Biocompatible Electrospun Biomaterials for Advancing Thermoregulating Wearable Sensors in Next-Generation Smart Textiles

✅ 全文
作者 Sandra Varnaite-Žuravliova; Žaneta Rukuižienė; Virginija Skurkytė-Papievienė; Paulė Bekampienė; Vykintė Trakšelytė; Julija Baltušnikaitė-Guzaitienė 期刊 Journal of Functional Biomaterials 发表日期 2026 ISSN 2079-4983 DOI 10.3390/jfb17020100 类型 原创研究 (Original Research)

📄 英文摘要 English Abstract

EN

The rapid growth of electronic devices, including wearable sensors, has increased electronic waste, driving interest in sustainable, biocompatible materials. Electrospun biomaterials have emerged as versatile substrates for multifunctional wearable textiles, offering flexibility, high surface area, tunable porosity, and biocompatibility. Using natural polymers (e.g., silk fibroin, cellulose, chitosan) and synthetic polymers (e.g., polycaprolactone, polylactic acid, PVDF), electrospinning produces nanofibrous mats capable of supporting thermal regulation, moisture management, and integrated sensing for pressure, temperature, humidity, or chemical detection. Nature-inspired designs, hybrid composites, and advanced architectures enable passive and active thermoregulation via phase-change materials, thermochromic dyes, hydrogels, and conductive nanofibers, while maintaining wearer comfort, breathability, and skin safety. Despite progress, challenges persist in durability, washability, energy efficiency, manufacturing scalability, and recyclability. This review provides a comprehensive overview of biomaterials, fabrication techniques, multifunctional sensor integration, and thermoregulation strategies, highlighting opportunities for next-generation wearable textiles that combine sustainability, adaptive thermal management, and high-performance sensing.

📄 中文摘要 Chinese Abstract

中文
生物相容性静电纺丝生物材料已成为多功能可穿戴纺织品的通用基底,具有柔韧性、高比表面积、可调控孔隙率和生物相容性。静电纺丝可由天然聚合物(如丝素蛋白、纤维素、壳聚糖)和合成聚合物(如聚己内酯、聚乳酸、聚偏氟乙烯)制备纳米纤维膜,从而支持热调节、湿管理以及对压力、温度、湿度或化学物质的集成传感。先进材料科学与可穿戴电子学的融合推动了智能纺织品的发展——这类织物嵌入功能组件,能够感知、响应并适应环境和生理刺激。热调节是长期佩戴舒适性的核心挑战,因为可穿戴设备与皮肤直接接触。被动方法包括相变材料、反射涂层和多孔结构,而主动系统则整合热电模块、微流道冷却和响应性聚合物。聚己内酯(PCL)、聚乳酸(PLA)、丝素蛋白和壳聚糖等生物相容性聚合物无毒、可生物降解且亲肤,静电纺丝可将其转化为可呼吸的纳米纤维膜,并可掺入功能添加剂。

📋 英文结构化总结 English Structured Summary

全文整理

EN

Background:

Biocompatible electrospun biomaterials have emerged as versatile substrates for multifunctional wearable textiles, offering flexibility, high surface area, tunable porosity, and biocompatibility. Electrospinning produces nanofibrous mats from natural polymers (e.g., silk fibroin, cellulose, chitosan) and synthetic polymers (e.g., polycaprolactone, polylactic acid, PVDF) that can support thermal regulation, moisture management, and integrated sensing for pressure, temperature, humidity, or chemical detection. The convergence of advanced materials science and wearable electronics has catalyzed smart textiles—fabrics embedded with functional components capable of sensing, responding, and adapting to environmental and physiological stimuli.

Thermal regulation is a core challenge in long-term wearable comfort because wearables are in direct contact with the skin. Passive approaches include phase change materials, reflective coatings, and porous structures, while active systems incorporate thermoelectric modules, microfluidic cooling, and responsive polymers. Biocompatible polymers such as PCL, PLA, silk fibroin, and chitosan are non-toxic, biodegradable, and skin-friendly, and electrospinning transforms them into breathable nanofibrous mats that can incorporate functional additives.

Methods:

N/A - Review article. The review provides a comprehensive overview of biomaterials, fabrication techniques, multifunctional sensor integration, and thermoregulation strategies, examining material selection, fabrication strategies, and sensor integration, while addressing the challenges and opportunities that lie ahead in realizing next-generation smart textiles.

Results:

Electrospun biomaterials enable passive and active thermoregulation via phase-change materials, thermochromic dyes, hydrogels, and conductive nanofibers while maintaining wearer comfort, breathability, and skin safety. Biocompatibility is described as a dynamic system-level response shaped by skin–textile interactions, encompassing non-irritating surface chemistry, breathability, moisture management, mechanical softness, flexibility, and resistance to microbial growth. Material architecture, mechanical compliance, and regulatory alignment through ISO 10993-aligned cytotoxicity and irritation assessments, ISO 20743 antimicrobial testing, and REACH/EN 1811 controls are central to reliable thermoregulating wearables.

Solution electrospinning offers broad material compatibility and ultrafine fibers, while melt electrospinning avoids solvents and produces more robust fibers for durable textile interfaces. Hybrid composites, nature-inspired designs, and advanced architectures enable simultaneous passive and active thermal management, moisture control, and real-time sensing. Challenges persist in durability, washability, energy efficiency, manufacturing scalability, and recyclability.

Data Summary:

The provided text reports limited quantitative statistics. The smart textiles market is projected to exceed $12 billion by 2025. Solution electrospinning can form ultrafine fibers with diameters from a few tens of nanometers to several micrometers, while melt electrospinning generally produces thicker fibers, often in the micrometer range. For metal components in prolonged skin contact, EN 1811:2023 under REACH sets a nickel-release compliance decision limit of ≤0.88 µg·cm−2·week−1.

Conclusions:

The literature indicates that biocompatible electrospun biomaterials are a promising foundation for thermoregulating wearable sensors and next-generation smart textiles. Thermoregulation, comfort, and safety emerge as co-designed features rather than competing objectives when electrospun, breathable, and mechanically compliant architectures are combined with validated material chemistries. Future research must focus on hybrid systems that combine passive and active thermal management, sustainable materials, and intelligent feedback mechanisms to optimize comfort and performance.

Practical Significance:

These materials support real-world applications in healthcare for remote patient monitoring, rehabilitation, and chronic disease management; in sports for performance optimization and injury prevention; in military uniforms for environmental hazard detection and vital monitoring; and in fashion for interactive and expressive clothing. They enable skin-friendly, breathable, and sustainable smart textiles that can monitor physiological parameters and autonomously regulate thermal comfort in dynamic environments.

📋 中文结构化总结 Chinese Structured Summary

中文

背景:

生物相容性静电纺丝生物材料已成为多功能可穿戴纺织品的通用基底,具有柔韧性、高比表面积、可调控孔隙率和生物相容性。静电纺丝可由天然聚合物(如丝素蛋白、纤维素、壳聚糖)和合成聚合物(如聚己内酯、聚乳酸、聚偏氟乙烯)制备纳米纤维膜,从而支持热调节、湿管理以及对压力、温度、湿度或化学物质的集成传感。先进材料科学与可穿戴电子学的融合推动了智能纺织品的发展——这类织物嵌入功能组件,能够感知、响应并适应环境和生理刺激。热调节是长期佩戴舒适性的核心挑战,因为可穿戴设备与皮肤直接接触。被动方法包括相变材料、反射涂层和多孔结构,而主动系统则整合热电模块、微流道冷却和响应性聚合物。聚己内酯(PCL)、聚乳酸(PLA)、丝素蛋白和壳聚糖等生物相容性聚合物无毒、可生物降解且亲肤,静电纺丝可将其转化为可呼吸的纳米纤维膜,并可掺入功能添加剂。

方法:

不适用——综述文章。该综述全面概述了生物材料、制备技术、多功能传感器集成和热调节策略,考察了材料选择、制备策略和传感器集成,并探讨了实现下一代智能纺织品所面临的挑战与机遇。

结果:

静电纺丝生物材料可通过相变材料、热致变色染料、水凝胶和导电纳米纤维实现被动与主动热调节,同时保持佩戴舒适性、透气性和皮肤安全性。生物相容性被描述为由皮肤—纺织品相互作用所塑造的动态系统级响应,涵盖无刺激性表面化学、透气性、湿管理、机械柔软性、柔韧性以及对微生物生长的抵抗能力。材料结构、机械顺应性,以及通过符合 ISO 10993 的细胞毒性和刺激性评估、ISO 20743 抗菌测试和 REACH/EN 1811 控制所实现的法规一致性,是可靠热调节可穿戴设备的关键。溶液静电纺丝具有较广的材料兼容性和超细纤维,而熔融静电纺丝可避免使用溶剂,并生成更坚固的纤维,适用于耐用的纺织品界面。杂化复合材料、仿生设计和先进结构可实现被动与主动热管理、湿度控制和实时传感的同步进行。耐久性、可洗涤性、能效、制造可扩展性和可回收性方面仍存在挑战。

数据摘要:

所提供文本报告的定量统计数据有限。预计到2025年,智能纺织品市场规模将超过120亿美元。溶液静电纺丝可形成直径从几十纳米到几微米的超细纤维,而熔融静电纺丝通常生成较粗的纤维,常处于微米级范围。对于与皮肤长期接触的金属部件,REACH 框架下的 EN 1811:2023 设定了镍释放合规判定限值为 ≤0.88 µg·cm⁻²·周⁻¹。

结论:

文献表明,生物相容性静电纺丝生物材料是热调节可穿戴传感器和下一代智能纺织品的有前景的基础。当静电纺丝、透气且机械顺应性良好的结构与经过验证的材料化学相结合时,热调节、舒适性和安全性表现为协同设计的功能,而非相互竞争的目标。未来研究应聚焦于结合被动与主动热管理、可持续材料和智能反馈机制的杂化系统,以优化舒适性和性能。

实践意义:

这些材料支持现实应用:在医疗健康领域用于远程患者监测、康复和慢性病管理;在体育领域用于运动表现优化和损伤预防;在军装领域用于环境危害检测和生命体征监测;在时尚领域用于交互式和表达性服装。它们使亲肤、透气且可持续的智能纺织品成为可能,能够监测生理参数,并在动态环境中自主调节热舒适性。

