong electron absorption ca­
~ 15%, while the length undergoes a smaller increase of 1% [97]. Silk pacity, which can improve the electronegativity of silk. NHCOO-PFOTS
yarn was stretched using a twist insertion technique to obtain humidity- can form strong chemical bonds with the surface of fabrics, such as silk,
sensitive silk “muscle” [225]. After degumming, the silk is twisted and and improve its hydrophobicity. The fabric-based TENG demonstrated
then folded from the middle and then twisted again to prepare the an impressive maximum output power of 2.08 W m− 2 at a resistance of
strands (Fig. 10a). The strand was heat-treated on a mandrel to obtain a 10 MΩ. Notably, the device exhibited negligible performance decay
mandrel wound yarn with a spiral structure. When the chirality of the even after 45,000 contact–separation cycles and 70 h of washing.
strands matches that of the wound yarn (homochirality: ZZ or SS; het­ Wireless power transmission can avoid the integration of wires, reduce
erochirality: ZS or SZ), the filament muscle with a spiral structure con­ the weight of the device, and provide continuous energy for textile
tract or elongates during moisture absorption (homochiral contraction electronic devices [235]. Multi-walled CNTs and chitin carbon were
and heterochiral elongation, respectively). When the relative humidity combined with SF to prepare omnipotent silk-based coils (OSCs) via
was changed from 20% to 80%, the contraction rate of silk muscle electrospinning (Fig. 10e) [236]. Fluor-alkylated organosilicon was
woven with heterochiral yarn reached 70%. The silk muscle was woven deposited on the surface of the OSCs by spraying to provide both hy­
into a smart wearable actuating textile that exhibited sleeve elongation drophobic and oil-repellent properties to minimize the effect of the
and contraction under different humidity conditions (Fig. 10b). external environmental humidity on the output power. Through the
The flexible and deformable nature of the fabric is a significant principle of resonant inductive coupling, the OSCs can continuously and
advantage in the preparation of sensing wearable textiles. Inspired by remotely provide energy for textile-based electronic devices. In addi­
the cavity-rich structure on the surface of sunflowers, an e-textile was tion, OSCs have water-washing resistance and antifouling properties,
prepared with a hierarchical structure by growing MoS2 nanosheets in and can be used stably for more than 50 cycles. This simple
situ on a carbonized silk fabric [226]. In addition, the cavity-rich manufacturing process has great commercial potential for smart
structural design of this fabric provides numerous active sites and can clothing and wearable electronics.
be used as an electrode material for flexible batteries. Coating silk yarns Silk can be used as a substrate material for flexible supercapacitors
with thermochromic dyes enables the fabrication of temperature sensors and batteries after carbonization to prepare silk-based smart wearable
that can detect the temperature of the human body. Spinning was energy storage textiles. MXenes are a recently developed family of 2D
combined with continuous impregnation and coating techniques to materials comprising early transition metal carbides and carbonitrides,
prepare thermochromic silks with superhydrophobicity and fast pro­ of which Ti3C2Tx is the most widely studied [237,238]. Ti3C2Tx exhibits
grammable thermochromic responses (Fig. 10c) [227]. The thermo­ hydrophilicity, electrical conductivity, and excellent ion-embedding
chromic silk exhibited excellent mechanical properties and cycling behavior; therefore, it can be used as an electrode material for super­
stability. With fiber lengths exceeding 10 km, these silks can be woven capacitors [239,240]. For example, 2D planar supercapacitors with
into fabric. Their temperature response time was as fast as 1 s, and they flexibility and cycling stability were prepared by coating thick Ti3C2Tx
could be reliably used for hundreds of cycles. sheets onto carbonized silk fabrics (Fig. 10f) [241]. The layered porous
Humidity and strain sensors can be prepared by loading GO onto the structure of the carbonized silk fabric provides a high deposition area for
