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近年来, 可穿戴电子产品得到了广泛的研究, 为健康监测、人类疾病诊断和治疗以及智能机器人提供了新的机会. 传感器是可穿戴电子产品的关键组成部分之一. 蚕丝(bombyx mori)材料具有高产量、优异的拉伸强度(0.5—1.3 GPa)和韧性(6 × 104—16 × 104 J/kg)、良好的生物相容性、可降解性以及易加工性等特征. 随着生物材料和相关制造技术的快速发展, 蚕丝基先进材料被研究应用在可穿戴传感器中. 本文首先介绍了蚕丝自下而上的层结构以及蚕丝基先进材料的形态和特点, 随后综述了近年来蚕丝在可穿戴传感领域的研究进展, 包括机械(应力、应变)传感器、电生理传感器、温度传感器及湿度传感器等. 讨论和总结了不同传感器的工作机制、结构和性能, 蚕丝蛋白在其中的作用以及它们在健康监测中的应用. 最后, 提出蚕丝基可穿戴传感器在实际应用中所面临的挑战和未来展望.In recent years, wearable electronics has received extensive attention, providing new opportunities for implementing health monitoring, human disease diagnosis and treatment, and intelligent robotics. Sensor is one of the key components of wearable electronics. Silk (Bombyx Mori) material shows unique features including high yield, excellent tensile strength (0.5–1.3 GPa) and toughness ((6–16) × 104 J/kg), good biocompatibility, programmable/controllable biodegradability, novel dielectric properties, and various material formats. With the rapid development of biomaterials and related manufacturing technologies, advanced silk-based materials have been studied and applied to wearable sensors. Here, we firstly introduce the five-level structure of silk fibroin from bottom to top and characteristics of silk-based advanced materials, and then review the research progress of silk-based advanced materials in wearable sensors in recent years, including mechanical sensors, electrophysiological sensors, temperature sensors and humidity sensors. The working mechanism, structure and performance of different sensors, the role of silk proteins in them, and their applications in health monitoring are discussed and summarized. Finally, the challenges and future prospects of silk-based wearable sensors in practical applications are put forward.
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Keywords:
- silk fiber /
- silk fibroin /
- wearable sensor /
- mesoscopic reconstruction
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图 1 蚕丝基先进材料应用于柔性电子领域的时间发展线 生物可吸收电子[3](2009); 超共形电子[21](2010); 柔性OTFTs[22](2011); 瞬态电子[5](2012); 共形无线生物传感器[30](2012); 柔性太阳能电池[31](2014); 生物摩擦发电机[32](2015); 生物忆阻器[33](2015); 碳化丝织物(CSF)可穿戴应变传感器[34](2016); 蚕丝衍生的碳基电子皮肤[35](2017年); 皮肤可拉伸电极[36](2018); 基于生物可降解和可拉伸蛋白质的传感器[37](2019); 全纺织电子皮肤[38](2019); 可调温度的电子皮肤[39] (2020)
Fig. 1. The timeline of the development of silk-based advanced materials for soft electronics: Bioresorbable electronics[3] (2009); ultraconformal bioelectronics[21](2010); flexible OTFTs[22] (2011); transient electronics[22](2012); conformal wireless biosensors[22](2012); flexible solar cells[31] (2014); bio-triboelectric generator[31] (2015); bio-memristor[33] (2015); carbonized silk fabric (CSF) wearable strain sensors[34] (2016); silk-derived carbon based E-skins[35] (2017); on-skin stretchable electrodes[36] (2018); biodegradable and stretchable protein-based sensor[37] (2019); all-textile electronic skin[38] (2019); electronic skin for human thermoregulation[39] (2020).
图 2 SF纤维和非纤维材料的层级网络结构示意图[46] Lv1: 氨基酸序列; Lv2: α-螺旋和β-折叠; Lv3: β-微晶; Lv4: β-晶体网络; Lv5: 纳米纤维网络
Fig. 2. Schema of the hierarchical network structures of SF fibers and none-fiber silk materials[46]. Lv1: the amino acid sequence; Lv2: α-helix & β-sheet; Lv3: β-crystallites; Lv4: crystal network; Lv5: nanofibrils network.