📖 英文全文 English Full Text

EN

pmc J Funct Biomater J Funct Biomater 2398 jfbio jfb Journal of Functional Biomaterials 2079-4983 Multidisciplinary Digital Publishing Institute (MDPI) PMC12942008 PMC12942008.1 12942008 12942008 41745562 10.3390/jfb17020100 jfb-17-00100 1 Review Biocompatible Electrospun Biomaterials for Advancing Thermoregulating Wearable Sensors in Next-Generation Smart Textiles https://orcid.org/0000-0001-7930-1751 Varnaitė-Žuravliova Sandra 1 * https://orcid.org/0009-0003-8699-6864 Rukuižienė Žaneta 1 Skurkytė-Papievienė Virginija 1 Bekampienė Paulė 1 Trakšelytė Vykintė 1 https://orcid.org/0000-0002-5097-3367 Baltušnikaitė-Guzaitienė Julija 1 2 Xu Tailin Academic Editor Douroumis Dennis Academic Editor 1 Department of Textile Technologies, Center for Physical Sciences and Technology, Demokratų str. 53, LT-48485 Kaunas, Lithuania; zaneta.rukuiziene@ftmc.lt (Ž.R.); virginija.skurkyte@ftmc.lt (V.S.-P.); paule.bekampiene@ftmc.lt (P.B.); vykinte.trakselyte@ftmc.lt (V.T.); julija.baltusnikaite@ftmc.lt (J.B.-G.) 2 Department of Production Engineering, Faculty of Mechanical Engineering and Design, Kaunas University of Technology, Studentų str. 56, LT-51424 Kaunas, Lithuania * Correspondence: sandra.varnaite.zuravliova@ftmc.lt 18 2 2026 2 2026 17 2 508428 100 23 12 2025 05 2 2026 12 2 2026 18 02 2026 27 02 2026 27 02 2026 © 2026 by the authors. 2026 https://creativecommons.org/licenses/by/4.0/ Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license . The rapid growth of electronic devices, including wearable sensors, has increased electronic waste, driving interest in sustainable, biocompatible materials. Electrospun biomaterials have emerged as versatile substrates for multifunctional wearable textiles, offering flexibility, high surface area, tunable porosity, and biocompatibility. Using natural polymers (e.g., silk fibroin, cellulose, chitosan) and synthetic polymers (e.g., polycaprolactone, polylactic acid, PVDF), electrospinning produces nanofibrous mats capable of supporting thermal regulation, moisture management, and integrated sensing for pressure, temperature, humidity, or chemical detection. Nature-inspired designs, hybrid composites, and advanced architectures enable passive and active thermoregulation via phase-change materials, thermochromic dyes, hydrogels, and conductive nanofibers, while maintaining wearer comfort, breathability, and skin safety. Despite progress, challenges persist in durability, washability, energy efficiency, manufacturing scalability, and recyclability. This review provides a comprehensive overview of biomaterials, fabrication techniques, multifunctional sensor integration, and thermoregulation strategies, highlighting opportunities for next-generation wearable textiles that combine sustainability, adaptive thermal management, and high-performance sensing. nanofibers electrospinning wearable-sensors multifunctionality biomaterials biocompatibility biosensor thermoregulating thermal properties smart textiles This research received no external funding. pmc-status-qastatus 0 pmc-status-live yes pmc-status-embargo no pmc-status-released yes pmc-prop-open-access yes pmc-prop-olf no pmc-prop-manuscript no pmc-prop-legally-suppressed no pmc-prop-has-pdf yes pmc-prop-has-supplement no pmc-prop-pdf-only no pmc-prop-suppress-copyright no pmc-prop-is-real-version no pmc-prop-is-scanned-article no pmc-prop-preprint no pmc-prop-in-epmc yes pmc-license-ref CC BY 1. Introduction The convergence of advanced materials science and wearable electronics has catalyzed the emergence of smart textiles—fabrics embedded with functional components capable of sensing, responding, and adapting to environmental and physiological stimuli. Among the myriad of innovations driving this field, biocompatible electrospun biomaterials have garnered significant attention for their potential to serve as foundational substrates in wearable sensors, particularly those designed for thermoregulation. Electrospinning (see Figure 1 ), a versatile and scalable technique, enables the fabrication of nanofibrous mats with high surface area-to-volume ratios, tunable porosity, and mechanical flexibility—attributes that are critical for seamless integration into textiles and for maintaining wearer comfort [ 1 ]. When engineered from biocompatible polymers such as polyvinylidene fluoride (PVDF), silk fibroin, or polylactic acid (PLA), these electrospun fibers not only support physiological compatibility but also offer functional properties like piezoelectricity and thermal responsiveness [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. The integration of such materials into wearable sensors has opened new avenues for real-time health monitoring, enabling the detection of vital signs such as skin temperature, hydration levels, and metabolic activity [ 9 , 10 , 11 ]. These sensors, when embedded in garments, can autonomously regulate thermal comfort by activating heating or cooling mechanisms in response to detected changes, thereby enhancing both performance and well-being in diverse environments [ 11 , 12 , 13 ]. Moreover, the shift toward sustainable and transient electronics has further underscored the importance of biodegradable and non-toxic materials in wearable systems. Electrospun biomaterials, particularly those derived from natural sources like silk fibroin, align with this vision by offering eco-friendly alternatives without compromising functionality [ 2 ]. The primary aim of this review is to provide a comprehensive overview of the current state, challenges, and future directions in the development of thermoregulating wearable sensors based on biocompatible electrospun biomaterials. As wearable technology becomes increasingly integrated into healthcare, sports, and personal wellness, the demand for materials that are both functional and skin-compatible has become paramount. Central to this discussion is the critical role of electrospinning technology in fabricating nanofibrous scaffolds from biocompatible polymers, which can be engineered to support thermal regulation in smart textiles. In this context, the review examines material selection, fabrication strategies, and sensor integration, while also addressing the challenges and opportunities that lie ahead in realizing next-generation smart textiles. The novelty of this review lies in its integration of biocompatible electrospun biomaterials, thermoregulation, and multifunctional wearable sensors, demonstrating how advanced fiber architectures enable simultaneous passive and active thermal management, moisture control, and real-time sensing. It highlights sustainable material selection, hybrid composites, and eco-friendly phase-change systems, connecting material design to recyclability, energy efficiency, and environmental impact. By linking fabrication strategies, functional performance, and practical challenges, this work provides a comprehensive framework for guiding the development of next-generation, skin-friendly, and multifunctional smart textiles. 1.1. Rise of Smart Textiles and Wearable Sensors The integration of electronics into textiles represents a pivotal advancement in the field of wearable technology, marking the emergence of smart fabrics—materials endowed with the capacity to sense, respond, and communicate with their surrounding environment. This progression reflects a broader trajectory in wearable systems, which have evolved from rudimentary fitness trackers into highly sophisticated, textile-embedded platforms capable of real-time physiological monitoring, environmental sensing, and adaptive functionality. Central to this transformation is the convergence of flexible electronics, nanotechnology, and advanced materials engineering, which collectively enable the seamless incorporation of sensors, actuators, and communication modules into fabric substrates. Consequently, garments are reconceptualized not as passive coverings but as dynamic interfaces that mediate interactions between the human body and its external milieu, with applications spanning health surveillance, environmental awareness, and individualized modes of expression. This paradigm shift underscores the interdisciplinary nature of smart textile research and highlights its potential to redefine both technological innovation and the cultural significance of clothing in contemporary society [ 12 , 13 , 14 , 15 ]. Smart textiles are generally classified into three categories: passive, active, and ultra-smart systems (see Figure 2 ). Passive textiles are capable of sensing external environmental or physiological stimuli, while active textiles not only detect changes but also respond through embedded actuators. Ultra-smart textiles extend these capabilities further by incorporating logic and decision-making functions, thereby enabling autonomous adaptation to dynamic conditions [ 14 ]. This classification reflects the progressive complexity and functionality of wearable systems, ranging from simple temperature sensors to garments that can adjust themselves in real time. Increasingly, these advanced functionalities are being realized through the integration of flexible sensors that monitor parameters such as temperature, strain, humidity, and biochemical markers, underscoring the interdisciplinary convergence of materials science, electronics, and nanotechnology in the development of next-generation wearable platforms. The proliferation of wearable sensors, which serve as the cornerstone of smart textiles, is driven by significant advancements in flexible electronics, nanomaterials, and miniaturization. These developments have enabled the creation of sensors with enhanced sensitivity, biocompatibility, and adaptability, capable of monitoring a broad spectrum of physiological parameters—including heart rate, respiration, skin temperature, and hydration—without compromising user comfort or mobility. Progress in materials science, particularly the incorporation of conductive polymers, carbon-based nanomaterials, and electrospun nanofibers, has facilitated the fabrication of sensors that are lightweight, stretchable, and conformable to the skin. Moreover, the integration of conductive fibers and printed electronics allows sensors to be seamlessly embedded into textile substrates, thereby supporting continuous, non-invasive monitoring while preserving the breathability and wearability of conventional garments. Collectively, these innovations highlight the interdisciplinary convergence of electronics, nanotechnology, and materials engineering in advancing next-generation smart textile systems [ 15 ]. In healthcare, smart textiles are being used for remote patient monitoring, rehabilitation, and chronic disease management. In sports, they optimize performance and prevent injury by tracking biomechanical data. Military applications include uniforms that detect environmental hazards or monitor soldier vitals. Even fashion is embracing smart textiles for interactive and expressive clothing. The market for smart textiles is expanding rapidly. According to Grand View Research, it is projected to exceed $12 billion by 2025, fueled by consumer demand, technological innovation, and cross-sector adoption [ 16 ]. However, challenges remain in durability, washability, energy autonomy, and data privacy. Researchers are exploring solutions such as energy-harvesting fabrics, biodegradable electronics, and secure data protocols to address these concerns. As the field evolves, biocompatible electrospun biomaterials are emerging as a promising foundation for wearable sensors. Their flexibility, breathability, and compatibility with human skin make them ideal for thermoregulating applications—ensuring comfort while enabling precise temperature control in dynamic environments. 1.2. Thermal Regulation as a Core Challenge in Long-Term Wearable Comfort As wearable technologies become increasingly integrated into daily life—from fitness trackers and smart clothing to medical monitoring systems—the issue of thermal regulation has emerged as a central challenge in ensuring sustained user comfort and device performance. Unlike conventional electronics, wearables are in direct contact with the skin, making heat management essential not only for operational stability but also for preventing discomfort, irritation, or even thermal injury. Human skin is highly sensitive to temperature fluctuations, and prolonged exposure to elevated temperatures from embedded electronics can lead to sweating, skin fatigue, and reduced adherence to the device. Conversely, inadequate warmth in cold environments can compromise sensor accuracy and user experience. Therefore, maintaining a stable microclimate between the skin and the wearable interface is vital for long-term usability. Recent advances in thermoregulating textiles have focused on both passive and active strategies. Passive approaches include the use of phase change materials (PCMs), reflective coatings, and porous structures that facilitate heat dissipation. The types of passive thermoregulating textiles are presented in Figure 3 . Active systems incorporate thermoelectric modules, microfluidic cooling, and responsive polymers that adapt to temperature changes in real time [ 17 , 18 ]. Electrospun nanofibers have shown promise in this domain due to their high surface area, tunable porosity, and ability to incorporate functional additives. For instance, integrating carbon-based nanomaterials or metallic nanoparticles into electrospun mats can enhance thermal conductivity, enabling efficient heat transfer away from the skin [ 11 , 12 , 13 , 19 ]. Moreover, biocompatible polymers such as silk fibroin and polycaprolactone (PCL) offer breathable and skin-friendly platforms for sensor integration. Despite these innovations, several challenges persist. Durability under repeated thermal cycles, washability, and energy efficiency remain key concerns. Additionally, balancing thermal regulation with other performance metrics—such as sensor sensitivity, mechanical flexibility, and aesthetic appeal—requires multidisciplinary design strategies [ 19 ]. Addressing these challenges is crucial for the next generation of smart textiles, particularly in healthcare, sports, and military applications where long-term wear is common. Future research must focus on hybrid systems that combine passive and active thermal management, sustainable materials, and intelligent feedback mechanisms to optimize comfort and performance [ 12 , 19 ]. 1.3. The Role of Biocompatible Materials and Electrospinning Technology The development of wearable sensors for smart textiles hinges on the use of materials that are both functional and safe for prolonged skin contact. Biocompatible polymers—such as polycaprolactone (PCL), polylactic acid (PLA), silk fibroin, and chitosan—have emerged as ideal candidates due to their non-toxic, biodegradable, and skin-friendly properties [ 2 , 4 , 5 , 6 , 7 , 8 , 9 ]. These materials offer mechanical flexibility, breathability, and compatibility with human tissue, making them suitable for long-term wearable applications. Electrospinning technology plays a pivotal role in transforming these polymers into nanofibrous mats with high surface area, tunable porosity, and excellent mechanical compliance. This technique uses electrostatic forces to draw polymer solutions into ultrafine fibers, producing structures that mimic the extracellular matrix and conform well to the skin [ 1 ]. The resulting mats are highly breathable and can be engineered to incorporate functional additives such as conductive nanoparticles, phase change materials, or antimicrobial agents, enabling multifunctional capabilities in smart textiles. For example, silk fibroin electrospun with carbon quantum dots has demonstrated promise in transient electronics due to its biodegradability and thermal responsiveness [ 2 ]. Similarly, electrospun PVDF and its copolymers have been explored for their piezoelectric properties, enabling self-powered sensing platforms in wearable systems [ 1 ]. Despite these advances, challenges remain in achieving consistent fiber morphology, mechanical robustness, and scalable manufacturing. Researchers are actively exploring hybrid materials that combine natural and synthetic polymers, as well as green solvents and integrated wireless modules, to create fully autonomous and sustainable smart textile systems [ 11 , 12 , 13 ]. 2. Biocompatibility in Thermoregulating Wearable Sensors The integration of thermoregulating sensors into wearable textiles involves continuous and intimate contact with human skin, often under dynamic conditions such as motion, perspiration, and fluctuating temperatures. In this context, biocompatibility becomes a functional necessity, not only to ensure skin safety, but also to maintain comfort and long-term usability of the device. While thermoregulating smart textiles are typically not classified as medical devices, they are nonetheless expected to comply with high standards of skin compatibility, particularly when intended for extended or repeated wear. In wearable thermoregulating sensors, biocompatibility extends beyond the mere absence of toxicity and encompasses a range of properties that contribute to skin comfort, biological inertness, and mechanical harmony with the body. These include non-irritating surface chemistry, breathability and effective moisture management, mechanical softness and flexibility, and resistance to microbial growth in humid, thermally active environments. Unlike implantable materials, which must be evaluated for systemic biological effects, wearable biomaterials primarily emphasize epidermal safety and comfort during motion and perspiration. To clarify the relevance of these factors in thermoregulating garments, the following section summarizes how material architecture governs moisture and heat at the skin-textile interface. Figure 4 schematically illustrates the system-level factors influencing biocompatibility in thermoregulating wearable sensors, as discussed in the subsequent sections. In this context, biocompatibility should be interpreted not as a static material property, but as a dynamic system-level response shaped by skin–textile interactions under real-use conditions. In addressing continuous skin contact under dynamic conditions, various studies have highlighted the importance of material design in enhancing moisture management and reducing skin irritation. Zhao et al. [ 20 ] demonstrated that manipulating the architectural (via fluorine-free waterborne coatings on fibrous substrates) properties of fabrics can significantly improve moisture-vapor transmission, effectively keeping liquids away from the skin and thus mitigating the risk of irritation; this aligns with findings from Park et al. [ 21 ], who evaluated moisture management in high-temperature-resistant nanofibrous membranes and underscored the coupling between breathability and thermal protection. These observations are consistent with Troynikov and Wardiningsih [ 22 ], who examined active garments and found that fabric architecture governs the stability of the skin microclimate during exertion, emphasizing how textile mechanics and porosity steer sweat management and comfort in practice. Taken together, these results set up the link between microstructure, microclimate, and perceived comfort during exertion. Taken together, these studies indicate that control of the skin microclimate through textile architecture is a primary driver of biocompatibility in thermoregulating wearables, rather than a secondary comfort-enhancing feature. Expanding on the relationship between comfort and functionality, Xie et al. [ 23 ] and Zhang et al. [ 24 ] indicated that carefully tailoring the properties of textile materials strikes a balance between breathability and water resistance, thereby facilitating both comfort and performance during prolonged wear. Wang et al. [ 25 ] further illustrated the application of these principles in healthcare electronics by demonstrating how MXene-based, porous, and breathable materials can maintain optimal sensing performance and antimicrobial properties even during motion, thereby enhancing both user comfort and device functionality. The versatility of these materials reflects the growing trend toward integrating comfort with technological performance in wearable health monitoring solutions. This convergence suggests a broader shift in wearable design philosophy, where biocompatibility and sensing performance are commonly co-optimized rather than treated as competing objectives. Mechanical harmony between wearable devices and the human body represents a second, equally critical dimension of biocompatibility, and emerges across studies as a limiting factor for long-term comfort and signal fidelity during motion. A consistent conclusion across studies is that mechanical mismatch, rather than chemical incompatibility alone, often underlies discomfort, irritation, and signal degradation during motion. Reviews by Xie et al. [ 23 ] and Khan et al. [ 26 ] emphasize that co-engineering biocompatibility and mechanical compliance within polymer and textile substrates is essential for achieving stable on-skin operation. Recent material strategies increasingly demonstrate that enhanced functionality in thermoregulating wearables does not need to compromise biocompatibility, but instead, it can reinforce comfort and long-term usability. Peng et al. [ 27 ] reported the fabrication of breathable, biodegradable, and antibacterial electronic skins that improve compatibility and comfort during operation. Wu et al. [ 28 ] expanded on this concept through the development of permeable electrodes designed to form conformal interfaces with skin, ensuring sustained comfort and functionality even during vigorous activities. Similarly, Liu et al. [ 29 ] showed that polyvinylidene fluoride-based membranes exhibit ultra-flexibility, strong waterproofing, and breathability, which are key attributes for electronic skin applications, highlighting the importance of integrating functional materials in wearable technology. These advancements exemplify the potential for smart textiles to improve the interface between the wearer and the garment, promoting both health and comfort. Further enhancing functionality at the skin-textile interface, Szewczyk et al. [ 30 ] demonstrated that oil-infused polymer fiber membranes can improve skin hydration, a critical factor for maintaining skin health during extended wear. In line with this, permeable triboelectric fiber mats designed by Maksoud et al. [ 31 ] exhibit mechanical properties closely matched to those of human skin, maintaining comfort and performance output even under intense motion. Collectively, these developments underscore the profound impact of advanced textile engineering on wearable technology and user experience. This body of work reinforces the view that material architecture enables simultaneous gains in comfort, durability, and functional performance during long-term wear. The integration of advanced textile design and material properties is crucial for maximizing comfort and functionality in wearable technologies. Continuous innovation in this field is essential for developing effective solutions that prioritize the wearer’s experience, particularly in active and healthcare applications. Importantly, this body of evidence indicates that material and structural choices at the textile level increasingly dictate system-level performance and user acceptance in thermoregulating wearables. Beyond individual material demonstrations, multiple studies indicate that mechanical softness, stretchability, and elastic recovery are decisive factors for long-term wearability. McLaren et al. [ 32 ] identified compliant sensor placement and deformable designs as key factors in improving user experience in neurological rehabilitation textiles, while analyses of wearable ECG systems [ 33 ] have linked mechanical compliance directly to reduced motion artifacts and improved patient safety. Stretchable and self-adhesive electrodes developed by Ding et al. in [ 34 ], along with survey-based evidence from Yin et al. in [ 35 ], further confirm that elasticity and shape recovery mitigate irritation during active use. Additional studies [ 36 , 37 , 38 , 39 , 40 ] reinforce the conclusion that soft mechanics enhance adhesion, reduce friction, and preserve sensing performance, positioning mechanical biocompatibility as a prerequisite for reliable thermoregulating wearables rather than an auxiliary comfort feature. Accordingly, mechanical biocompatibility should be regarded as a prerequisite for reliable thermoregulating wearables, rather than merely an auxiliary comfort consideration. In exploring the critical aspect of regulatory alignment regarding biocompatibility in thermoregulating wearable sensors, it is vital to underscore the importance of adherence to established safety standards, particularly in the context of new material formulations and their interactions with biological systems. Patel et al. in [ 41 ] and Sharma et al. in [ 42 ] highlighted the imperative for rigorous safety evaluations aligned with ISO 10993 standards, which address aspects such as cytotoxicity (ISO 10993-5 [ 43 ]) and irritation testing on reconstructed human epidermis (ISO 10993-23 [ 44 ]) [ 45 ]. This shift towards continuous on-body monitoring necessitates that all materials used in wearable technologies undergo thorough assessment of their effects on human tissues to ensure long-term usability without adverse reactions. European regulatory adoption has reinforced this shift, with EN ISO 10993-23:2021/A1:2025 [ 46 ] clarifying RhE endpoints and moving decisively away from legacy animal models. Advancing this discussion, Liu et al. in [ 47 ] examined the significance of biocompatibility for wearable sensors crafted from innovative materials such as self-healing hydrogels, emphasizing that the effectiveness of these sensors depends heavily on maintaining skin-friendly interfaces while delivering consistently high performance across variable environments. Similar concerns were echoed by Ereifej et al. in [ 48 ], who noted that cytotoxicity testing serves as a preliminary step for evaluating the compatibility of various biomaterials in medical devices, thereby establishing a foundation for their safe application. These regulatory frameworks collectively reposition biocompatibility from a material-level checklist to a system-level validation process aligned with continuous, on-body use. As such, regulatory alignment functions not only as a compliance requirement but also as a design constraint that shapes material selection and device architecture from early stages of development. Moreover, Choi et al. in [ 49 ] underscored the need for biocompatibility assessments in wearable sensors employing ionic liquids, advocating in vitro testing on human keratinocyte and fibroblast cells to ensure that these materials do not elicit toxic responses. Such regulatory scrutiny is echoed by other research, which has demonstrated that the use of biocompatible materials, particularly naturally derived substrates such as silk fibroin, facilitates the development of soft, skin-tolerant textile sensors that comply with ISO testing protocols [ 50 ]. Wang et al. in [ 51 ] further linked material stability in health-monitoring applications to consistent performance at the skin interface. Antimicrobial performance has been investigated as a co-requirement in humid microclimates, where microbial growth can pose significant challenges. Windmiller and Wang in [ 52 ] reviewed on-body chemical and biochemical sensing and underscored that antimicrobial nanomaterial must be integrated with careful consideration of comfort and safety. Baldo et al. in [ 53 ] surveyed biodegradable and transient sensors and concluded that natural or hydrolysable matrices can reduce long-term bioburden. Sen et al. in [ 54 ] discussed antimicrobial electrospun fibers for durable, long-contact applications, while Shafique et al. in [ 55 ] analyzed hydrogel-based sensors and highlighted low cytotoxicity and skin comfort under moisture-rich conditions. Krysiak et al. in [ 56 ] examined antimicrobial treatments in flexible textiles, explicitly linking hygiene performance with mechanical comfort. Liakos et al. in [ 57 ] tested cellulose acetate electrospun pads loaded with essential oils and demonstrated suppression of common pathogens without sacrificing breathability. Yin et al. in [ 58 ] presented silk-sheathed conductive wires that provided splash resistance and electrical insulation in a skin-friendly, washable format. Across these studies, authors consistently identified ISO 20743 [ 59 ] (along with AATCC 100 [ 60 ] where applicable) as the appropriate, textile-specific standard for evaluating antibacterial efficacy. This consensus emphasizes that antimicrobial performance must be assessed within textile-relevant testing frameworks to meaningfully support long-term skin compatibility. Finally, to close the safety loop beyond comfort and hygiene, sensitization and chemical compatibility have been framed by researchers as critical to long-term wear. Iadaresta et al. in [ 61 ] showed that textile-related chemicals such as benzothiazole can migrate to the skin under wear-like conditions, reinforcing the need for chemical safety and low-irritant formulations. He et al. in [ 62 ] developed integrated textile sensor patches based on silk-derived carbon textiles and demonstrated non-invasive measurement using skin-tolerant materials, underscoring that device-level chemistry and surface finishes must meet dermatological safety expectations. Armengol et al. in [ 63 ] discussed allergenic risks associated with textile finishes and emphasized the importance of regulating dyes, crosslinkers, and auxiliary agents to minimize the incidence of allergic contact dermatitis in both medical and consumer textiles. In the regulatory context, the harmonized standard EN 1811:2023 [ 64 ] under REACH [ 65 ] sets the nickel-release test method and compliance decision limit (≤0.88 µg·cm −2 ·week −1 ) for metal components in prolonged skin contact, thereby guiding the selection of snaps, connectors, and electrodes in wearable systems. Wang et al. in [ 66 ] reviewed surface-engineered biomaterials for wound management and demonstrated that benign coatings and passivation strategies can effectively reduce sensitization risks, offering translatable approaches to wearable biosensors. In parallel, Wang et al. in [ 67 ] explored biodegradable polysaccharide matrices for humidity sensing as a route to achieving function performance using inherently low-irritant chemistries. Zeybek, B. & Duman, M. in [ 68 ] examined electrospun sensing platforms and emphasized the importance of chemical stability and biocompatibility in minimizing dermal irritation. Similarly, Liu et al. in [ 69 ] and Tang et al. in [ 70 ] investigated tunable composite nanogenerators and reinforced that active-layer engineering must account for skin-exposure chemistry from the earliest stages of design. Collectively, these findings emphasize that chemical stability and sensitization control are integral components of biocompatibility, particularly for thermoregulating wearables intended for prolonged skin contact. Altogether, the literature converges on a practical, evidence-based definition of biocompatibility for thermoregulating textile wearables. This definition encompasses electrospun, breathable, and mechanically compliant architectures that preserve the skin microclimate and mechanical comfort; material chemistries validated through ISO 10993-aligned cytotoxicity and irritation assessments, alongside textile-specific antimicrobial testing (ISO 20743 [ 59 ]); and article-level controls on sensitizers and metallic components through REACH [ 65 ] and EN 1811 [ 64 ], with RoHS [ 71 ] constraints applied where electronic elements are involved. Within this framework, thermoregulation, comfort and safety are no longer competing objectives but instead emerge as co-designed features of next-generation smart textiles. 