surface of silk fabrics. Functional groups on the GO surface generate a high loading of an electrode material. The supercapacitor exhibited a
protons when in contact with water molecules to reduce the electrical surface capacitance of 362 mF cm− 2. Silk can also be used as a substrate
impedance in humid environments [228,229]. Silk-based wearable material for flexible batteries after carbonization. Liang et al. fabricated
humidity-sensing textiles prepared by the continuous chemical plating a sandwich-structured C@Si@G composite using carbonized silk fibers
of conductive interdigital electrodes and spraying of a GO-sensing layer (C), silicon nanoparticles as the interlayer, and graphene (G) as the outer
on silk fabrics were used to detect human respiration [230]. GO loaded layer via a simple chemical reaction and carbonization process
on the surface of silk fabric is reduced to rGO by heat treatment, which (Fig. 10g) [242]. The presence of functional groups and doped nitrogen
has good electrical conductivity, as well as UV shielding and hydro­ atoms on the surface of the underlying carbonized silk fibers enhanced
phobicity. This system was used as a smart wearable strain-sensing the number of accessible active sites, whereas the fibrous structure
textile to monitor human activity information [231]. Silk fabrics can promoted accelerated electron conduction. The sandwich structure and
also be endowed with unidirectional moisture-wicking functionality doped nitrogen synergistically extended the reversible cycling time of Si
through surface modifications. The Janus wettability of lotus leaves was and improved its electrochemical performance. As the anode material
mimicked to prepare a smart wearable biofluid-sensing textile using silk for lithium-ion batteries, C@Si@G-15 (Si, 15 wt%) demonstrated stable
fabric as the backing material and silk yarn coated with conductive cycle performance with a discharge capacity of 972 mA h g− 1 at
carbon paint as the electrode [232]. This smart wearable textile can 0.2 A g− 1 after 120 cycles as well as a discharge capacity of 1070 mA h

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1
g− at 1 A g− 1 after 300 cycles. their washing and friction resistance. Researchers should focus on the
Silk-based smart wearable textiles combine sensing, energy har­ effect of integrating various functional electronic devices into silk tex­
vesting, energy storage, and actuation to monitor and regulate human tiles while maintaining their original properties. Silk textiles exhibit
activity, thereby driving the Fourth Industrial Revolution in the textile excellent flexibility and air and moisture permeabilities. When devel­
and fashion industries [243,244]. The pursuit of high-quality physical oping new silk-based smart wearable textiles, it is essential to consider
health is driving the growth of smart wearables. The advantages of silk- the potential impact of the electronic components on the textile
based smart wearable textiles in the wearables field have attracted the properties.
interest of researchers. For industrial development, it is crucial that silk-
based smart wearable textiles undergo further improvements in terms of

Fig. 11. Application of silk in the field of intelligent radiation refrigerated textiles. (a) Schematic diagram of electrospun nanosilk, (b) Diagram of outdoor tem­
perature measuring device, (c) Temperature changes of electrospun nanofilaments, electrospun microfilaments, raw silk and ambient air over a single day.
Reproduced with permission [249]. Copyright 2021 Wiley-VCH. (d) A diagram of Al3O2 nanoparticles on the surface of NP-silk fabric and a comparison of the
outdoor temperature of NP-silk fabric with silk fabric and cotton fabric, (e) Comparison of water vapor transmittance of NP-silk fabrics with silk fabrics, cotton fabrics
and Tyvek (pe textiles). Reproduced with permission [26]. Copyright 2021 Springer Nature. (f) UV resistance of ALD-TiO2 silk fabric, (g) Radiative cooling effect of
ALD-TiO2 silk fabric and (h) Surface temperature change of ALD-TiO2 silk fabric and original silk fabric under infrared light irradiation. Reproduced with permission.
Reproduced with permission [251]. Copyright 2021 Elsevier.