图 3 蚕丝基材料的介观功能化 (a) SF和GO之间的键合[47]; (b) 热处理下β片和无规则卷曲之间可调控的结构变化[17]; (c) 一种蚕丝基忆阻器[33]; (d) 用于生物摩擦发电机的蚕丝纳米纤维膜[32]; (e) β-折叠衍生的碳结构的基本示意图[64]
Fig. 3. Mesoscopic functionalization of silk-based materials: (a) The chemical bonding between SF and GO[47]; (b) the revisable structure changes of β-sheets and random coils under high thermal treatment[17]; (c) a silk-based memristor[33]; (d) silk nanofiber membrane for bio-triboelectric generator[32]; (e) schematic of β-sheet-derived carbon basic structural units[64].
图 4 蚕丝基应变传感器的设计 (a)一种皮芯结构的石墨/蚕丝柔性应变传感器[34]; (b)一种基于碳化蚕丝织物的可穿戴应变传感器[65]; (c)一种用于监测人体运动的RSF基水凝胶[67]; (d)一种RSF基的单电极TENG和应变传感器整合平台[68]
Fig. 4. Design of silk-based strain sensor: (a) A graphite/silk flexible strain sensor with sheath-core structure[34]; (b) a wearable strain sensor based on carbonized silk fabric[65]; (c) an RSF-based hydrogel for monitoring human movement[67]; (d) an RSF-based single electrode TENG and strain sensor integrated platform[68].
图 5 蚕丝基压力传感器的设计 (a)一种RSF基的生物相容和可降解压力传感器[37]; (b)一种蚕丝包裹的纤维基压力传感器[69]; (c)一种基于蚕丝织物的无线压力传感器[38]
Fig. 5. Design of silk-based pressure sensor: (a) An RSF-based biocompatible and degradable pressure sensor[37]; (b) a silk fiber wrapped fibrous pressure sensors[69]; (c) an wireless pressure sensor based on silk fabric[38].
图 6 RSF基电生理传感器的设计 (a)一种用于EMG监测的RSF塑化电极[36]; (b)一种Ca2+改性的RSF胶粘剂[72]; (c)一种用于ECG监测的可穿戴Ag NW/RSF电极[73]
Fig. 6. Design of RSF-based electrophysiological sensors: (a) An RSF plasticized electrode for EMG monitoring[36]; (b) a Ca2+ modified RSF adhesive[72]; (c) a wearable Ag NW/RSF electrode for ECG monitoring[73].
图 7 蚕丝基温度和湿度传感器的设计 (a)一种蚕丝衍生的可穿戴温度和压力传感器[74]; (b)一种可监测温度和压力蚕丝基电子织物[69]; (c)一种基于RSF的可自愈的多功能电子纹身[75]; (d)一种可控温的RSF基耐热电子皮肤[39]
Fig. 7. Design of silk-based temperature and humidity sensor: (a) A silk-derived wearable temperature and pressure sensor[74]; (b) a silk-based electronic fabric for temperature and pressure sensing[69]; (c) a self-healable multifunctional electronic tattoos based on RSF[75]; (d) an RSF-based heat-resistant electronic skin for thermoregulation[39].
表 1 蚕丝基可穿戴传感器的材料特性和功能总结
Table 1. Summary of properties and functions of silk-based wearable sensors.
传感器类型 传感材料 基底材料 信号 应用 文献 应变 蚕丝纤维和Gr Ecoflex 电阻 关节运动 [34] 应变 碳化的丝织物 Ecoflex 电阻 人体运动 [65] 应变 PSB PSB 电阻 手指运动 [67] 应变 Ag NWs RSF膜 电流 人体运动 [68] 压力 CSFM PDMS 电流 脉搏运动 [35] 应变+压力 Ag NFs和Ecoflex RSF膜 电容 手臂运动 [37] 压力 蚕丝纤维和Ag NWs Ecoflex 电容 智能织物 [69] 压力 rGO 蚕丝织物 电阻 脉搏运动 [48] 压力 Ag NWs 蚕丝织物 电容 手臂运动 [38] 电生理 Au RSF膜 电阻 肌电图 [36] 电生理 Ag/AgCl RSF水凝胶 电压 心电图 [72] 电生理 Ag NWs RSF水凝胶 电压 心电图 [73] 温度+压力 碳化的丝纤维 PET 电阻 电子皮肤 [74] 温度 离子液体和丝纤维 Ecoflex 电阻 智能织物 [69] 温度+加热器 Ag NFs + Pt RSF膜 电阻 电子皮肤 [39] 湿度 Gr RSF膜 电阻 表皮电子 [75] 应变+湿度+温度 IDE (Ag NWs) RSF膜 电容 呼吸监测 [81] -
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Google Scholar
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Google Scholar
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