3. Electrospinning of Biomaterials for Thermoregulating Textile Interfaces 3.1. Principles and Advances in Electrospinning for Functional Fiber Fabrication The principle of electrospinning technology lies in the ability of a conductive polymer, either in solution or melt form, to generate continuous fibrous structures under a high-voltage electric field through elongation between a spinning electrode and a collector. For laboratory-scale polymer trials, a single-tip or single-nozzle configuration is commonly employed, where a polymer droplet is placed onto the spinning electrode [ 72 , 73 ]. Upon application of an electric field, the droplet deforms into a conical structure known as a Taylor cone, from which a fine polymer jet is ejected once the applied voltage exceeds the threshold required to overcome the surface tension of the liquid polymer [ 74 ]. Studies demonstrate that this versatile setup can be effectively used to fabricate functional material prototypes for wearable sensor and textile applications [ 72 , 73 ]. When polymer feeding is continuous, uninterrupted fiber production can be achieved, enabling scalability toward industrial manufacturing [ 75 ]. Beyond sensing performance, thermoregulation is a critical function of wearable textile interfaces, as maintaining skin temperature within a comfortable range directly influences user comfort, physiological performance, and long-term wearability. Electrospinning is particularly well suited for thermoregulating textiles due to its ability to produce highly porous, lightweight, and breathable fibrous membranes with precisely tunable morphology. The inherently high surface-area-to-volume ratio of electrospun nanofibers promotes efficient heat dissipation and moisture evaporation, which are essential mechanisms for passive cooling. By controlling fiber diameter, porosity, alignment, and layer thickness, electrospun mats can be engineered to serve either as thermal insulation layers, by trapping air within the fibrous structure, or as cooling layers that enhance sweat evaporation and convective heat transfer at the skin-textile interface. The most commonly employed electrospinning techniques are solution electrospinning and melt electrospinning, each offering distinct advantages and limitations depending on the intended application. Solution electrospinning involves dissolving a polymer in a suitable solvent to form a spinnable solution. Under a high-voltage electric field, a charged jet is ejected from the needle tip, and as the jet travels toward the collector, the solvent evaporates, leaving behind a solidified fiber [ 76 ]. Solvent evaporation drives significant jet thinning, enabling the formation of ultrafine fibers with diameters from a few tens of nanometers to several micrometers, which makes the technique well suited for applications that demand high surface area, fine porosity, and delicate structural features. Achieving such fiber quality requires multiple factors to act simultaneously under favorable conditions, including parameters related to the solution, the operating setup, and the surrounding environment. These interconnected conditions ultimately govern the process’s production rate and shape the physicochemical and morphological characteristics of the resulting materials [ 76 ]. The schematic representation of the electrospinning processing parameters are presented in Figure 5 . A major advantage of solution electrospinning in the context of wearable sensors and thermoregulating textiles is its broad material compatibility. A wide range of polymers, including biopolymers, conductive polymers, carbon-based nanomaterial composites, and stimuli-responsive materials, can be electrospun from solution [ 77 ]. This versatility enables the fabrication of fibers with precisely tailored electrical, thermal, and mechanical properties. Additionally, because solution electrospinning typically operates at ambient or moderately elevated temperatures, it is well suited for incorporating thermally sensitive bioactive molecules, such as enzymes, antibodies, growth factors, or even living cells, without compromising their structural integrity or biological function [ 77 , 78 ]. This capability is particularly valuable for next-generation smart textiles that integrate biosensing or therapeutic functionalities. However, solution electrospinning also presents challenges. The use of volatile, flammable, or toxic solvents raises environmental, safety, and regulatory concerns, particularly for wearable applications where fibers come into direct contact with the skin [ 79 ]. Residual solvent trapped within fibers can compromise mechanical performance, biocompatibility, and long-term stability, making complete solvent removal essential. Furthermore, solvent evaporation rates strongly influence fiber morphology, potentially leading to defects such as beads, pores, or inconsistent diameters if processing conditions are not carefully controlled. In contrast, melt electrospinning eliminates the need for solvents entirely. In this approach, the polymer is heated above its melting temperature to form a viscous melt, which is then electrospun under a high-voltage field. As the molten jet travels toward the collector, it solidifies through cooling, forming continuous fibers [ 80 ]. Because no solvent evaporation occurs, the jet experiences less thinning, resulting in fibers that are generally thicker—often in the micrometer range—compared to solution-spun fibers [ 81 ]. While this may limit applications requiring nanoscale features, it provides advantages for structural components where mechanical robustness is essential. Melt electrospinning is inherently more environmentally friendly, as it avoids solvent emissions and reduces the need for post-processing purification. It is also well suited for large-scale industrial production, particularly when combined with techniques such as melt electrowriting, which enables precise fiber placement. The high polymer concentration in the melt contributes to enhanced mechanical strength, making melt-spun fibers attractive for durable textile interfaces, especially those intended for repeated washing, stretching, or mechanical stress. Nevertheless, melt electrospinning has its own limitations. Only thermoplastic, thermally stable polymers can be processed, which restricts material selection [ 82 ]. High processing temperatures may degrade sensitive additives, preventing the incorporation of bioactive molecules or certain conductive fillers. Additionally, heating polymers to their melting point results in higher energy consumption, which can increase production costs. The higher viscosity of polymer melts also makes it more challenging to achieve very fine fiber diameters, limiting the achievable porosity and surface area compared to solution electrospinning. A comparison of melt electrospinning and solution electrospinning is presented in Table 1 . The simplified comparison of solution electrospinning and melt-spinning is presented in Figure 6 . Traditional electrospinning provides limited control over fiber alignment, patterning, and functional anisotropy, which are important parameters for both sensing accuracy and thermal management. To overcome these limitations, various electrospinning process modifications (e.g., magnetic-field or airflow assistance) and hardware adaptations (e.g., spinneret or collector design) have been developed. For example, magnetic field-assisted electrospinning enables control over jet trajectory through the incorporation of magnetic nanoparticles (e.g., Fe 3 O 4 , Fe 2 O 3 , CoFe 2 O 4 ) into polymer solutions [ 83 ] or by using magnetically patterned collectors [ 84 ]. These approaches yield highly aligned nanofibers with improved electrical conductivity and mechanical responsiveness, which can also facilitate directional heat transport within textile structures [ 85 ]. Airflow-assisted electrospinning introduces additional aerodynamic forces through pressurized air streams during coaxial or side-by-side spinning. This modification influences jet stretching, drying rate, and fiber morphology, allowing enhanced control over porosity and thickness—key parameters for regulating heat and moisture transport in wearable textiles [ 85 ]. For applications requiring high deposition precision, such as patterned heating or cooling zones, techniques like near-field electrospinning and melt electrowriting are employed, in which the spinneret-to-collector distance is reduced to the sub-millimeter to centimeter range to achieve accurate fiber placement [ 86 , 87 , 88 ]. Spinneret design plays a critical role in defining fiber morphology, porosity, and functional integration. Spinnerets used for wearable sensor and thermoregulating textile fabrication range from needleless (free-surface) systems [ 89 ] to single, double (coaxial or side-by-side) [ 90 ], and multifluid spinnerets [ 79 ]. Needleless electrospinning, which utilizes rotating drums or discs as spinning sources [ 91 ], offers high production rates but provides limited control over fiber uniformity and alignment. In contrast, multifluid spinnerets offer enhanced fluid dynamic control and enable advanced fiber architectures. Concentric (uniaxial) spinnerets facilitate core–shell fiber formation, allowing encapsulation of sensitive biomolecules or conductive fillers (e.g., PEDOT: PSS), while parallel or side-by-side configurations produce Janus fibers with spatially distinct functionalities [ 92 ]. Such architectures are particularly valuable for thermoregulating textiles, where different fiber domains can independently manage moisture transport, thermal insulation, or sensing. Finally, collector geometry significantly influences fiber organization. Flat collectors typically produce randomly oriented fiber mats, while rotating or cylindrical collectors enable semi-aligned to highly aligned structures [ 93 ]. Fiber alignment not only improves mechanical and electrical properties but also affects directional heat transfer and airflow through the textile, further enhancing thermoregulating performance. 3.2. Electrospun Biomaterial Design: Polymers, Solvents, Additives, and Functionalization Strategies Material selection plays a decisive role in determining both the sensing and thermoregulating performance of electrospun wearable textile interfaces. Electrospinning relies on a delicate balance between electrostatic forces, surface tension, and viscosity of the fiber-forming polymer and, in the case of solution electrospinning, the solvent system. Beyond spinnability, the choice of polymers, solvents, and additives directly influences fiber morphology, porosity, wettability, electrical conductivity, mechanical flexibility, moisture transport, and thermal behavior. Therefore, the primary criteria for material and additive selection include biocompatibility, biodegradability, functional response, and long-term stability during skin contact. The main fiber-forming biomaterials used in electrospun wearable systems can be broadly classified into natural, synthetic, and composite polymers. Natural biopolymers derived from biological sources—such as proteins (collagen, gelatin, silk fibroin, elastin) and polysaccharides (chitosan, alginate, hyaluronic acid, starch, cellulose and its derivatives)—are inherently biocompatible and biodegradable. Many of these materials exhibit favorable hygroscopicity, moisture absorption, and breathability, making them particularly suitable for skin-contact layers that promote evaporative cooling and thermal comfort. Synthetic polymers, including polycaprolactone (PCL), polylactic acid (PLA), polyglycolic acid (PGA), poly(lactic-co-glycolic acid) (PLGA), polyurethane (PU), and polyethylene oxide (PEO), offer superior mechanical durability, elasticity, and processability. Their tunable mechanical properties enable integration into stretchable textile substrates while maintaining structural integrity under repeated deformation. Blending natural and synthetic polymers is a widely adopted strategy to simultaneously optimize thermal insulation, moisture management, sensing performance, and mechanical robustness, which is essential for thermoregulating textile interfaces exposed to dynamic environmental and physiological conditions. Solvent selection is a critical factor for biomaterial applications in wearable sensors and thermoregulating textiles, as it directly influences polymer compatibility, toxicity, and solution processability, with key parameters including volatility, conductivity, and viscosity. Typical solvents for various fiber-forming polymers are summarized in Table 2 . Certain acids, such as acetic acid, formic acid, and lactic acid, can serve dual roles as both solvents and functional additives, modifying solution conductivity, viscosity, and pH to enable finer fibers with increased porosity. Such morphological control enhances breathability, moisture transport, and cooling efficiency, which are essential for thermoregulating textile interfaces. The choice of polymer-solvent systems also governs fiber morphology, porosity, mechanical performance, and functional integration in electrospun textiles. Biopolymers offer excellent biocompatibility, moisture management, and eco-friendliness, but often rely on potentially hazardous solvents that complicate large-scale, safe production. In contrast, synthetic polymers provide mechanical robustness, thermal stability, and compatibility with functional additives such as phase-change materials and conductive fillers, although solvent toxicity and environmental impact remain challenges. Hybrid strategies that combine natural and synthetic polymers or employ benign solvent systems are increasingly important for producing durable, multifunctional, and skin-safe wearable textiles. Careful optimization of solvent choice, polymer concentration, and electrospinning parameters is therefore essential to balance fiber quality, functional performance, and sustainability, ultimately supporting the commercial translation of next-generation thermoregulating and sensor-enabled smart textiles. Salts are commonly incorporated to increase solution conductivity, improve spinnability, and achieve finer and more uniform fiber morphologies. Reported examples include NaCl, LiCl, FeCl 3 , CuSO 4 , and AgNO 3 [ 94 ]. Beyond their role in fiber formation, salts can impart additional functional properties relevant to wearable systems. For instance, metal-containing salts or nanoparticles can enhance electrical signal transmission in sensing layers [ 95 ], while AgNO 3 provides both electrical conductivity and antimicrobial functionality [ 96 ]. From a thermoregulation perspective, such additives may also contribute indirectly by improving thermal conductivity or enabling integration with active heating or temperature-sensing elements. Surfactants play a particularly important role in tailoring fiber morphology and surface properties. By reducing surface tension, surfactants such as Triton X-100 improve spinnability and fiber uniformity, while also facilitating the dispersion of functional additives including carbon nanotubes, graphene, or other nanomaterials [ 97 , 98 ]. Certain surfactants, such as sodium dodecyl sulfate, can increase solution conductivity [ 99 ], whereas others enable precise control over wettability [ 100 ]. This tunability is especially valuable for thermoregulating textiles, where hydrophilic surfaces promote sweat absorption and evaporation for cooling, while hydrophobic layers act as moisture or thermal barriers to reduce heat loss in colder environments [ 100 ]. Such functionality is essential for multilayer textile systems designed for adaptive thermal regulation. Electrospun nanofibers can be functionalized using three primary strategies: polymer blending, incorporation of functional additives, or encapsulation, each offering distinct advantages for wearable smart textiles. Polymer blending enables synergistic effects that enhance thermal, mechanical, and sensing performance beyond that of individual components [ 101 ]. Incorporation of functional additives, such as conductive polymers, metal nanoparticles, carbon-based nanomaterials, or inorganic MXenes (listed in Table 3 ), can transform passive biomaterials into multifunctional systems, improving electrical conductivity, thermal management, and sensing capabilities. Conductive polymers such as PEDOT: PSS and polypyrrole provide lightweight flexibility but may degrade under repeated bending or washing and often require toxic solvents. Carbon-based nanomaterials, including graphene and carbon nanotubes, offer superior conductivity, thermal performance, and mechanical reinforcement; however, dispersion, aggregation, and potential cytotoxicity remain challenges. Metal nanoparticles such as silver and gold contribute high conductivity, antibacterial properties, and photothermal effects, though cost, environmental impact, and long-term stability must be considered. Inorganic MXenes deliver multifunctional conductivity and electrochemical responsiveness, but are prone to oxidation and require careful processing for durability. Encapsulation, typically achieved via coaxial electrospinning, allows incorporation of phase-change materials (PCMs) to absorb, store, and release thermal energy, providing passive thermal buffering while preserving a soft and breathable interface. Overall, while these strategies enable advanced thermoregulating and sensing functions, their integration demands careful optimization of biocompatibility, durability, washability, and environmental sustainability, highlighting the trade-offs between performance, safety, and practical applicability in next-generation wearable textiles. Furthermore, the incorporation of thermally conductive fillers, such as carbon-based nanomaterials or MXenes, enables controlled heat distribution within electrospun mats. This capability is beneficial for both passive heat dissipation and integration with active thermal management systems, including electrically driven heating or temperature feedback mechanisms. Once fabricated, electrospun nanofibers must be assembled into functional configurations suitable for wearable and thermoregulating textile interfaces. Common assembly strategies include layer-by-layer stacking and direct deposition onto functional substrates. Layer-by-layer stacking allows the construction of multilayer architectures with spatially separated functions, such as an inner hydrophilic cooling layer, a middle sensing or conductive layer, and an outer protective or insulating layer [ 98 ]. Direct deposition onto textile fabrics or polymer substrates ensures good adhesion, electrical contact, and preservation of stretchability—key requirements for wearable applications [ 79 ]. These hierarchical structures closely mimic natural skin thermoregulation mechanisms and enhance both user comfort and device functionality. Finally, post-processing steps such as thermal annealing, chemical cross-linking, or encapsulation are often employed to improve mechanical durability, wash resistance, and long-term thermal stability, ensuring reliable performance of electrospun thermoregulating textile interfaces under real-world conditions. 4. Biocompatible Polymers with Thermoregulatory Potential 4.1. Natural Biopolymers for Passive and Active Thermoregulation Electrospun materials from natural and synthetic polymers can be engineered for both passive (e.g., insulation, conduction) and active (adaptive heat regulation) thermal management, making them highly versatile for applications in electronics, textiles, and energy systems. Radiant cooling textiles are becoming a practical and energy-efficient solution for passive personal thermal management, helping people stay comfortable outdoors. Passive systems rely on the properties of the electrospun fibers to control heat flow without external input. Electrospun mats of natural polymers (e.g., cellulose, silk fibroin, chitosan) provide low thermal conductivity due to their porous nanofiber structure, making them effective thermal insulators [ 18 , 107 , 108 ]. Active thermal management systems involve materials that respond dynamically to temperature changes. Electrospun fibers can encapsulate phase change materials (PCMs, such as paraffin or fatty acids) that absorb heat when temperatures rise and release it when they drop, enabling adaptive regulation. Active thermoregulation typically requires functional additives (e.g., PCMs, carbon nanotubes, graphene, metallic nanoparticles) [ 109 , 110 ]. Materials such as PCMs and thermally conductive films, although increasingly explored within the field, still exhibit inherently limited thermal transport properties. Consequently, the efficiency of heat transfer between the human body—the primary thermal source—and the cooling system remains constrained. Furthermore, most materials employed for personal thermal management are not derived from bio-based feedstocks. Even in cases where wood or cotton is incorporated as the structural matrix, their biocompatibility and prospects for large-scale commercialization have not been comprehensively assessed. Natural biopolymer PCMs include lipid, lignin, polysaccharides, proteins, and other biopolymers. The advantages of natural polymers include eco-friendliness, biodegradability, and low toxicity, and they can also withstand temperature fluctuations, making them useful for passive thermal management [ 111 ]. Another important feature is that, when using biopolymers at high temperatures, crosslinking, the incorporation of various nanofillers, or blending different polymers can be employed to stabilize thermal performance. 4.1.1. Silk Fibroin: High Thermal Conductivity, Breathable and Its Mechanical Properties Compared with synthetic fibers, silkworm silk is naturally degradable, and products derived from it are environmentally friendly [ 112 ]. Natural silk fibroin (SF) exhibits tensile strength of 300–740 MPa and can absorb energy before tearing, giving it high strength [ 111 , 113 ]. SF is thermally stable (above 250°) [ 114 ], exhibits excellent biocompatibility and good biodegradability, and its degraded products are non-toxic [ 115 , 116 , 117 ]. Additionally, SF is easily processed to tune mechanical and structural properties and can be chemically functionalized (e.g., cross-linked or modified to impart new properties) [ 118 , 119 ]. SF has been widely used in tissue engineering [ 117 ], wound dressings. Composite biomaterials incorporating SF are designed to improve mechanical properties, particularly in humid environments. Emerging applications include 2D silk film electronics [ 115 , 116 , 117 , 118 , 119 , 120 ]. One study explored biologically derived silk fibroin films for the production of thermoregulatory patches. Experimental results demonstrated temperature reductions of 2.5 and 8.2 °C on simulated skin surfaces under outdoor and indoor conditions, respectively [ 116 ]. SF has also been utilized in sensors due to its biocompatibility, biodegradability, and low manufacturing costs. However, silk fibroin-based sensors alone have limited mechanical strength, electrical conductivity, or moisture resistance. Combining SF with aramid fibers forms a composite material that enhances sensor performance [ 117 ]. The thermal conductivity of silk fibroin fibers has also been investigated. A rarely studied axial-direction analysis revealed that thermal conductivity decreases as the temperature increases from 13 °C to 26 °C. At room temperature, SF exhibits higher thermal conductivity than most textile fibers [ 118 ]. 4.1.2. Cellulose and Its Derivatives: Porous, Hydrophilic, Moisture-Regulating Cellulose, a natural biopolymer, contains many hydroxyls (-OH) groups, which make it inherently hydrophilic. This hydrophilicity gives cellulose excellent moisture absorption, swelling and wetting properties. These properties are advantageous for many applications, including hydrogels, sorbents, biomedical devices, but can be disadvantageous when water resistance, dimensional stability, or durability in humid conditions are required. Cellulose chains form strong hydrogen bonds, giving the polymer a robust structure. A characteristic feature of cellulose is its semi-crystalline structure, consisting of a mixture of crystalline and amorphous regions. Additionally, cellulose exhibits excellent mechanical (elastic) properties under pressure, which are direction-dependent and influenced by crystal size. Increasing the number of hydrogen bonds significantly enhances mechanical strength and affects porosity [ 121 , 122 , 123 , 124 , 125 ]. Cellulose is biodegradable and non-toxic, making it suitable for applications in tissue engineering and regenerative medicine. Cellulose-based materials are commonly used in drug delivery systems, controlled/sustained release systems, excipients, hydrogels, scaffolds and for biomedical surfaces [ 123 ]. Cellulose-based antimicrobial coatings and films are used in textiles and packaging, while water-resistant cellulose materials find applications in medical devices, packaging, and diagnostic tools [ 126 , 127 , 128 , 129 ]. Most research has focused on balancing cellulose hydrophilicity. Scientists have developed cellulose hydrogels using ionic liquids or NaOH/urea solutions. The production of such hydrogels allows precise control over crystallinity, porosity and hydrophilicity, which is critical for the fabrication of sensors [ 119 ]. Other researchers have explored the addition of plasticizers, such as glycerol. Incorporating glycerol into regenerated films enhances flexibility, reduces stiffness, and significantly modifies water interactions, resulting in a disruption of the hydrogen bond network [ 130 ]. 4.1.3. Chitosan and Alginate: Antibacterial, Humidity Buffering, Compatible with Phase-Change Systems A significant role in chitosan’s antibacterial activity is played by its physicochemical properties, including cationic structure, molecular weight, degree of deacetylation, and concentration. Chitosan is easily processed: high molecular weight chitosan is less soluble, while low molecular weight chitosan is more soluble and often more bioactive and antimicrobial. Biological interactions with other substances depend on the degree of deacetylation. Viscosity is influenced by molecular weight and can be adjusted through temperature and concentration. Chitosan is biodegradable and can be broken down by lysozyme. It also exhibits excellent emulsification and water binding properties. These functional characteristics vary depending on its physicochemical profile. Due to the presence of reactive chemical groups, chitosan can be easily functionalized or chemically modified [ 130 , 131 ]. Key properties of electrospun chitosan nanofibers are presented in Figure 7 . Because chitosan contains a large number of amino and carboxyl groups, it can form chelate complexes with metals. In particular, the antimicrobial activity of silver (Ag) ions against Gram-negative and Gram-positive bacteria is well established. Chitosan-silver complexes are used in medicine, for example, as part of protective coatings, patches, and orthopedic products, helping reduce the risk of postoperative infection [ 132 ]. The main mechanism of chitosan’s antibacterial activity depends on its molecular weight, degree of deacetylation, physicochemical properties (concentration, pH, contact time), structure, and reactive hydroxyl groups. Chitosan can even inhibit bacterial growth by interacting with bacterial surface structures and forming metal chelates [ 133 ]. Chitosan can be applied in biomedical, food, cosmetic, and pharmaceutical sectors, for example as bandages and tissue engineering scaffolds, or even as a carrier component for anticancer drugs. In agriculture, it serves as a plant protection agent and growth stimulant, and it is also used in wastewater treatment. In the packaging sector, chitosan is applied for the production of biodegradable packaging [ 134 , 135 , 136 , 137 ]. Alginate is a high-molecular-weight biopolymer capable of forming gels with multivalent cations (e.g., Ca 2+ ). Its viscosity is strongly dependent on molecular weight, pH, concentration, and composition and dissolves. Alginate dissolves well in water but is insoluble (or poorly soluble) in most organic solvents. A notable property is its mucoadhesiveness, allowing it to adhere to mucosal tissues. It can absorb large amounts of water. Due to its excellent biocompatibility, alginate is widely used in drug delivery, wound healing, and tissue engineering. In the food industry, it functions as a thickener, stabilizer, and gelling agent. Additionally, alginate is applied for cell encapsulation, immobilization, and microgranules, wastewater treatment (metal binding), biological recycling, and hydrogel production [ 138 , 139 , 140 , 141 ]. 4.2. Synthetic Biopolymers with Enhanced Mechanical and Thermal Properties 4.2.1. Polycaprolactone (PCL): Flexible Matrix, Blends Well with PCMs or Fillers The synthetic biopolymer polycaprolactone (PCL) is insoluble in water, but soluble in most organic solvents. It is very flexible, although its mechanical properties depend strongly on molecular weight and crystallinity. PCL is easily shaped and highly compatible with other polymers. It exhibits shape memory behavior due to its flexible chains and low melting point. PCL is biocompatible and its biodegradability is slow, taking up to about 3 years, and depends heavily on its intrinsic parameters. PCL undergoes degradation through two common pathways: (i) enzymatic degradation (also called surface erosion mechanism) and (ii) hydrolytic degradation (also known as bulk erosion mechanism). Bulk and surface degradation of PCL are presented in Figure 8 . Surface enzymatic erosion of PCL causes substantial mass loss without significantly altering molecular weight (represents decrease of orange colour column size) because hydrolysis at the surface occurs faster than water can diffuse into the polymer bulk, resulting in gradual thinning from the outside inward (represents intensiveness of orange colour in the Figure 8 . PCL’s hydrophobicity is relatively high [ 142 , 143 , 144 , 145 ]. This polymer is widely used in the biomedical field, including tissue engineering scaffolds, drug delivery systems, fand long-term implants (e.g., bone scaffolds). It is also applied in water purification and other industrial areas [ 143 , 144 , 145 ]. 4.2.2. Polyurethane (PU): Elastic, Breathable, Comfortable for Skin-Contact Sensors The synthetic polymer polyurethane (PU) exhibits good elongation and tensile strength, excellent abrasion resistance, high elasticity and tear resistance. It also possesses very good thermal properties, works over a wide temperature range, good thermal properties, functioning over a wide temperature range, provides effective thermal insulation, good moisture resistance, and demonstrates excellent resistance to mechanical stress, fatigue, abrasion. However, this polymer is poorly degradable and is particularly susceptible to UV radiation and thermal degradation. Biocompatibility is limited, with only certain Pus being suitable for biomedical application PU offers versatile processing options in various forms, including spraying, foaming, molding. Recycling is limited to thermoplastic PUs, and its use in medical applications is generally restricted [ 146 , 147 , 148 , 149 ]. 4.2.3. Polylactic Acid (PLA): Thermally Insulating, Biodegradable, Forms Stable Nanofibers Polylactic acid (PLA) is an insulating polymer that is highly biodegradable and can be composted under appropriate humidity and temperature conditions. Its thermal resistance depends on crystallinity and its mechanical properties are sensitive to processing conditions. PLA is compatible with a variety of fabrication methods, including sewing threads, 3D printing, thermoforming and foam molding, and finds applications in biomedical devices [ 150 , 151 , 152 ]. Similarly, PCL, due to its biobased and biodegradable nature, is an attractive alternative to traditional fossil-based insulators for specific applications. However, PCL often requires additional processing, such as annealing or incorporation into composites, to achieve enhanced thermal insulation performance [ 153 ]. 4.3. Material Comparison and Performance in Thermoregulating Textiles 4.3.1. Biocompatibility vs. Thermal Control Trade-Offs Biomaterials can be broadly classified into three principal categories based on their source and production pathway. The first category comprises polymers directly extracted or fractionated from natural biomass, including starch, cellulose, arabinoxylan, and lignin. The second category consists of polymers chemically synthesized from bio-derived monomers, such as polylactic acid (PLA) and cellulose acetate (CA). The third category encompasses microbially biosynthesized polymers, notably polyhydroxyalkanoates (PHAs) and various polysaccharides. The schematic representation of general steps for extraction of bioactive compounds from plant materials is presented in Figure 9 [ 154 ]. Biopolymers such as poly(caprolactone) (PCL), poly(ethylene glycol) (PEG), poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA), chitosan, and gelatin are commonly employed in electrospinning due to their high biocompatibility and ability to undergo biodegradation in physiological environments. However, these materials exhibit markedly different mechanical properties, which can influence the performance and structural stability of the resulting electrospun fibers [ 155 ]. PLA provides strength and rigidity for structural applications, while PEG is soft and flexible, supporting cell interactions but lacking mechanical support. PLGA combines strength and flexibility, making it versatile, and gelatin offers cell compatibility though with less strength than synthetics. Chitosan has low modulus but can be reinforced through cross-linking, and PCL is elastic and durable, enabling long-lasting fibers. Together, these materials allow electrospun fibers to be tailored for specific functional needs across diverse applications [ 155 ]. Advantages and limitations of natural and synthetic electrospun polymers are presented in Table 4 . Natural polymers provide comfort and eco-friendliness, while synthetics enable engineered thermal regulation. The future lies in hybrid electrospun textiles that merge both strengths for sustainable, high-performance thermoregulating fabrics. 