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7. Silk-based radiative cooling intelligent clothing (ALD) is a chemical vapor method for forming functional thin films on
substrate surfaces. The gas-phase precursors alternately enter the reac­
Silk has a high level of gloss and thermal and wet comfort. It has been tion chamber to form thin films on the fiber surface. Ultrathin films
used in clothing, quilts, and other textiles for thousands of years. constructed using ALD have the characteristics of high shape preserva­
Another great advantage of using silk clothing is its cooling sensation on tion, uniformity, and high bonding fastness to the fiber interfaces [250].
the skin. Researchers have found that the randomly stacked silk fibers in Ultrathin amorphous TiO2 films were deposited using ALD on the sur­
the cocoons protect the pupae from temperature fluctuations. These silk faces of silk fibers and fabrics with a thickness of only 5/1000 and a
fibers have a self-assembled hierarchical structure that imparts high content of 5.33% [251]. This functional coating improved the UV
solar reflectivity and thermal emissivity, which can provide a radiation- resistance of silk. After 672 h of UV exposure, the tensile strength of the
cooling effect, where the skin feel cool when it comes into direct contact modified silk fiber was still 87.17% of that of the original fiber. Under
with silk fabric [245,246]. outdoor irradiation, the cooling effect of the ALD-coated fabric reached
According to research, refrigeration accounts for at least 15% of the 10.1 ◦ C (Fig. 11 f–h). The deposition of a TiO2 film on the silk surface
global electricity consumption, which is expected to increase with the also improved its mechanical properties and washing durability. After
intensification of global warming and lead to massive consumption of 20 intensive washing cycles (comparable to 200 household or com­
resources and the associated environmental pollution. Therefore, the mercial washing cycles), the UV protection factor of the ALD-coated
development of environmentally friendly passive cooling methods is of fabric remained almost unchanged. The two modification methods
great significance [26]. Silk-based intelligent clothing with a passive enabled the fabrication of an intelligent wearable fabric with the effect
radiation-cooling effect can achieve independent cooling of the human of passive radiation cooling during the day while retaining the wearing
body, improve wearer comfort, reduce energy consumption, and is of performance of the silk. Compared with portable and lightweight smart
great significance for environmental protection. In addition, the fabric wearable devices, silk-based radiation-cooling apparel requires exten­
can be used to provide an excellent cooling for integrated electronic sive usage, thus necessitating large-scale and cost-effectiveness
wearable devices to reduce the effects of heat generation by the devices manufacturing.
and increase the service life and stability of the electronic equipment. Currently, the colors of silk-based radiation-cooled garments are
Passive radiation during the day can cool the human body. This tech­ limited to white or silver, which cannot satisfy the demand for fash­
nology can be applied to textiles to achieve stable and effective cooling ionable and colorful clothing. Colored fabrics lead to greater light ab­
of the human body. Among the many textiles, silk is the best choice as it sorption, which affects the cooling effect of silk-based radiation-cooled
has a radiation cooling effect. However, the amide bonds between amino garments. Therefore, it is challenging to prepare colored silk-based ra­
acids, such as tyrosine, tryptophan, and phenylalanine, and the main diation-cooled garments. Recently, our team developed a colorless
chain of silk fibers are broken after long-term sunlight exposure [247]. radiation-cooling device. Wang et al. developed a scalable electro­
This results in yellowing of the fiber and a reduction in its mechanical spinning/inkjet printing method based on quantum-dot photo­
properties, which affects the wearability of the silk. Silk fibers show high luminescence to achieve a sub-ambient multicolor radiation cooler
absorption in the UV region, which decreases the total reflectivity of silk [252]. The multicolored radiative cooler is based on a cellulose acetate
to sunlight and degrades the radiation-cooling effect. Consequently, in nanofiber film as the base material and contains a top layer of photo­
recent years, studies have focused on improving the solar reflection luminescent perovskite quantum dots as a top layer. The radiative cooler
performance of silk to improve its radiation-cooling effect and UV can display green, yellow and red colors in the sunlight and achieves a
resistance. cooling effect of 5.4–2.2 ◦ C. This strategy provides a valuable reference
Thousands of parallel nanofibers are densely arranged inside silk for the preparation of color-based radiation-cooled clothing.
fibers, which also contain voids with diameters of hundreds of nano­ Existing radiative-cooling technology provides better results out­
meters. These fiber voids scatter light and guide it to the fiber axis to doors; however, many people work or study indoors. Therefore, silk-
prevent it from entering the cocoon. However, during this process, the based radiation-cooling clothing needs to be improved to achieve in­
silk absorbs some of the light, reducing the daytime passive radiation- door cooling. Most silk-based radiation-cooling fabrics are loaded with
cooling effect [246,248,249]. A modified electrospinning method was functional coatings, which limits the long-term durability of the fabric as
used to reorganize silk fibers [249]. In the case of a silk fiber with an the coatings can be removed by washing and friction. In addition,
average diameter of 0.25 μm, the reflectivity in the wavelength range of functional coatings can influence the moisture and air permeabilities of
400–900 nm is maximized for diameters of 0.25–1.76 μm. The substrate fabrics. Therefore, future research should focus on the comfort perfor­
temperature of the electrospun nanofiber membrane under direct sun­ mance and durability of silk-based radiation-cooling clothing.
light was 7.5 ◦ C lower than that of the control (Fig. 11 a–c). However,
recycled silk prepared by electrospinning has poor mechanical proper­ 8. Conclusion and outlook
ties, limiting its application in clothing.
Fiber-surface modification can minimize the effects of processing on The unique structure of silk provides excellent mechanical proper­
the mechanical properties of fibers, which is the mainstream method ties, comfort, biocompatibility, and controlled degradability. Methods
currently used by researchers. Al3O2 nanoparticles were applied to the such as feeding conductive nanomaterials to silkworms, coating the fiber
surface of silk fabric using tetrabutyl titanate as a coupling agent to surface with conductive functional materials, and preparing carbonized
improve the reflectivity of silk in the UV region so that the total silk via heat treatment, are effective for imparting silk with electrical
reflectivity of silk fabric in sunlight reached approximately 95% [26]. conductivity. Silk also exhibits hygroscopic swelling and the piezo­
Under daytime sunlight, the temperature of nanoprocessed silk (NP-silk) electric effect, with different absorption capacities for water molecules
was 3.5 ◦ C below the ambient temperature, and the temperature of in the liquid and gaseous states. In addition, silk can be processed into
simulated skin decreased by 8 ◦ C. The strategy of introducing Al3O2 various shapes, and silk proteins are rich in reactive groups that can be
nanoparticles onto the silk surface retains the good wearability of silk, combined with other functional nanomaterials to provide new func­
and the water vapor permeability and wicking distance of nano­ tionality. Owing to these advantages, silk and its derivatives are widely
processed silk were similar to those of the original silk (Fig. 11 d,e). used in actuators, sensors, electronic skins, self-generating devices,
Tetrabutyl titanate can form hydrogen bonds and strong covalent bonds energy-storage devices, microneedles, and radiation-cooling smart
with Al2O3 and silk, respectively. This sub-bonding design strategy im­ textiles.
proves the adhesion of Al2O3 nanoparticles to silk, but the nanoparticles Silk currently faces many challenges and obstacles in its develop­
can still be removed during repeated washing cycles, which could ment process. Silk needs to be fed, coated, and carbonized by heat
potentially harm the environment and user. Atomic layer deposition treatment to obtain electrical conductivity. However, these methods

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T. Xing et al. Chemical Engineering Journal 474 (2023) 145534

degrade some of the original properties of the silk, resulting in a poor Laboratory for Modern Silk, Soochow University (Grant No. SDGC2148),
comprehensive performance of the prepared wearable electronics. and National Local Joint Laboratory for Advanced Textile Processing
Optimizing the retention of the original silk properties while imparting and Clean Production (Grant No. 17). Tonghe Xing, Annan He, and
high electrical conductivity should be a future development direction. In Zhiyu Huang contributed equally to this work.
addition, advanced functional materials, such as silk-based hydrogels,
are limited by their poor conductivity. Hower it can be endowed with References
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