4.3.2. Blending Strategies (e.g., Natural/Synthetic Hybrids) for Combined Benefits Blending natural and synthetic polymers into hybrid systems combines the eco-friendliness and biocompatibility of natural materials with the mechanical durability and tunable properties of synthetic polymers. Common strategies for blending include physical mixing, nanocomposite formation and coaxial electrospinning. These hybrid systems offer enhanced mechanical strength, improved thermal conductivity, better phase change stability, and controlled degradation, making them highly suitable for thermal energy storage, thermoregulating textiles, and other advanced functional materials. A notable example is coaxial electrospinning, which produces core–shell nanofibers: natural polymers form the shell to ensure biocompatibility, while synthetic polymers or PCMs in the core provide thermal regulation [ 158 , 159 , 160 ]. These hybrids can be fabricated into lightweight, breathable structures suitable for smart textiles, wearable devices and biomedical applications. Their improved heat storage and release capabilities support personal thermal regulation and thermal energy storage systems. By combining natural polymers for reduced environmental impact with synthetics for robustness, hybrid systems create balanced, high-performance materials optimized for long-term use [ 161 , 162 , 163 , 164 ]. 5. Thermoregulation Strategies Using Electrospun Biomaterials 5.1. Passive Thermoregulation via Structural Design Electrospinning is a widely used and cost-effective method for fabricating membranes with tailored structures for passive thermoregulation through precise control fiber morphology and porosity. The high surface area, tunable porosity, and controllable morphology of electrospun nanofibers make them particularly well-suited for personal thermal management applications [ 165 , 166 ]. Nature-inspired designs have emerged as a powerful strategy for creating effective thermoregulating textiles. For example, the feather structure of P. roseus has been mimicked to produce a PAC@T smart textile that has cooling properties which are achieved due to its micro and nano fibers and pores (see Figure 10 ). This type of material exhibits breathability, durability, and enhances mechanical strength [ 166 ]. Another nature inspired textile that can be used for personal thermal management as well as for protection against fire was inspired by hyper-white beetle scales. This material has flame retardants with high whiteness and pore structures inspired by biomimetic structures that are introduced into polyurethane coatings. Composite textiles are prepared by a scraping-coating technique [ 167 ]. Another thermoregulating textile was analyzed by Q. Gao with colleagues—a smart dual-sided nonwoven textile with coating of PI nanofibrous membranes with AgNWs. Results of tests showed that this material has electrical and thermal properties suitable for smart textiles with personal thermal management. Compared to other AgNW coated textiles it displayed better IR reflection performance. Increasing the AgNW content was observed to promote the formation of highly interconnected AgNW networks, characterized by exceptionally low sheet resistance (0.23 Ω sq −1 ) and strong infrared reflectance exceeding 80%, substantially outperforming conventional textile materials. The dual-layer nonwoven structure, when oriented with the AgNW-coated surface outward, exhibits a favorable passive thermoregulatory effect [ 168 ]. Also, dual-mode membrane- porous composite (see Figure 11 ) aimed at passive thermoregulation created by Q. Zhang with colleagues can be used for thermal isolation. Polyimide nanofiber membrane, made by electrospinning, with incorporated fluorine-containing and aliphatic structures shows a possibility for materials to adapt to seasonal and weather changes meaning it has good thermal isolation and can transfer heat when needed [ 169 ]. The polyimide composite membrane exhibits a hierarchical nanofibrous structure, combining micro and nanos pores that reduce solid conduction and suppress internal air convection. Its chemical composition, including fluorine containing and aliphatic segments, enables dual-mode thermal behavior, allowing the fabric to either retain heat or enhance radiative cooling depending on environmental conditions [ 169 , 170 ]. In another article, a composite that is produced through electrospun polymer matrix combining the fibrous polymer matrix with SiO 2 aerogel was investigated. The material has strawberry inspired structures for better thermal insulation and absorption properties. It was discovered that integrated SiO 2 aerogel helps to achieve high porosity which enhances thermal insulation by trapping air within the structure. The strawberry like composite membrane demonstrates a low thermal conductivity of 0.028 W/m·K, indicating excellent thermal insulation performance [ 171 ]. Silica/polyimide composite nanofiber membranes via an electrospinning process can enhance the thermal insulation performance of conventional polyimide nanofiber membranes. According to T. Zhuo by doping with SiO 2 nanoparticles, a low thermal conductivity of the membrane is achieved. Thermal resistance properties appear, because of the resistance to heat transfer between the SiO 2 NPs and PI nanofibers. This result indicates that the membrane can prevent the heat of fire from damaging materials superhydrophobicity [ 172 ]. Also, it was found out that when PAMPS nanofibers are added to PU, it increases the number of pores and decreases pore diameter. This method helps to create windproof (thermal insulation) material, because of the decreased pore diameter. Also, it was stated that for increasing thermal insulation, it is better to use sequential electrospinning mode to produce hybrid layers (structure containing different materials to enhance properties) than simultaneous electrospinning mode [ 173 ]. 5.2. Moisture-Driven Thermal Management Wearable devices as well as smart textiles pose additional requirements of thermal comfort and safety. It may limit body heat dissipation and may lead to thermal stress and discomfort even at moderate exposure temperatures. Effective regulation of perspiration is essential, as the evaporation of sweat requires heat absorption to stabilize body temperature [ 174 , 175 , 176 ]. Decreased or increased localized sweat loss is indicative of hyperhidrosis or hypohidrosis and often assists in stroke diagnosis [ 177 ]. An increasing interest in environmentally friendly materials has motivated industrialists to develop and use biopolymers for various applications such as humidity buffering. Y. Zhang with colleagues created a superhydrophobic self-cleaning PTFE nanofiber membrane. The material SNM-PTFE was created through one-step electrospinning process and achieved superhydrophobic properties by stabilizing the SiO 2 aerogel protrusions. This material exhibits exceptional chemical stability, remarkable resistance to elevated temperatures, pronounced water repellency, and highly effective self-cleaning behavior, all of which arise from its engineered surface architecture composed of micro- and nanostructured features [ 178 ]. G. Parisi and colleagues in [ 179 ] examined electrospun polyvinylidene fluoride (PVDF) fiber meshes incorporating a photoresponsive, switchable surface capable of transitioning from a hydrophobic to a hydrophilic state upon UV irradiation, and subsequently reverting to hydrophobicity following thermal treatment (see Figure 12 ). These properties help collect and release humidity from the material when needed, because of different atmospheric conditions [ 179 ]. Hydrophilic methylcellulose–polyvinyl alcohol biopolymer formed from sugarcane exhibits excellent humidity buffering behavior, with high water absorption, strong moisture retention, and low vapor transmission. These properties result from the abundant hydroxyl groups in methylcellulose, PVA, and starch, which form hydrogen bonds with water. These kinds of materials are a possibility for industrial application of sugarcane base to form various products [ 180 ]. Also, super hydroscopic and fast moisture absorption can be achieved by using facile and two-step electrospinning. The moisture absorption properties are achieved by coating nanofiber with LiCl via impregnation. Structure plays a crucial part in determination of the properties of fiber. The porous nanofibrous structure significantly increases the moisture absorption and transport rates [ 181 ]. For enhancing thermal comfort sweat management innovations such as moisture pumping textiles can be used. Such materials help to travel moisture from the skin to the environment. This can be realized by arranging hydrophobic polyester coils and hydrophilic microfiber polyester coils on a bi-layer knitted fabric (moisture travels through the hydrophobic layer into the hydrophilic layer). Using microfiber polyester helps to achieve better transition speed for this type of material, so that transmission speed would match the diffusion speed [ 182 ]. Another way that moisture pumping can be achieved in fabrics is by using Janus (membrane that has opposite properties on each side membranes [ 183 ]). X. He with colleagues analyzed a material—electrospun polyurethane nanofiber onto superhydrophilic gauze. As the material mentioned before, it has a moisture- pumping mechanism, ensures wearers comfort and is a suitable option for wearable health monitoring applications [ 184 ]. 5.3. Thermoresponsive Electrospun Materials for Active Thermal Regulation The use of phase change materials (PCMs) has been widely reported as an effective strategy to improve thermal comfort and reduce thermal stress in wearable applications [ 185 ]. PCMs function as heat reservoirs by absorbing and releasing thermal energy through a solid–liquid phase transition, which is associated with high latent heat storage capacity [ 148 , 186 ]. The schematic diagram of PCM work and phase transition of Polyurethane solid–solid phase change materials (SSPCMs) are presented in Figure 13 . To enable their incorporation into textiles, PCMs are frequently microencapsulated (μPCMs), preventing leakage during phase transition and allowing their integration into fibrous systems [ 187 ]. Microencapsulated PCMs are particularly suitable for textile applications, as their polymeric shells preserve structural integrity under repeated thermal cycling and mechanical deformation. Several fabrication approaches have been explored to incorporate μPCMs into fibres. Ahn et al. in [ 186 ] demonstrated the successful production of μPCM-polymer fibre composites using conventional dry-jet wet-quench spinning techniques, achieving PCM loadings of up to 80 wt %. While high μPCM content resulted in reduced mechanical strength and elasticity, the thermal energy storage performance of μPCM-cellulose acetate and cellulose fibres indicated strong potential for smart textile applications requiring passive thermoregulation. Industrial studies have further confirmed the durability of PCM-loaded fibres, reporting stable thermal performance over more than 100 heating-cooling cycles [ 188 ]. Despite their effectiveness, most commercially available PCMs are derived from non-renewable sources, raising environmental concerns. Consequently, increasing attention has been directed toward bio-based PCMs. Natural fatty acids such as myristic, palmitic, and stearic acids, as well as octadecanol, have been encapsulated using gelatin–pectin biopolymer shells, producing sustainable PCM composites with excellent thermoregulation properties and no leakage during phase transition [ 189 ]. Similarly, palmitic acid encapsulated within biodegradable polylactic acid (PLA) shells, using poly(vinyl alcohol) (PVA) as an emulsifier, has demonstrated effective thermal regulation while improving environmental compatibility [ 190 ]. These developments highlight the growing shift toward sustainable and biocompatible PCM systems. Electrospinning has emerged as a particularly versatile platform for integrating PCMs into textiles due to its high porosity, conformability, and compatibility with sensitive materials. Huang et al. in [ 191 ] developed coaxial PAN/PEG electrospun fibres doped with Al 2 O 3 nanoparticles (see Figure 14 ), achieving stable heat capacity and enhanced fibre durability. Reviews by McCord et al. in [ 192 ] and Das et al. in [ 102 ] further demonstrated that core–shell electrospun designs significantly improve PCM encapsulation efficiency and thermal cycling stability, especially when biocompatible shells such as PVA or polyurethane are used. More recent work by Zhang et al. in [ 193 ] reported a hybrid electrospun membrane incorporating PVA, PCM microcapsules, and nano-silica, achieving both thermal energy storage and passive cooling through solar reflectance and mid-infrared emission. Crosslinking strategies, such as photo-crosslinking, have also been shown to enhance PCM retention and wash durability, maintaining thermal functionality after repeated laundering cycles [ 194 ]. Beyond passive thermal buffering, smart textiles increasingly incorporate materials that provide real-time thermal feedback. Thermochromic materials, which reversibly change colour in response to temperature variations, offer an intuitive and non-intrusive method for thermal sensing. Lee et al. in [ 195 ] developed thermochromic electric heating textiles in woven and knitted structures, demonstrating that double-layer woven fabrics exhibit superior heating performance, tensile strength, and clearer colour transitions compared to knitted counterparts. The effectiveness of colour change was found to depend not only on fabric structure but also on yarn composition and insulation, with soybean yarns showing particularly pronounced thermochromic responses. Recent advances have extended thermochromic functionality into electrospun systems. Supian et al. in [ 196 ] highlighted the rapid development of reversible thermochromic polymer nanocomposites, while Ma et al. in [ 197 ] demonstrated electrospun membranes containing leuco dyes capable of colour change under skin-relevant temperatures. Simpler approaches using commercially available thermochromic powders embedded in PMMA nanofibres have also shown effective colour transitions [ 198 ]. However, challenges remain regarding wash-fastness and long-term durability. Solutions such as flexible binders, sol–gel coatings, and plasma surface treatments have been shown to improve dye fixation and resistance to water exposure [ 199 , 200 ]. Recent studies suggest that combining thermochromic materials with PCMs within composite fibre architectures can simultaneously provide visual feedback and thermal regulation (see Figure 15 ) [ 201 , 202 ]. Another emerging class of thermoresponsive materials is temperature-sensitive hydrogels. Hydrogels based on poly(N-isopropylacrylamide) (PNIPAM) exhibit a lower critical solution temperature (LCST) near 32 °C, enabling rapid volumetric contraction or swelling in response to small changes in skin temperature. Huang et al. in [ 203 ] developed a temperature-responsive self-contracting nanofibre/hydrogel composite using electrospun poly(lactic acid-co-trimethylene carbonate) (PLATMC) nanofibres combined with methacrylate gelatin hydrogel layers. Although hydrogels typically suffer from weak mechanical properties, biaxial orientation techniques have been shown to significantly enhance their mechanical strength and durability [ 204 ]. Recent studies further demonstrate that PNIPAM-based blends with chitosan, hyaluronic acid, or alginate improve biocompatibility, mechanical resilience, and self-recovery after deformation [ 205 , 206 ]. In contrast to passive systems, active heating textiles enable on-demand thermal regulation through Joule heating. Nanoconductive fibres incorporating materials such as MXenes have demonstrated excellent electrical and photothermal heating performance while maintaining flexibility and durability under repeated mechanical deformation (see Figure 16 ) [ 105 , 106 ]. However, challenges related to oxidation stability and skin safety persist. Encapsulation strategies using hydrophobic biopolymers have been proposed to preserve conductivity while minimizing skin irritation [ 207 ]. Importantly, Joule heating systems must balance electrical performance with breathability and comfort, particularly when integrated with PCMs or hydrogels. Despite significant progress, comparative studies evaluating these thermoresponsive systems under realistic use conditions, such as sweating, washing, bending, and long-term skin contact, remain limited. Long-term biocompatibility data are especially scarce, particularly for nanomaterial-based systems. As a result, current research is increasingly focused on multimodal textile architectures that integrate PCMs, thermochromic feedback, hydrogels, and conductive heating within layered or coaxial electrospun structures. These multifunctional designs offer a promising pathway toward adaptive, durable, and sustainable smart textiles capable of dynamic thermal regulation, user feedback, and enhanced wearer comfort. 6. Thermally Integrated Multifunctional Sensor Systems Smart, wearable textiles are fabrics, with ability to sense external stimulation and to respond to it in a certain way. The external stimuli can be thermal, mechanical, chemical, electrical, magnetic, optical, etc. [ 208 , 209 ], with the integration of functional materials such as silver nanoparticles [ 210 ], graphene [ 103 ], or conductive polymers [ 211 ], nanofiber textiles can sense, respond, and interact with the user’s environment or body. This review part discusses about electrospun conductive biomaterial-based composites for temperature sensing. Electrospinning is a technique, which allows the incorporation of functional materials, such as nanoparticles, into the fibers, creating composites suitable for various applications, including thermal regulation. There are four levels of smartness for biomaterials, namely inert, active, responsive, and autonomous or intelligent ( Figure 17 ). Inert biomaterials provide biocompatibility without eliciting adverse effects, meaning they do not trigger toxic or harmful responses within the body. Active biomaterials enable a unidirectional, non-regulated release of therapeutic agents. Responsive biomaterials are capable of detecting specific environmental or physiological cues and subsequently initiating therapeutic release. Autonomous biomaterials not only sense such signals but also dynamically adjust their functional properties in response to changing conditions, thereby sustaining the delivery of enhanced or alternative therapeutic modalities [ 212 , 213 ]. In nature, biopolymer exists in the form of proteins, cellulose, starch, gelatin, chitosan (CS), polysaccharides, collagen, and nucleic acids Polymers by itself cannot improve thermal conductivity [ 214 , 215 , 216 ]. Thus, so many researchers are functionalizing bio composites by embedding various conductive additives. 6.1. Conductive Biomaterial-Based Composites for Temperature Sensing Body temperature is a fundamental physiological indicator of human health. Although the body maintains a narrow thermal range under normal conditions, even slight deviations often signal the onset or progression of disease. Because temperature fluctuations accompany a wide variety of pathological states, continuous and accurate monitoring has become a central objective in the development of wearable biomedical devices. Numerous studies have demonstrated that wearable temperature sensors must combine high sensitivity, mechanical stability, and long-term reliability to function effectively in real world environments [ 93 , 217 ]. To meet these requirements, researchers have increasingly turned to advanced materials and fabrication strategies capable of producing flexible, skin conformal, and multifunctional sensing platforms. This chapter provides a comprehensive overview of the principles, materials, and emerging electrospun systems that underpin modern wearable temperature sensors. A sensor operates by converting a nonelectrical physical quantity into an electrical signal that can be processed, quantified, and interpreted. A broad range of materials—including semiconductors, ceramics, metals, and organic polymers—can serve as sensing elements. The intrinsic properties of these materials determine not only the sensitivity and stability of the device but also its potential to integrate multiple sensing functions within a single platform [ 218 ]. Tactile sensing, a closely related field, involves the spatial measurement of diverse stimuli such as pressure, strain, shear, temperature, and humidity [ 219 ]. Among these, temperature remains a central physiological parameter for real time monitoring of vital signs [ 220 , 221 ]. The convergence of tactile and thermal sensing in wearable systems has motivated the exploration of materials that are flexible, biocompatible, and capable of multimodal signal transduction. Electrospinning has emerged as a powerful technique for producing nanofibrous materials with high surface area to volume ratios, tunable porosity, and excellent mechanical flexibility. When conductive nanomaterials—such as carbon nanotubes (CNTs) or graphene—are incorporated into biopolymer matrices, the resulting composites exhibit temperature dependent electrical behavior suitable for wearable sensing applications [ 222 ]. These electrospun conductive composites respond to thermal changes through variations in electrical conductivity, enabling lightweight, breathable, and skin compatible temperature sensors. Their structural versatility also allows integration into textiles, patches, and other conformal formats required for continuous physiological monitoring. Temperature sensors used in wearable systems typically rely on one of three primary mechanisms: thermo-sensitive mechanisms, thermo-resistive mechanisms and thermo-electric mechanisms ( Figure 18 ). Thermo-sensitive sensors detect temperature through changes in the electrical resistance of the active layer. These resistance variations arise from temperature induced modifications in charge transport pathways within the sensing material [ 223 , 224 , 225 , 226 ]. Thermo resistive sensors operate on the principle that electrical resistance varies with temperature due to changes in material conductivity. The temperature coefficient of resistance (TCR) is a key parameter governing their performance. For example, Shin et al. [ 227 ] fabricated a NiO based thermoresistive sensor by coating NiO nanoparticle ink onto PET, demonstrating the importance of rapid response and long-term stability in wearable thermistors. Thermoelectric sensors exploit the Seebeck effect, in which a temperature gradient generates an electrical voltage. This mechanism enables self-powered sensing in some configurations, making thermoelectric devices attractive for long term wearable applications [ 227 ]. Nanocomposite systems offer enhanced performance due to synergistic interactions between polymer matrices and nanoscale fillers. Ben Shimon and Ya’akobovitz [ 104 ] developed flexible, biocompatible temperature sensors using carbon nanotube (CNT PDMS) composites. Thermal mismatch between CNTs and PDMS induces strain within the conductive network, altering electrical pathways and enabling temperature dependent resistance changes. These sensors exhibit excellent flexibility, low weight, and high reproducibility under repeated mechanical loading, making them suitable for on skin deployment. Material selection plays a critical role in sensor comfort and durability. Natural polymers (cellulose, silk, chitosan) provide biodegradability and skin friendliness. While, synthetic polymers (polyurethane, polyacrylonitrile) offer mechanical strength, elasticity, and long-term stability under harsh conditions [ 228 , 229 ]. Electrospinning and electrospraying are versatile techniques for functionalizing thermal textiles. Electrospun phase change fibers offer several advantages, including the elimination of encapsulation steps, controllable fiber dimensions, and cost-effective processing [ 230 ]. Besides CNT, graphene, boron nitride and silicon nitride nanoparticles, phase change materials are very popular components in thermal management systems [ 231 ]. PCMs are widely used in thermal management systems and can be classified: by chemical nature as organic PCMs (o PCMs), inorganic PCMs (io PCMs) and eutectic PCMs (eu PCMs). By physical behavior as solid–solid, solid–liquid, solid–gas and liquid–gas PCMs [ 192 , 232 , 233 , 234 ]. PCMs are particularly attractive for smart textiles due to their ability to regulate heat flow without significant temperature change. Biopolymer based PCMs have been incorporated into medical products such as bandages, where they absorb and store body or external heat and subsequently release it gradually [ 235 ]. Despite their advantages, PCMs face challenges such as leakage and fluidity during melting. Electrospinning provides an effective strategy to confine PCMs within form stable nanofibers, improving reliability and expanding applicability [ 192 ]. Incorporating conductive fillers such as CNTs or graphene further enhances thermal conductivity, enabling both passive heat dissipation and active temperature control [ 232 ]. A comprehensive overview of electrospun PCM reinforced nanofibers and their additives is presented in Table 5 . Wearable sensors can be organized into four major categories [ 218 ]: single multifunctional sensors, planar integrated sensors, three-dimensional assembled sensors, stacked or hybrid integrated sensors. For temperature sensing, carbon-based nanomaterials-including CNTs, graphene, boron nitride, silicon nitride nanoparticles, and carbon nanofibers-are frequently integrated into electrospun biopolymer matrices due to their exceptional electrical and thermal performance [ 246 , 247 ]. Stacked or hybrid architectures integrate multiple sensing modalities—such as temperature, pressure, and humidity—within a single layered device. These systems use resistive, thermoelectric, or other mechanisms to achieve simultaneous, compact, and interference resistant detection. As an example of stacked or hybrid structure multifunctional temperature sensor Yu X et al. [ 219 ] demonstrated a multifunctional tactile sensor capable of detecting pressure, temperature, and material type concurrently, illustrating the potential of layered integration for real time health monitoring. Electrospun conductive materials, particularly those incorporating CNTs or graphene, are highly promising for thermal management due to their high conductivity and structural tunability. When integrated into stacked or hybrid systems, they enable both passive heat dissipation and active temperature regulation, supporting complex sensing tasks in next generation wearable electronics [ 218 ]. Wearable temperature sensing technologies have advanced significantly through innovations in materials science, nanocomposites, and electrospinning. The integration of conductive nanomaterials, biopolymers, and phase change materials has enabled flexible, lightweight, and multifunctional sensing platforms capable of real time physiological monitoring. 6.2. Simultaneous Antibacterial, Breathable, and Thermal Properties Electrospinning has emerged as a versatile, cost-effective, and efficient technique for producing micro- and nanofibrous structures with controlled morphology and composition [ 213 , 248 , 249 , 250 ]. Owing to their thin, lightweight nature, electrospun nanofiber mats can be seamlessly integrated into wearable systems, including textile fabrics. These nanofibrous platforms are particularly suitable for sensor applications, enabling the detection of physical parameters such as movement, temperature, and humidity [ 73 ]. This foundational capability makes electrospinning an ideal method for engineering multifunctional materials that combine thermal regulation, breathability, and antibacterial performance. Biopolymers enriched with functional additives offer a promising route toward materials that simultaneously exhibit thermoregulating and antibacterial properties. Such multifunctionality is typically achieved by incorporating phase change materials (PCMs) to manage heat flow and antimicrobial agents-such as metal nanoparticles or bioactive compounds-to inhibit bacterial growth. This dual-function design enables the development of advanced smart textiles suitable for medical, environmental, and wearable applications. Several studies have demonstrated the effectiveness of integrating PCMs and conductive or reinforcing additives into electrospun fibers. Wu et al. [ 244 ] fabricated PEG/PVA composite membranes via green electrospinning, achieving excellent flexibility, breathability, and thermal regulation. The incorporation of carbon nanotubes (CNTs) significantly enhanced mechanical strength and increased thermal conductivity by 40.4% at only 1.5 wt % CNT loading. The membranes exhibited a practical phase-change temperature range (26.9–38.9 °C) and high latent heat values, confirming their suitability for wearable thermal management. Similarly, Qin et al. [ 158 ] developed antibacterial, thermoregulating textiles using coaxial electrospinning, with PAN/curcumin forming the sheath and n-octadecane serving as the PCM core. These materials demonstrated strong potential for applications in clothing, food preservation, and biomedical products. Wang et al. [ 159 ] further advanced this field by synthesizing curcumin-based polyurethane (Cur-PU) films with excellent antibacterial activity and systematically characterized their thermal, mechanical, and biocompatibility properties. Curcumin has been widely explored as a natural antimicrobial agent in electrospun systems. Leng et al. in [ 251 ] encapsulated curcumin in PCEC nanoparticles and incorporated them into PVA/collagen composite films, demonstrating strong antibacterial performance. Additional studies have produced curcumin-loaded PLA/PVP nanofibers [ 252 ] and chitosan–collagen nanofibrous mats [ 253 ], both showing significant potential for wound healing and biomedical applications. Lin et al. in [ 254 ] fabricated hydrophilic HCP and HCPG nanofiber membranes that effectively reduced bacterial adhesion, particularly against S. aureus . Likewise, Khanzada et al. in [ 255 ] developed Aloe Vera/PVA nanofibers with inherent antibacterial activity, highlighting the versatility of natural bioactive compounds in electrospun systems. Nanoparticles have also been employed to impart multifunctionality to electrospun membranes. Costa et al. in [ 256 ] produced biodegradable PCL membranes functionalized with Ag, TiO 2 , and MgO nanoparticles, achieving high filtration efficiency and strong antibacterial effects. Notably, integrating PCL/MgO membranes within cotton layers improved thermal comfort, demonstrating the synergistic benefits of nanoparticle incorporation (see Figure 19 ). Peng et al. in [ 27 ] extended these concepts to electronic skin (e-skin) applications by developing a flexible, breathable, biodegradable nanofiber-based triboelectric system incorporating Ag nanowires. This work illustrates the potential of multifunctional nanofibers in next-generation wearable electronics. Further innovations have focused on enhancing UV protection, waterproofing, and breathability alongside thermal regulation. Wang et al. [ 257 ] created anti-UV, thermo-regulating membranes using ZnO nanoparticles in coaxially electrospun octadecane/PAN fibers. Additional work demonstrated strong thermal energy storage in PEG/PA6/TiO 2 composites [ 247 , 257 ]. Yi et al. [ 258 ] produced waterproof-breathable CNT-loaded membranes that blocked liquid water while allowing sweat vapor to escape, improving wearer comfort. Xu et al. in [ 259 ] developed dual-mode fabrics combining n-eicosane/PVDF/Cu 7 S 4 membranes with electrospun PAN layers, achieving both thermal management and breathability (see Figure 20 ). Feng et al. in [ 160 ] fabricated coaxial PU/PEG membranes with temperature-responsive moisture permeability, enabling sweat evaporation and thermal buffering. Zhang et al. in [ 260 ] produced PBSe/PO3G-BPU membranes with excellent waterproofing (see Figure 21 ) and breathability, further expanding the range of high-performance wearable materials. Qiao et al. in [ 261 ] prepared PEG/PEO/CNT phase-change composite fibers via centrifugal electrostatic spinning, demonstrating excellent flexibility, thermal conductivity, and energy storage capacity (see Figure 22 ). These results underscore the strong potential of PCM-integrated nanofibers for flexible wearable thermal management. Collectively, these studies highlight the rapid advancement of elect

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中文

# 用于推进下一代智能纺织品的热调节可穿戴传感器的生物相容性静电纺丝生物材料

## 摘要

电子设备(包括可穿戴传感器)的快速增长增加了电子废弃物,推动了人们对可持续、生物相容性材料的兴趣。静电纺丝生物材料已成为多功能可穿戴纺织品的多功能基底,具有柔韧性、高比表面积、可调节的孔隙率和生物相容性。利用天然聚合物(如丝素蛋白、纤维素、壳聚糖)和合成聚合物(如聚己内酯、聚乳酸、聚偏氟乙烯),静电纺丝技术可制备出能够支持热调节、湿度管理以及压力、温度、湿度或化学检测集成传感的纳米纤维毡。仿生设计、混合复合材料和先进架构通过相变材料、热致变色染料、水凝胶和导电纳米纤维实现被动和主动热调节,同时保持穿戴者的舒适性、透气性和皮肤安全性。尽管取得了进展,但在耐用性、耐洗性、能效、制造可扩展性和可回收性方面仍存在挑战。本综述全面概述了生物材料、制备技术、多功能传感器集成和热调节策略,突出了将可持续性、自适应热管理和高性能传感相结合的下一代可穿戴纺织品的机会。

**关键词:** 纳米纤维;静电纺丝;可穿戴传感器;多功能性;生物材料;生物相容性;生物传感器;热调节;热性能;智能纺织品

## 1. 引言

先进材料科学与可穿戴电子技术的融合催化了智能纺织品的出现——智能纺织品是嵌入了功能组件的面料,能够感知、响应并适应环境和生理刺激。在推动该领域发展的众多创新中,生物相容性静电纺丝生物材料因其作为可穿戴传感器(特别是为热调节设计的传感器)基础基底的潜力而受到极大关注。静电纺丝(见图1)是一种多功能且可扩展的技术,能够制备具有高比表面积与体积比、可调孔隙率和机械柔韧性的纳米纤维毡——这些属性对于无缝集成到纺织品中以及保持穿戴者舒适性至关重要[1]。当使用聚偏氟乙烯(PVDF)、丝素蛋白或聚乳酸(PLA)等生物相容性聚合物进行工程化设计时,这些静电纺丝纤维不仅支持生理相容性,还提供压电性和热响应性等功能特性[1,2,3,4,5,6,7]。这些材料集成到可穿戴传感器中,为实时健康监测开辟了新途径,能够检测皮肤温度、水合水平和代谢活动等生命体征[9,10,11]。当嵌入服装中时,这些传感器可通过响应检测到的变化来激活加热或冷却机制,从而自主调节热舒适性,在不同环境中提升性能和幸福感[11,12,13]。此外,向可持续和瞬态电子器件的转变进一步凸显了可生物降解和无毒材料在可穿戴系统中的重要性。静电纺丝生物材料,特别是源自天然来源(如丝素蛋白)的材料,符合这一愿景,可在不牺牲功能性的前提下提供环保替代品[2]。

本综述的主要目的是提供基于生物相容性静电纺丝生物材料的热调节可穿戴传感器开发方面的当前现状、挑战和未来方向的全面概述。随着可穿戴技术日益集成到医疗保健、体育和个人健康领域,对兼具功能性和皮肤相容性的材料需求已变得至关重要。本讨论的核心是静电纺丝技术在从生物相容性聚合物制备纳米纤维支架方面的关键作用,这些支架可被工程化以支持智能纺织品中的热调节。在此背景下,本综述考察了材料选择、制备策略和传感器集成,同时讨论了实现下一代智能纺织品所面临的挑战和机遇。

本综述的创新之处在于将生物相容性静电纺丝生物材料、热调节和多功能可穿戴传感器相整合,展示先进的纤维架构如何同时实现被动和主动热管理、湿度控制和实时传感。它强调了可持续材料选择、混合复合材料和环保相变系统,将材料设计与可回收性、能效和环境影响联系起来。通过将制备策略、功能性能和实际挑战联系起来,本工作为指导下一代皮肤友好型多功能智能纺织品的开发提供了全面框架。

### 1.1. 智能纺织品与可穿戴传感器的崛起

电子器件集成到纺织品中代表了可穿戴技术领域的关键进步,标志着智能面料的出现——这些材料具有感知、响应和与周围环境通信的能力。这一进步反映了可穿戴系统的更广泛发展轨迹,其已从原始的健身追踪器演变为高度复杂的、嵌入式的纺织平台,能够进行实时生理监测、环境感知和自适应功能。这一转型的核心是柔性电子、纳米技术和先进材料工程的融合,共同促进了传感器、执行器和通信模块无缝集成到织物基底中。因此,服装被重新概念化,不再是被动的覆盖物,而是调节人体与其外部环境之间相互作用的动态界面,应用范围涵盖健康监测、环境意识和个性化表达方式。这一范式转变凸显了智能纺织品研究的跨学科性质,并强调了其重新定义技术创新的潜力以及服装在当代社会文化意义中的重要性[12,13,14,15]。

智能纺织品通常分为三类:被动型、主动型和超智能系统(见图2)。被动型纺织品能够感知外部环境或生理刺激,而主动型纺织品不仅能检测变化,还能通过嵌入式执行器作出响应。超智能纺织品通过整合逻辑和决策功能进一步扩展了这些能力,从而实现对动态条件的自主适应[14]。这种分类反映了可穿戴系统日益复杂和功能性增强的进程,范围从简单的温度传感器到能够实时自动调整的服装。这些先进功能越来越多地通过集成柔性传感器来实现,用于监测温度、应变、湿度和生化标志物等参数,凸显了材料科学、电子学和纳米技术在开发下一代可穿戴平台中的跨学科融合。

作为智能纺织品基石的可穿戴传感器的激增,得益于柔性电子、纳米材料和小型化的重大进步。这些发展使得制造具有更高灵敏度、生物相容性和适应性的传感器成为可能,能够监测广泛的生理参数——包括心率、呼吸、皮肤温度和水合状态——而不影响用户舒适度或活动性。材料科学的进步,特别是导电聚合物、碳基纳米材料和静电纺丝纳米纤维的整合,促进了轻质、可拉伸且顺应皮肤的传感器的制造。此外,导电纤维和印刷电子学的集成允许传感器无缝嵌入纺织基底中,从而支持持续、非侵入性的监测,同时保持传统服装的透气性和可穿戴性。总体而言,这些创新凸显了电子学、纳米技术和材料工程在推进下一代智能纺织系统中的跨学科融合[15]。

在医疗保健领域,智能纺织品正被用于远程患者监测、康复和慢性病管理。在体育领域,它们通过追踪生物力学数据来优化表现和预防伤害。军事应用包括可检测环境危害或监测士兵生命体征的制服。甚至时尚界也在拥抱智能纺织品以实现交互式和表现性的服装。智能纺织品市场正在迅速扩大。根据Grand View Research的数据,到2025年预计将超过120亿美元,受消费需求、技术创新和跨行业采用推动[16]。然而,在耐用性、耐洗性、能源自主性和数据隐私方面仍然存在挑战。研究人员正在探索能量收集织物、可生物降解电子器件和安全数据协议等解决方案以应对这些问题。随着该领域的发展,生物相容性静电纺丝生物材料正成为可穿戴传感器有前景的基础。其柔韧性、透气性和与人体皮肤的相容性使其成为热调节应用的理想选择——在动态环境中确保舒适性的同时实现精确的温度控制。

### 1.2. 热调节作为长期可穿戴舒适性的核心挑战

随着可穿戴技术日益融入日常生活——从健身追踪器和智能服装到医疗监测系统——热调节问题已成为确保持续用户舒适度和设备性能的核心挑战。与传统电子产品不同,可穿戴设备直接接触皮肤,使得热管理不仅对运行稳定性至关重要,而且对防止不适、刺激甚至热损伤也至关重要。人体皮肤对温度波动高度敏感,长时间暴露于嵌入式电子设备产生的高温下会导致出汗、皮肤疲劳并降低设备贴合度。相反,在寒冷环境中保暖不足会损害传感器精度和用户体验。因此,在皮肤和可穿戴设备界面之间维持稳定的微气候对于长期可用性至关重要。

热调节纺织品的最新进展集中在被动和主动两种策略上。被动方法包括使用相变材料(PCM)、反射涂层和多孔结构以促进散热。被动式热调节纺织品的类型如图3所示。主动系统集成了热电模块、微流控冷却和响应性聚合物,可实时适应温度变化[17,18]。静电纺丝纳米纤维由于其高比表面积、可调孔隙率和整合功能性添加剂的能力而在此领域显示出前景。例如,将碳基纳米材料或金属纳米颗粒整合到静电纺丝毡中可增强热导率,实现从皮肤高效传热[11,12,13,19]。此外,丝素蛋白和聚己内酯(PCL)等生物相容性聚合物为传感器集成提供了透气且皮肤友好的平台。尽管有这些创新,但仍存在一些挑战。在反复热循环下的耐用性、耐洗性和能效仍是关键问题。此外,平衡热调节与传感器灵敏度、机械柔韧性和美观等其他性能指标需要多学科设计策略[19]。解决这些挑战对下一代智能纺织品至关重要,特别是在医疗保健、体育和军事等长期穿戴普遍存在的应用中。未来研究必须聚焦于结合被动和主动热管理、可持续材料和智能反馈机制的混合系统,以优化舒适度和性能[12,19]。

### 1.3. 生物相容性材料和静电纺丝技术的作用

智能纺织品可穿戴传感器的开发取决于使用兼具功能性和长期皮肤接触安全性的材料。生物相容性聚合物——如聚己内酯(PCL)、聚乳酸(PLA)、丝素蛋白和壳聚糖——因其无毒、可生物降解且皮肤友好的特性而成为理想候选[2,4,5,6,7,8,9]。这些材料提供机械柔韧性、透气性和与人体组织的相容性,使其适合长期可穿戴应用。静电纺丝技术在将这些聚合物转化为具有高比表面积、可调孔隙率和优异机械顺应性的纳米纤维毡方面发挥着关键作用。该技术利用静电力将聚合物溶液拉伸成超细纤维,产生模拟细胞外基质且与皮肤良好贴合的结构[1]。所得纤维毡具有高度透气性,可通过工程化设计整合功能性添加剂,如导电纳米颗粒、相变材料或抗菌剂,从而在智能纺织品中实现多功能能力。例如,与碳量子点一起静电纺丝的丝素蛋白因其可生物降解性和热响应性而在瞬态电子器件中显示出前景[2]。类似地,静电纺丝PVDF及其共聚物因其压电特性而被探索应用于可穿戴系统中的自供电传感平台[1]。尽管有这些进展,但在实现一致的纤维形态、机械鲁棒性和可扩展制造方面仍然存在挑战。研究人员正在积极探索结合天然和合成聚合物的混合材料,以及绿色溶剂和集成无线模块,以创建完全自主和可持续的智能纺织系统[11,12,13]。

## 2. 热调节可穿戴传感器的生物相容性

热调节传感器集成到可穿戴纺织品中涉及在运动、出汗和温度波动等动态条件下与人体的持续和密切接触。在此背景下,生物相容性成为一种功能性必要条件,不仅是为了确保皮肤安全,而且是为了维持设备的舒适性和长期可用性。虽然热调节智能纺织品通常不被归类为医疗器械,但它们仍需符合高标准的皮肤相容性,特别是当预期用于长期或反复穿戴时。

在可穿戴热调节传感器中,生物相容性超越了单纯的毒性缺失,涵盖了一系列有助于皮肤舒适性、生物惰性和与身体机械和谐性的特性。这些包括非刺激性表面化学、透气性和有效湿度管理、机械柔软性和灵活性,以及在潮湿、热活性环境中的抗微生物生长能力。与需要评估全身性生物效应的植入式材料不同,可穿戴生物材料主要强调表皮安全性和运动出汗过程中的舒适性。为阐明这些因素在热调节服装中的相关性,以下部分总结了材料架构如何控制皮肤-纺织界面的湿度和热量。图4示意性地说明了后续章节中讨论的影响热调节可穿戴传感器生物相容性的系统级因素。在此背景下,生物相容性不应被解释为静态的材料属性,而应被理解为在实际使用条件下由皮肤-纺织相互作用塑造的动态系统级响应。

在应对动态条件下的持续皮肤接触方面,多项研究强调了材料设计在增强湿度管理和减少皮肤刺激方面的重要性。Zhao等人[20]证明,通过在纤维基底上使用无氟水性涂层来操纵织物的架构性能可以显著改善湿蒸气透过率,有效防止液体接触皮肤,从而降低刺激风险;这与Park等人[21]的发现一致,他们评估了耐高温纳米纤维膜中的湿度管理,强调了透气性与热保护之间的耦合。这些观察与Troynikov和Wardiningsih[22]的研究结果一致,他们检验了主动型服装并发现织物架构在运动过程中控制皮肤微气候的稳定性,强调纺织力学和孔隙率如何在实践中引导汗液管理和舒适性。总而言之,这些结果建立了微观结构、微气候和运动中感知舒适性之间的联系。综合来看,这些研究表明,通过纺织架构控制皮肤微气候是热调节可穿戴设备生物相容性的主要驱动因素,而非次要的舒适性增强特征。

在舒适性与功能性关系的扩展上,Xie等人[23]和Zhang等人[24]指出,仔细调整纺织材料特性可平衡透气性和耐水性,从而在长期穿戴过程中兼顾舒适性和性能。Wang等人[25]进一步说明了这些原理在医疗保健电子学中的应用,证明基于MXene的多孔透气材料即使在运动过程中也能保持最佳传感性能和抗菌特性,从而增强用户舒适性和设备功能性。这些材料的多功能性反映了在可穿戴健康监测解决方案中将舒适性与技术性能相整合的日益增长的趋势。这种融合表明可穿戴设计理念的更广泛转变,其中生物相容性和传感性能通常被共同优化,而非被视为竞争目标。

可穿戴设备与人体之间的机械和谐是生物相容性的第二维度,同样至关重要,并在各研究中作为运动中长期舒适性和信号保真度的限制因素出现。跨研究的一致结论是,机械失配(而非单纯的化学不相容性)通常是运动过程中不适、刺激和信号退化的根本原因。Xie等人[23]和Khan等人[26]的综述强调,在聚合物和纺织基底中共同设计生物相容性和机械顺应性对于实现稳定的皮肤上操作至关重要。最近的材料策略越来越多地证明,热调节可穿戴设备中增强的功能性不需要妥协生物相容性,反而可以强化舒适性和长期可用性。Peng等人[27]报告了透气、可生物降解和抗菌电子皮肤的制备,可在操作过程中改善相容性和舒适性。Wu等人[28]通过开发设计用于与皮肤形成保形界面的可渗透电极扩展了这一概念,确保即使在剧烈活动中也能维持持续的舒适性和功能性。同样,Liu等人[29]表明基于聚偏氟乙烯的膜表现出超柔性、强防水性和透气性,这是电子皮肤应用的关键属性,突出了在可穿戴技术中整合功能材料的重要性。这些进展例证了智能纺织品改善穿戴者与服装界面的潜力,促进了健康和舒适性。在皮肤-纺织界面进一步增强功能性方面,Szewczyk等人[30]证明浸油聚合物纤维膜可改善皮肤水合作用——这是延长穿戴期间维持皮肤健康的关键因素。与此一致,Maksoud等人[31]设计的可渗透摩擦电纤维毡表现出与人体皮肤密切匹配的机械性能,即使在剧烈运动下也能保持舒适性和性能输出。总体而言,这些发展凸显了先进纺织工程对可穿戴技术和用户体验的深远影响。这项工作强化了这样的观点:材料架构可在长期穿戴中同时实现舒适性、耐用性和功能性能的提升。

先进纺织设计和材料特性的整合对于最大化可穿戴技术的舒适性和功能性至关重要。该领域的持续创新对于开发优先考虑穿戴者体验的有效解决方案至关重要,特别是在主动型和医疗保健应用中。重要的是,这些证据表明,在纺织层面的材料和结构选择越来越多地决定热调节可穿戴设备的系统级性能和用户接受度。

除个体材料展示外,多项研究表明机械柔软性、可拉伸性和弹性回复是长期可穿戴性的决定性因素。McLaren等人[32]将顺应性传感器放置和可变形设计确定为改善神经康复纺织品用户体验的关键因素,而可穿戴ECG系统的分析[33]直接将机械顺应性与减少运动伪影和改善患者安全性联系起来。Ding等人在[34]中开发的可拉伸和自粘合电极,以及Yin等人在[35]中的调查证据进一步证实,弹性和形状恢复可减轻主动使用中的刺激。[36,37,38,39,40]中的其他研究强化了软力学增强粘附、减少摩擦和保持传感性能的结论,将机械生物相容性定位为可靠热调节可穿戴设备的前提条件,而非辅助舒适性特征。因此,机械生物相容性应被视为可靠热调节可穿戴设备的前提条件,而不仅仅是辅助舒适性考量。

在探索关于热调节可穿戴传感器生物相容性的法规协调关键方面时,强调遵守既定安全标准的重要性至关重要,特别是在新材料配方及其与生物系统相互作用方面。Patel等人在[41]中和Sharma等人在[42]中强调了对齐ISO 10993标准进行严格安全评估的必要性,该标准涉及细胞毒性(ISO 10993-5[43])和重建人体表皮刺激测试(ISO 10993-23[44])等方面[45]。这种向持续在体监测的转变要求可穿戴技术中使用的所有材料对其对人体组织的影响进行全面评估,以确保长期可用性而不产生不良反应。欧洲法规采纳加强了这一转变,EN ISO 10993-23:2021/A1:2025[46]澄清了RhE终点并果断远离传统的动物模型。

推进这一讨论,Liu等人在[47]中检查了生物相容性对于由自愈水凝胶等创新材料制成的可穿戴传感器的重要性,强调这些传感器的有效性在很大程度上依赖于在多变环境中保持皮肤友好界面同时提供持续高性能。Ereifej等人在[48]中也表达了类似关切,他们注意到细胞毒性测试是评估医疗器械中各种生物材料相容性的初步步骤,从而为其安全应用奠定基础。这些法规框架共同将生物相容性从材料级检查表重新定位为与持续在体使用相一致的系统级验证过程。因此,法规协调不仅作为合规要求发挥作用,而且作为从开发早期阶段塑造材料选择和设备架构的设计约束。

此外,Choi等人在[49]中强调了对采用离子液体的可穿戴传感器进行生物相容性评估的必要性,倡导在人类角质形成细胞和成纤维细胞上进行体外测试以确保这些材料不会引发毒性反应。这种法规审查在其他研究中得到回应,这些研究证明生物相容性材料的使用,特别是天然衍生的基底如丝素蛋白,可促进符合ISO测试协议的柔软、皮肤耐受性纺织传感器的开发[50]。Wang等人在[51]中进一步将医疗监测应用中的材料稳定性与皮肤界面的一致性能联系起来。

抗菌性能已作为潮湿微气候中的共同要求被研究,其中微生物生长可能带来重大挑战。Windmiller和Wang在[52]中综述了在体化学和生化传感,强调抗菌纳米材料的整合必须仔细考虑舒适性和安全性。Baldo等人在[53]中调查了可生物降解和瞬态传感器并得出结论,天然或可水解基质可降低长期生物负荷。Sen等人在[54]中讨论了用于持久长期接触应用的抗菌静电纺丝纤维,而Shafique等人在[55]中分析了基于水凝胶的传感器并强调了在富含水分条件下的低细胞毒性和皮肤舒适性。Krysiak等人在[56]中检查了柔性纺织品中的抗菌处理,明确将卫生性能与机械舒适性联系起来。Liakos等人在[57]中测试了载有精油的醋酸纤维素静电纺丝垫,证明在不影响透气性的情况下抑制常见病原体。Yin等人在[58]中提出了丝包覆的导电丝线,以皮肤友好、可清洗的格式提供飞溅电阻和电气绝缘。跨这些研究,作者一致认为ISO 20743[59](适用时连同AATCC 100[60])是评估抗菌功效的适当纺织特定标准。这一共识强调必须在纺织相关测试框架内评估抗菌性能,以有意义地支持长期皮肤相容性。

最后,为在舒适性和卫生之外闭合安全回路,致敏和化学相容性已被研究人员框架化为对长期穿戴至关重要。Iadaresta等人在[61]中显示纺织相关化学品如苯并噻唑可在类穿戴条件下迁移到皮肤,强化了化学安全性和低刺激性配方的必要性。He等人在[62]中开发了基于丝衍生碳纺织品的集成纺织传感器贴片,并使用皮肤耐受材料展示非侵入式测量,强调设备级化学和表面处理必须符合皮肤科安全预期。Armengol等人在[63]中讨论了与纺织整理相关的过敏风险,并强调调节染料、交联剂和辅助剂以最小化医疗和消费纺织品中过敏性接触性皮炎发生率的重要性。在法规背景下,REACH[65]下的统一标准EN 1811:2023[64]为长期皮肤接触的金属部件设定了镍释放测试方法和合规判定限值(≤0.88 µg·cm⁻²·week⁻¹),从而指导可穿戴系统中按扣、连接器和电极的选择。Wang等人在[66]中综述了用于伤口管理的表面工程生物材料,证明良性涂层和钝化策略可有效降低致敏风险,为可穿戴生物传感器提供可转化方法。同时,Wang等人在[67]中探索了用于湿度感应的可生物降解多糖基质,作为使用固有低刺激性化学物质实现功能性能的途径。Zeybek, B.和Duman, M.在[68]中检查了静电纺丝传感平台并强调化学稳定性和生物相容性在最小化皮肤刺激方面的重要性。同样,Liu等人在[69]中和Tang等人在[70]中调查了可调复合纳米发电机并强化主动层工程必须从设计最早阶段考虑皮肤暴露化学。总体而言,这些发现强调化学稳定性和致敏控制是生物相容性的组成部分,特别是对于预期长期皮肤接触的热调节可穿戴设备。

综上,文献汇聚于热调节纺织可穿戴设备生物相容性的实用循证定义。该定义包括保持皮肤微气候和机械舒适性的静电纺丝、透气和机械顺应性架构;通过ISO 10993对齐的细胞毒性和刺激评估以及纺织特定抗菌测试(ISO 20743[59])验证的材料化学;以及通过REACH[65]和EN 1811[64]对致敏剂和金属部件进行物品级控制,在涉及电子元件时应用RoHS[71]约束。在该框架内,热调节、舒适性和安全性不再是相互竞争的目标,而是作为下一代智能纺织品的共同设计特征出现。

## 3. 用于热调节纺织界面的生物材料静电纺丝

### 3.1. 功能纤维制备的静电纺丝原理与进展

静电纺丝技术的原理在于导电聚合物(溶液或熔体形式)在高压电场下通过纺丝电极和收集器之间的拉伸生成连续纤维结构的能力。对于实验室规模的聚合物试验,通常采用单尖端或单喷嘴配置,其中聚合物液滴置于纺丝电极上[72,73]。在施加电场时,液滴变形为称为泰勒锥的锥形结构,一旦施加的电压超过克服液态聚合物表面张力所需的阈值,细聚合物射流便从锥体喷射而出[74]。研究表明,这种多功能装置可有效用于制造可穿戴传感器和纺织应用的功能材料原型[72,73]。当聚合物供给连续时,可实现不间断的纤维生产,从而能够向工业制造扩展[75]。

除传感性能外,热调节是可穿戴纺织界面的关键功能,因为将皮肤温度维持在舒适范围内直接影响用户舒适度、生理性能和长期可穿戴性。静电纺丝特别适用于热调节纺织品,因为其能够生产具有精确可调形态的高度多孔、轻质和透气的纤维膜。静电纺丝纳米纤维固有的高比表面积与体积比促进有效的散热和水分蒸发——这些是被动冷却的基本机制。通过控制纤维直径、孔隙率、排列和层厚度,静电纺丝毡可被工程化设计为通过在纤维结构内捕获空气的热绝缘层,或增强皮肤-纺织界面汗液蒸发和对流热传递的冷却层。

最常用的静电纺丝技术是溶液静电纺丝和熔体静电纺丝,每种技术根据预期应用提供不同的优势和局限性。溶液静电纺丝涉及将聚合物溶解在合适溶剂中以形成可纺溶液。在高压电场下,带电射流从针尖喷出,当射流朝向收集器行进时,溶剂蒸发,留下固化的纤维[76]。溶剂蒸发驱动显著的射流变细,使超细纤维的形成成为可能,其直径从几十纳米到几微米不等,这使得该技术非常适合需要高比表面积、精细孔隙率和精细结构特征的应用。实现这种纤维质量需要多种因素在有利条件下同时作用,包括与溶液、运行设置和周围环境相关的参数。这些相互关联的条件最终决定工艺的生产率并塑造所得材料的物理化学和形态特征[76]。静电纺丝加工参数的示意图表示如图5所示。

在可穿戴传感器和热调节纺织品的背景下,溶液静电纺丝的一个主要优势是其广泛的材料兼容性。多种聚合物,包括生物聚合物、导电聚合物、碳基纳米材料复合材料和刺激响应性材料,可从溶液中静电纺丝[77]。这种多功能性使得制造具有精确定制的电、热和机械性能的纤维成为可能。此外,由于溶液静电纺丝通常在环境或中等升高的温度下运行,其非常适合整合热敏性生物活性分子,如酶、抗体、生长因子甚至活细胞,而不会损害其结构完整性或生物功能[77,78]。这种能力对于集成生物传感或治疗功能的下一代智能纺织品特别有价值。

然而,溶液静电纺丝也存在挑战。使用易燃、易挥发或有毒的溶剂会引发环境、安全和监管方面的担忧,特别是对于纤维直接接触皮肤的可穿戴应用[79]。纤维内残留的溶剂会损害机械性能、生物相容性和长期稳定性,使完全去除溶剂成为必要。此外,溶剂蒸发速率强烈影响纤维形态,如果处理条件未得到仔细控制,可能导致珠状、孔洞或直径不一致等缺陷。

相比之下,熔体静电纺丝完全消除了对溶剂的需求。在这种方法中,聚合物被加热到其熔化温度以上以形成粘性熔体,然后在高压场下进行静电纺丝。当熔融射流向收集器行进时,通过冷却固化,形成连续纤维[80]。由于不发生溶剂蒸发,射流经历的变细较少,导致纤维通常比溶液纺纤维更粗——通常在微米范围内[81]。虽然这可能限制需要纳米级特征的应用,但它为机械鲁棒性至关重要的结构部件提供了优势。熔体静电纺丝本质上更加环保,因为它避免了溶剂排放并减少了对后处理纯化的需求。它也适合大规模工业生产,特别是当与熔体电写等技术结合时,可实现精确的纤维放置。熔体中高的聚合物浓度有助于增强机械强度,使熔体纺纤维对耐用的纺织界面具有吸引力,特别是那些预期用于反复洗涤、拉伸或机械应力的界面。

然而,熔体静电纺丝有其自身的局限性。只有热塑性、热稳定的聚合物可以被加工,这限制了材料选择[82]。高加工温度可能降解敏感添加剂,阻止生物活性分子或某些导电填料的整合。此外,将聚合物加热到其熔点导致更高的能耗,这可能增加生产成本。聚合物熔体较高的粘度也使得实现非常细的纤维直径更具挑战性,限制了与溶液静电纺丝相比可达到的孔隙率和比表面积。熔体静电纺丝和溶液静电纺丝的对比列于表1。溶液静电纺丝和熔体纺丝的简化对比如图6所示。

传统静电纺丝对纤维排列、图案化和功能各向异性的控制有限,这些参数对于传感精度和热管理都很重要。为克服这些限制,已开发了各种静电纺丝工艺改进(如磁场或气流辅助)和硬件适应(如喷丝头或收集器设计)。例如,磁场辅助静电纺丝通过将磁性纳米颗粒(如Fe₃O₄、Fe₂O₃、CoFe₂O₄)掺入聚合物溶液[83]或使用磁性图案化收集器[84]来实现对射流轨迹的控制。这些方法产生具有改进的电导率和机械响应性的高度排列的纳米纤维,这也有助于纺织结构内的定向热传输[85]。气流辅助静电纺丝通过同轴或并排纺丝过程中的加压气流引入额外的空气动力。该修改影响射流拉伸、干燥速率和纤维形态,允许增强对孔隙率和厚度的控制——这是调节可穿戴纺织品中热量和水分传输的关键参数[85]。对于需要高沉积精度的应用,如图案化加热或冷却区域,采用近场静电纺丝和熔体电写等技术,其中喷丝头到收集器的距离减小到亚毫米至厘米范围以实现精确的纤维放置[86,87,88]。

喷丝头设计在定义纤维形态、孔隙率和功能整合方面发挥着关键作用。用于可穿戴传感器和热调节纺织品制造的喷丝头范围从无针(自由表面)系统[89]到单喷嘴、双喷嘴(同轴或并排)[90]和多流体喷丝头[79]。无针静电纺丝利用旋转鼓或圆盘作为纺丝源[91],提供高生产率,但对纤维均匀性和排列的控制有限。相比之下,多流体喷丝头提供增强的流体动力学控制并实现先进的纤维架构。同心(单轴)喷丝头促进核-壳纤维形成,允许封装敏感生物分子或导电填料(如PEDOT:PSS),而平行或并排配置产生具有空间不同功能的Janus纤维[92]。这种架构对于热调节纺织品特别有价值,其中不同的纤维域可独立管理水分传输、热绝缘或传感。

最后,收集器几何形状显著影响纤维组织。平面收集器通常产生随机取向的纤维毡,而旋转或圆柱形收集器实现半排列到高度排列的结构[93]。纤维排列不仅改善机械和电性能,还影响通过纺织品的定向热传递和气流,进一步增强热调节性能。

### 3.2. 静电纺丝生物材料设计:聚合物、溶剂、添加剂和功能化策略

材料选择在决定静电纺丝可穿戴纺织界面的传感和热调节性能方面起决定性作用。静电纺丝依赖于纤维形成聚合物的静电力、表面张力和粘度之间的微妙平衡,对于溶液静电纺丝,还涉及溶剂系统。除可纺性外,聚合物、溶剂和添加剂的选择直接影响纤维形态、孔隙率、润湿性、电导率、机械柔韧性、水分传输和热行为。因此,材料和添加剂选择的主要标准包括生物相容性、可生物降解性、功能响应和皮肤接触期间的长期稳定性。

用于静电纺丝可穿戴系统的主要纤维形成生物材料可大致分为天然、合成和复合聚合物。源自生物来源的天然生物聚合物——如蛋白质(胶原蛋白、明胶、丝素蛋白、弹性蛋白)和多糖(壳聚糖、海藻酸、透明质酸、淀粉、纤维素及其衍生物)——本质上是生物相容性和可生物降解的。这些材料中的许多表现出有利的吸湿性、吸湿性和透气性,使其特别适合促进蒸发冷却和热舒适性的皮肤接触层。合成聚合物包括聚己内酯(PCL)、聚乳酸(PLA)、聚乙醇酸(PGA)、聚(乳酸-乙醇酸共聚物)(PLGA)、聚氨酯(PU)和聚环氧乙烷(PEO),提供优越的机械耐久性、弹性和可加工性。其可调的机械性能使其能够集成到可拉伸的纺织基底中,同时在反复变形下保持结构完整性。

将天然和合成聚合物混合是广泛采用的策略,用于同时优化热绝缘、湿度管理、传感性能和机械鲁棒性,这对于暴露于动态环境和生理条件下的热调节纺织界面至关重要。

溶剂选择是可穿戴传感器和热调节纺织品中生物材料应用的关键因素,因为它直接影响聚合物相容性、毒性和溶液可加工性,关键参数包括挥发性、电导率和粘度。各种纤维形成聚合物的典型溶剂汇总于表2。某些酸如乙酸、甲酸和乳酸可作为溶剂和功能添加剂双重作用,调节溶液电导率、粘度和pH,以实现具有更高孔隙率的更细纤维。这种形态控制增强了透气性、水分传输和冷却效率——这些对热调节纺织界面至关重要。

聚合物-溶剂体系的选择也决定了静电纺丝纺织品中纤维形态、孔隙率、机械性能和功能整合。生物聚合物提供出色的生物相容性、湿度管理和环保性,但通常依赖于潜在的有害溶剂,使大规模安全生产复杂化。相比之下,合成聚合物提供机械鲁棒性、热稳定性以及与相变材料和导电填料等功能添加剂的相容性,尽管溶剂毒性和环境影响仍然是挑战。结合天然和合成聚合物或采用良性溶剂体系的混合策略对于生产耐用、多功能和皮肤安全的可穿戴纺织品越来越重要。因此,仔细优化溶剂选择、聚合物浓度和静电纺丝参数对于平衡纤维质量、功能性能和可持续性至关重要,最终支持下一代热调节和传感智能纺织品的商业转化。

盐通常被纳入以增加溶液电导率、改善可纺性并实现更细更均匀的纤维形态。已报道的例子包括NaCl、LiCl、FeCl₃、CuSO₄和AgNO₃[94]。除在纤维形成中的作用外,盐可赋予与可穿戴系统相关的额外功能属性。例如,含金属盐或纳米颗粒可增强传感层中的电信号传输[95],而AgNO₃提供电导率和抗菌功能[96]。从热调节的角度看,这些添加剂也可通过改善热导率或实现与主动加热或温度感应元件的整合而间接贡献。

表面活性剂在定制纤维形态和表面性能方面发挥着特别重要的作用。通过降低表面张力,Triton X-100等表面活性剂改善可纺性和纤维均匀性,同时促进碳纳米管、石墨烯或其他纳米材料等功能添加剂的分散[97,98]。某些表面活性剂如十二烷基硫酸钠可增加溶液电导率[99],而其他可实现对润湿性的精确控制[100]。这种可调性对于热调节纺织品特别有价值,其中亲水性表面促进汗液吸收和蒸发以实现冷却,而疏水性层充当湿度或热屏障以减少较冷环境中的热损失[100]。这种功能性对于设计用于自适应热调节的多层纺织系统至关重要。

静电纺丝纳米纤维可使用三种主要策略进行功能化:聚合物共混、掺入功能添加剂或封装,每种都为可穿戴智能纺织品提供独特的优势。聚合物共混实现协同效应,增强热、机械和传感性能超越单一组件[101]。掺入功能添加剂如导电聚合物、金属纳米颗粒、碳基纳米材料或无机MXene(列于表3)可将被动生物材料转化为多功能系统,改善电导率、热管理和传感能力。导电聚合物如PEDOT:PSS和聚吡咯提供轻质柔韧性,但在反复弯曲或洗涤下可能降解,且通常需要有毒溶剂。碳基纳米材料包括石墨烯和碳纳米管,提供优越的电导率、热性能和机械增强;然而,分散、聚集和潜在细胞毒性仍然是挑战。银和金等金属纳米颗粒贡献高电导率、抗菌性能和光热效应,尽管必须考虑成本、环境影响和长期稳定性。无机MXene提供多功能电导率和电化学响应性,但易于氧化并需要仔细加工以确保耐久性。封装通常通过同轴静电纺丝实现,允许掺入相变材料(PCM)以吸收、储存和释放热能,提供被动热缓冲同时保持柔软透气的界面。总体而言,虽然这些策略能够实现先进的热调节和传感功能,但其整合需要仔细优化生物相容性、耐用性、耐洗性和环境可持续性,突出了下一代可穿戴纺织品中性能、安全性和实际适用性之间的权衡。

此外,掺入热导电填料如碳基纳米材料或MXene可在静电纺丝毡内实现受控的热分布。这种能力对于被动散热和与主动热管理系统(包括电驱动加热或温度反馈机制)的整合都是有益的。

一旦制造完成,静电纺丝纳米纤维必须组装成适用于可穿戴和热调节纺织界面的功能配置。常见的组装策略包括逐层堆叠和直接沉积到功能基底上。逐层堆叠允许构建具有空间分离功能的多层架构,如内部亲水冷却层、中间传感或导电层和外部保护或绝缘层[98]。直接沉积到纺织面料或聚合物基底上可确保良好的粘附性、电接触和可拉伸性的保持——可穿戴应用的关键要求[79]。这些分层结构密切模仿自然皮肤热调节机制,并增强用户舒适性和设备功能性。

最后,后处理步骤如热退火、化学交联或封装常用于改善机械耐用性、耐洗性和长期热稳定性,确保静电纺丝热调节纺织界面在实际条件下的可靠性能。

## 4. 具有热调节潜力的生物相容性聚合物

### 4.1. 用于被动和主动热调节的天然生物聚合物

来自天然和合成聚合物的静电纺丝材料可被工程化用于被动(如绝缘、传导)和主动(自适应热调节)热管理,使其在电子、纺织和能源系统应用中高度多能。辐射冷却纺织品正成为实用且节能的被动个人热管理解决方案,帮助人们在户外保持舒适。被动系统依赖静电纺丝纤维的特性在无外部输入的情况下控制热流。天然聚合物(如纤维素、丝素蛋白、壳聚糖)的静电纺丝毡由于其多孔纳米纤维结构提供低热导率,使其成为有效的热绝缘体[18,107,108]。主动热管理系统涉及对温度变化动态响应的材料。静电纺丝纤维可封装相变材料(PCM,如石蜡或脂肪酸),在温度升高时吸收热量并在温度下降时释放,实现自适应调节。主动热调节通常需要功能添加剂(如PCM、碳纳米管、石墨烯、金属纳米颗粒)[109,110]。

PCM和导热膜等材料,尽管在该领域越来越多地被探索,但本质上仍表现出有限的热传输特性。因此,人体(主要热源)和冷却系统之间的热传递效率仍然受到限制。此外,用于个人热管理的大多数材料并非源自生物基原料。即使在木材或棉花被用作结构基质的情况下,其生物相容性和大规模商业化前景也未得到全面评估。

天然生物聚合物PCM包括脂质、木质素、多糖、蛋白质和其他生物聚合物。天然聚合物的优势包括环保性、可生物降解性和低毒性,并且它们还可承受温度波动,使其对被动热管理有用[111]。另一个重要特征是,当在高温下使用生物聚合物时,可采用交联、各种纳米填料的掺入或不同聚合物的共混来稳定热性能。

#### 4.1.1. 丝素蛋白:高热导率、透气性及其机械性能

与合成纤维相比,蚕丝天然可降解,衍生产品环保[112]。天然丝素蛋白(SF)表现出300-740 MPa的拉伸强度,并能在撕裂前吸收能量,具有高强度[111,113]。SF热稳定(250°以上)[114],表现出优异的生物相容性和良好的可生物降解性,其降解产物无毒[115,116,117]。此外,SF易于加工以调节机械和结构性能,并且可进行化学功能化(例如交联或改性以赋予新性能)[118,119]。SF已广泛用于组织工程[117]、伤口敷料。结合SF的复合生物材料旨在改善机械性能,特别是在潮湿环境中。新兴应用包括二维丝膜电子器件[115,116,117,118,119,120]。一项研究探索了生物衍生丝素蛋白膜用于生产热调节贴片。实验结果证明,在室外和室内条件下模拟皮肤表面的温度分别降低2.5和8.2°C[116]。SF也已用于传感器中,归因于其生物相容性、可生物降解性和低制造成本。然而,基于丝素蛋白的传感器单独具有有限的机械强度、电导率或耐湿性。将SF与芳纶纤维结合形成复合材料,可增强传感器性能[117]。丝素蛋白纤维的热导率也已被研究。一项鲜有研究的轴向分析显示,当温度从13°C升高到26°C时,热导率降低。在室温下,SF表现出比大多数纺织纤维更高的热导率[118]。

#### 4.1.2. 纤维素及其衍生物:多孔、亲水、湿度调节

纤维素是一种天然生物聚合物,含有许多羟基(-OH),使其本质上亲水。这种亲水性赋予纤维素优异的吸湿性、溶胀和润湿性能。这些特性对许多应用有利,包括水凝胶、吸附剂、生物医学设备,但当需要耐水性、尺寸稳定性或在潮湿条件下的耐久性时可能是不利的。纤维素链形成强氢键,赋予聚合物坚固的结构。纤维素的特征是其半结晶结构,由结晶和无定形区域的混合物组成。此外,纤维素在压力下表现出优异的机械(弹性)性能,这些性能是方向依赖性的并受晶体大小影响。增加氢键数量显著增强机械强度并影响孔隙率[121,122,123,124,125]。

纤维素可生物降解且无毒,使其适合用于组织工程和再生医学应用。纤维素基材料常用于药物递送系统、受控/持续释放系统、赋形剂、水凝胶、支架和生物医学表面[123]。纤维素基抗菌涂层和薄膜用于纺织和包装,而耐水纤维素材料应用于医疗设备、包装和诊断工具[126,127,128,129]。

大多数研究集中在平衡纤维素亲水性。科学家们已使用离子液体或NaOH/尿素溶液开发了纤维素水凝胶。这种水凝胶的生产允许精确控制结晶度、孔隙率和亲水性,这对于传感器的制造至关重要[119]。其他研究人员探索了增塑剂如甘油的添加。将甘油掺入再生膜中增强柔韧性、降低刚度,并显著改变水相互作用,导致氢键网络的破坏[130]。

#### 4.1.3. 壳聚糖和海藻酸盐:抗菌、湿度缓冲、与相变系统相容

壳聚糖抗菌活性中的重要作用由其物理化学性质发挥,包括阳离子结构、分子量、脱乙酰度和浓度。壳聚糖易于加工:高分子量壳聚糖溶解度较低,而低分子量壳聚糖更易溶且通常更具生物活性和抗菌性。与其他物质的生物相互作用取决于脱乙酰度。粘度受分子量影响,可通过温度和浓度调节。壳聚糖可生物降解,可被溶菌酶分解。它还表现出优异的乳化和水结合性能。这些功能特性取决于其物理化学概况。由于存在反应性化学基团,壳聚糖可容易地功能化或化学改性[130,131]。静电纺丝壳聚糖纳米纤维的主要性能如图7所示。

由于壳聚糖含有大量氨基和羧基,它可与金属形成螯合物。特别是,银(Ag)离子对革兰氏阴性和革兰氏阳性细菌的抗菌活性已得到充分证实。壳聚糖-银复合物用于医学中,例如作为保护涂层、贴片和整形外科产品的一部分,帮助降低术后感染风险[132]。壳聚糖抗菌活性的主要机制取决于其分子量、脱乙酰度、物理化学性质(浓度、pH、接触时间)、结构和反应性羟基。壳聚糖甚至可通过与细菌表面结构相互作用并形成金属螯合物来抑制细菌生长[133]。

壳聚糖可应用于生物医学、食品、化妆品和制药行业,例如作为绷带和组织工程支架,或甚至作为抗癌药物的载体组分。在农业中,它作为植物保护剂和生长刺激剂,也用于废水处理。在包装行业,壳聚糖用于生产可生物降解包装[134,135,136,137]。

海藻酸盐是一种高分子量生物聚合物,能够与多价阳离子(如Ca²⁺)形成凝胶。其粘度强烈依赖于分子量、pH、浓度和组成和溶解度。海藻酸盐在水中溶解良好,但在大多数有机溶剂中不溶(或微溶)。一个值得注意的特性是其粘膜粘附性,允许其粘附于粘膜组织。它能吸收大量水分。由于其优异的生物相容性,海藻酸盐广泛用于药物递送、伤口愈合和组织工程。在食品工业中,它作为增稠剂、稳定剂和胶凝剂。此外,海藻酸盐应用于细胞封装、固定化和微粒、废水处理(金属结合)、生物回收和水凝胶生产[138,139,140,141]。

### 4.2. 具有增强机械和热性能的合成生物聚合物

#### 4.2.1. 聚己内酯(PCL):柔性基质,与PCM或填料良好混合

合成生物聚合物聚己内酯(PCL)不溶于水,但溶于大多数有机溶剂。它非常柔韧,尽管其机械性能强烈依赖于分子量和结晶度。PCL易于成型并与其他聚合物高度相容。由于其柔性链和低熔点,它表现出形状记忆行为。PCL具有生物相容性,其可生物降解性较慢,最多需要约3年,且严重依赖于其内在参数。PCL通过两种常见途径降解:(i)酶促降解(也称为表面侵蚀机制)和(ii)水解降解(也称为本体侵蚀机制)。PCL的本体和表面降解如图8所示。PCL的表面酶侵蚀导致大量质量损失而分子量无显著变化(表示橙色柱尺寸的减少),因为表面处的水解比水扩散到聚合物本体中更快,导致从外向内逐渐变薄(表示图8中橙色强度的增强)。PCL的疏水性相对较高[142,143,144,145]。该聚合物广泛应用于生物医学领域,包括组织工程支架、药物递送系统和长期植入物(如骨支架)。它还应用于水净化和其他工业领域[143,144,145]。

#### 4.2.2. 聚氨酯(PU):弹性、透气、皮肤接触传感器舒适

合成聚合物聚氨酯(PU)表现出良好的伸长率和拉伸强度、优异的耐磨性、高弹性和抗撕裂性。它还具有非常好的热性能,在宽温度范围内工作,提供有效的热绝缘、良好的耐湿性,并表现出优异的抗机械应力、抗疲劳、抗磨损性。然而,该聚合物降解性差,且特别易受紫外线辐射和热降解影响。生物相容性有限,只有某些PU适合生物医学应用。PU提供多种形式的多种加工选项,包括喷涂、发泡、成型。回收仅限于热塑性PU,其在医学应用中的使用通常受到限制[146,147,148,149]。

#### 4.2.3. 聚乳酸(PLA):热绝缘、可生物降解、形成稳定纳米纤维

聚乳酸(PLA)是一种绝缘聚合物,具高度可生物降解性,并可在适当的湿度和温度条件下堆肥。其耐热性取决于结晶度,其机械性能对加工条件敏感。PLA与多种制造方法相容,包括缝纫线、3D打印、热成型和泡沫成型,并应用于生物医学设备[150,151,152]。类似地,PCL由于其生物基和可生物降解性质,是特定应用中传统化石基绝缘体的有吸引力的替代品。然而,PCL通常需要额外加工,如退火或掺入复合材料中,以实现增强的热绝缘性能[153]。

### 4.3. 热调节纺织品的材料比较和性能

#### 4.3.1. 生物相容性与热控制权衡

生物材料可根据其来源和产生途径大致分为三大类。第一类包括直接从天然生物质提取或分离的聚合物,包括淀粉、纤维素、阿拉伯木聚糖和木质素。第二类包括由生物衍生单体化学合成的聚合物,如聚乳酸(PLA)和醋酸纤维素(CA)。第三类包括微生物生物合成的聚合物,特别是聚羟基链烷酸酯(PHA)和各种多糖。从植物材料中提取生物活性化合物的常规步骤示意图表示如图9所示[154]。

聚(己内酯)(PCL)、聚(乙二醇)(PEG)、聚(乳酸)(PLA)、聚(乳酸-乙醇酸共聚物)(PLGA)、壳聚糖和明胶等生物聚合物常用于静电纺丝中,归因于其高生物相容性和在生理环境中可生物降解的能力。然而,这些材料表现出明显不同的机械性能,这可能影响所得静电纺丝纤维的性能和结构稳定性[155]。PLA为结构应用提供强度和刚度,而PEG柔软灵活,支持细胞相互作用但缺乏机械支持。PLGA结合强度和柔韧性,使其多功能,明胶提供细胞相容性但强度低于合成材料。壳聚糖具有低模量但可通过交联增强,PCL有弹性且耐用,可实现持久的纤维。总之,这些材料允许静电纺丝纤维针对不同应用中的特定功能需求进行定制[155]。天然和合成静电纺丝聚合物的优缺点列于表4。天然聚合物提供舒适性和环保性,而合成材料可实现工程化热调节。未来在于将两者优势相结合的混合静电纺丝纺织品,用于可持续、高性能的热调节织物。

#### 4.3.2. 共混策略(如天然/合成杂化物)以获得综合效益

将天然和合成聚合物共混为混合系统,结合了天然材料的环保性和生物相容性与合成聚合物的机械耐久性和可调性能。常见的共混策略包括物理混合、纳米复合形成和同轴静电纺丝。这些混合系统提供增强的机械强度、改进的热导率、更好的相变稳定性和受控的降解,使其高度适用于热能储存、热调节纺织品和其他先进功能材料。一个值得注意的例子是同轴静电纺丝,其生产核-壳纳米纤维:天然聚合物形成壳以确保生物相容性,而合成聚合物或PCM在核中提供热调节[158,159,160]。这些杂化物可制造成适合智能纺织品、可穿戴设备和生物医学应用的轻质、透气结构。它们改进的储热和释放能力支持个人热调节和热能储存系统。通过结合天然聚合物以减少环境影响与合成材料以增强鲁棒性,混合系统创建了为长期使用优化的平衡、高性能材料[161,162,163,164]。

## 5. 使用静电纺丝生物材料的热调节策略

### 5.1. 通过结构设计进行被动热调节

静电纺丝是一种广泛使用且具有成本效益的方法,通过精确控制纤维形态和孔隙率来制造具有定制结构的用于被动热调节的膜。静电纺丝纳米纤维的高比表面积、可调孔隙率和可控形态使其特别适用于个人热管理应用[165,166]。

仿生设计已成为创建有效热调节纺织品的强大策略。例如,已模拟P. roseus的羽毛结构以生产具有冷却性能的PAC@T智能纺织品,这是由于其微纳米纤维和孔隙实现的(见图10)。这种类型的材料表现出透气性、耐用性,并增强机械强度[166]。另一种用于个人热管理以及防火的仿生纺织品受到超白甲虫鳞片的启发。这种材料具有高白度阻燃剂和受生物仿生结构启发的孔结构,引入聚氨酯涂层中。复合纺织品通过刮涂技术制备[167]。

Q. Gao及其同事分析了另一种热调节纺织品——一种具有PI纳米纤维膜和AgNWs涂层涂层的智能双面非织造纺织品。测试结果显示,这种材料具有适合具有个人热管理的智能纺织品的电学和热学性能。与其他AgNW涂层纺织品相比,它显示出更好的红外反射性能。AgNW含量的增加促进高度互连AgNW网络的形成,其特征为异常低的方块电阻(0.23 Ω sq⁻¹)和超过80%的强红外反射率,大大优于传统纺织材料。当双层非织造结构以AgNW涂层表面朝外定向时,表现出有利的被动热调节效应[168]。

同样,Q. Zhang及其同事创造的用于被动热调节的双模式膜-多孔复合材料(见图11)可用于热隔离。由静电纺丝制备的含氟和脂肪族结构的聚酰亚胺纳米纤维膜显示材料适应季节和天气变化的可能性,意味着其具有良好的热隔离性并能在需要时传递热量[169]。聚酰亚胺复合膜表现出分层纳米纤维结构,结合减少固体传导和抑制内部空气对流的微纳孔。其化学组成包括含氟和脂肪族片段,赋予双模式热行为,允许织物根据环境条件保留热量或增强辐射冷却[169,170]。

在另一篇文章中,研究了通过将纤维聚合物基质与SiO₂气凝胶结合通过静电纺丝聚合物基质生产的复合材料。该材料具有受草莓启发的结构以获得更好的热绝缘和吸收性能。发现整合的SiO₂气凝胶有助于实现高孔隙率,通过在结构内捕获空气来增强热绝缘。草莓状复合膜表现出0.028 W/m·K的低热导率,表明优异的热绝缘性能[171]。

通过静电纺丝工艺的二氧化硅/聚酰亚胺复合纳米纤维膜可增强传统聚酰亚胺纳米纤维膜的热绝缘性能。根据T. Zhuo的研究,通过掺杂SiO₂纳米颗粒,实现了膜的低热导率。出现热阻性能,是因为SiO₂ NPs和PI纳米纤维之间热传递的阻力。该结果表明膜可防止火灾热量损坏材料超疏水性[172]。

此外,还发现当PAMPS纳米纤维添加到PU中时,增加了孔隙数量并降低了孔径。这种方法有助于创造防风(热绝缘)材料,因为孔径降低。此外,还指出为增加热绝缘,使用顺序静电纺丝模式生产混合层(包含不同材料以增强性能的结构)优于同时静电纺丝模式[173]。

### 5.2. 水分驱动的热管理

可穿戴设备以及智能纺织品对热舒适性和安全性提出额外要求。它可能限制身体散热并可能导致中等暴露温度下的热应力和不适。有效调节汗液是必要的,因为汗液蒸发需要吸热以稳定体温[174,175,176]。减少或增加的局部汗液损失是多汗症或少汗症的指标,通常有助于中风诊断[177]。

对环保材料日益增长的兴趣已激励工业家开发和将生物聚合物用于各种应用如湿度缓冲。Y. Zhang及其同事创造了一种超疏水自清洁PTFE纳米纤维膜。材料SNM-PTFE通过一步法静电纺丝工艺创造,并通过稳定SiO₂气凝胶凸起来实现超疏水性能。该材料表现出优异的化学稳定性、对高温的显著抵抗力、显著的拒水性和高效的自清洁行为,所有这些均源自其由微纳结构特征组成的工程化表面架构[178]。

G. Parisi及其同事在[179]中检查了包含光响应、可切换表面的静电纺丝聚偏氟乙烯(PVDF)纤维网,其在UV照射下能够从疏水状态过渡到亲水状态,并在热处理后恢复疏水性(见图12)。这些特性有助于在不同大气条件下根据需要从材料中收集和释放湿度[179]。

由甘蔗形成的亲水性甲基纤维素-聚乙烯醇生物聚合物表现出优异的湿度缓冲行为,具有高吸湿性、强保湿性和低蒸气透过性。这些特性源自甲基纤维素、PVA和淀粉中丰富的羟基,这些羟基与水形成氢键。这些类型的材料为基于甘蔗形成各种产品的工业应用提供了可能性[180]。

此外,可通过使用简便的两步静电纺丝实现超强吸湿和快速吸湿。吸湿性能通过浸渍法用LiCl涂覆纳米纤维实现。结构在确定纤维性能中起关键作用。多孔纳米纤维结构显著增加吸湿和传输速率[181]。

为增强热舒适,汗液管理创新如汗液泵送纺织品可被使用。这类材料帮助将水分从皮肤传输到环境。这可通过在双层针织物上排列疏水聚酯线圈和亲水超细纤维聚酯线圈来实现(水分通过疏水层传输到亲水层)。使用超细纤维聚酯有助于实现这种材料的更好传输速度,使传输速度匹配扩散速度[182]。

织物中实现汗液泵送的另一种方法是使用Janus(每侧具有相反属性的膜)[183]。X. He及其同事分析了一种材料——静电纺丝聚氨酯纳米纤维到超亲水性纱布上。如前所述,该材料具有汗液泵送机制,确保穿戴者舒适性,是可穿戴健康监测应用的合适选择[184]。

### 5.3. 用于主动热调节的热响应性静电纺丝材料

相变材料(PCM)的使用已被广泛报道为改善可穿戴应用中热舒适性和减少热应力的有效策略[185]。PCM通过固-液相变作为热储存器吸放热能,该过程与高潜热储存能力相关[148,186]。聚氨酯固-固相变材料(SSPCM)的工作和相变示意图如图13所示。

为使其能够集成到纺织品中,PCM经常被微封装(μPCM),防止相变期间泄漏并允许其集成到纤维系统中[187]。微封装PCM特别适用于纺织应用,因为其聚合物壳在反复热循环和机械变形下保持结构完整性。已经探索了几种制造方法将μPCM集成到纤维中。Ahn等人在[186]中证明使用传统干喷湿淬纺丝技术成功生产μPCM-聚合物纤维复合材料,实现高达80 wt%的PCM负载。虽然高μPCM含量导致机械强度和弹性降低,但μPCM-醋酸纤维素和纤维素纤维的热能储存性能表明对需要被动热调节的智能纺织应用具有强大潜力。工业研究进一步确认了PCM负载纤维的耐用性,报告在100多次加热-冷却循环中的稳定热性能[188]。

尽管有效,但大多数商业可用的PCM源自不可再生来源,引发环境问题。因此,越来越多的关注指向生物基PCM。肉豆蔻酸、棕榈酸和硬脂酸等天然脂肪酸以及十八醇已使用明胶-果胶生物聚合物壳封装,生产具有出色热调节性能且在相变期间无泄漏的可持续PCM复合材料[189]。类似地,使用聚乙烯醇(PVA)作为乳化剂封在可生物降解聚乳酸(PLA)壳中的棕榈酸已证明在改善环境相容性的同时实现有效的热调节[190]。这些发展突出了向可持续和生物相容性PCM系统的日益转变。

静电纺丝已成为将PCM集成到纺织品中的特别多功能平台,由于其高孔隙率、顺应性和与敏感材料的相容性。Huang等人在[191]中开发了掺杂Al₂O₃纳米颗粒的同轴PAN/PEG静电纺丝纤维(见图14),实现稳定的热容量和增强的纤维耐久性。McCord等人在[192]中和Das等人在[102]中的综述进一步证明,核-壳静电纺丝设计显著改善PCM封装效率,特别是当使用PVA或聚氨酯等生物相容性壳时。Zhang等人在[193]中最近的工作报告了一种混合静电纺丝膜,结合PVA、PCM微胶囊和纳米二氧化硅,通过太阳反射率和中红外发射实现热能储存和被动冷却。光交联等交联策略也已显示可增强PCM保留和洗涤耐久性,在反复洗涤循环后保持热功能性[194]。

除被动热缓冲外,智能纺织品越来越多地整合提供实时热反馈的材料。热致变色材料响应温度变化可逆地改变颜色,提供直观且非侵入式的热感应方法。Lee等人在[195]中开发了机织和针织结构中的热致变色电加热纺织品,证明双层机织织物表现出优于针织对应物的加热性能、拉伸强度和更清晰的颜色转变。颜色变化的有效性被发现不仅取决于织物结构,还取决于纱线组成和绝缘性,其中大豆纱线表现出特别显著的热致变色响应。最近的进展已将热致变色功能扩展到静电纺丝系统。Supian等人在[196]中强调了可逆热致变色聚合物纳米复合材料的快速发展,而Ma等人在[197]中证明了含有能够在皮肤相关温度下变色的隐色染料的静电纺丝膜。嵌入PMMA纳米纤维中的商业可用热致变色粉末的更简单方法也已显示出有效的颜色转变[198]。然而,在洗涤牢度和长期耐久性方面仍然存在挑战。柔性粘合剂、溶胶-凝胶涂层和等离子体表面处理等解决方案已显示可改善染料固定和耐水性[199,200]。最近的研究表明,将热致变色材料与PCM结合在复合纤维架构中可同时提供视觉反馈和热调节(见图15)[201,202]。

另一类新兴的热响应性材料是温度敏感水凝胶。基于聚(N-异丙基丙烯酰胺)(PNIPAM)的水凝胶在接近32°C时表现出低临界溶液温度(LCST),使得响应皮肤温度的微小变化能够快速体积收缩或溶胀。Huang等人在[203]中开发了温度响应性自收缩纳米纤维/水凝胶复合材料,使用静电纺丝聚(乳酸-共-三亚甲基碳酸酯)(PLATMC)纳米纤维与甲基丙烯酸明胶水凝胶层结合。尽管水凝胶通常具有弱的机械性能,但双轴取向技术已显示可显著增强其机械强度和耐久性[204]。最近的研究进一步证明基于PNIPAM与壳聚糖、透明质酸或海藻酸盐的共混改善了生物相容性、机械韧性和变形后的自恢复[205,206]。

与被动系统相反,主动加热纺织品通过焦耳加热实现按需热调节。包含MXenes等材料的纳米导电纤维已证明具有出色的电学和光热加热性能,同时在反复机械变形下保持柔韧性和耐久性(见图16)[105,106]。然而,与氧化稳定性和皮肤安全相关的挑战持续存在。已提出使用疏水性生物聚合物的封装策略以保持电导率同时最小化皮肤刺激[207]。重要的是,焦耳加热系统必须在电性能与透气性和舒适性之间取得平衡,特别是当与PCM或水凝胶整合时。尽管取得了重大进展,但在出汗、洗涤、弯曲和长期皮肤接触等现实使用条件下评估这些热响应性系统的比较研究仍然有限。长期生物相容性数据特别稀缺,特别是对于基于纳米材料的系统。因此,当前研究越来越聚焦于在分层或同轴静电纺丝结构内整合PCM、热致变色反馈、水凝胶和导电加热的多模式纺织架构。这些多功能设计为朝向自适应、耐久和可持续智能纺织品的有前景的途径,能够进行动态热调节、用户反馈和增强穿戴者舒适性。

## 6. 热集成多功能传感器系统

智能可穿戴纺织品是能够感知外部刺激并以某种方式响应的织物。外部刺激可以是热的、机械的、化学的、电的、磁的、光学的等[208,209],随着银纳米颗粒[210]、石墨烯[103]或导电聚合物[211]等功能材料的集成,纳米纤维纺织品可感知、响应并与用户的环境或身体相互作用。本综述部分讨论基于静电纺丝导电生物材料的复合材料用于温度传感。静电纺丝是一种允许将纳米颗粒等功能材料整合到纤维中的技术,创造适用于包括热调节在内的各种应用的复合材料。生物材料的四个智能水平为惰性、主动、响应和自主或智能(图17)。惰性生物材料提供生物相容性而不引起不良反应,意味着它们不会在体内引发毒性或有害反应。主动生物材料实现单向、非调节的治疗剂释放。响应性生物材料能够检测特定的环境或生理线索并随后启动治疗释放。自主生物材料不仅能感知这些信号,而且能根据条件变化动态调整其功能特性,从而维持增强或替代治疗模式的递送[212,213]。

在自然界中,生物聚合物以蛋白质、纤维素、淀粉、明胶、壳聚糖(CS)、多糖、胶原蛋白和核酸的形式存在。聚合物本身不能改善热导率[214,215,216]。因此,许多研究人员通过嵌入各种导电添加剂来功能化生物复合材料。

### 6.1. 用于温度传感的导电生物材料基复合材料

体温是人体健康的基本生理指标。尽管身体在正常条件下维持窄的热范围,但即使轻微偏差也常预示疾病的发生或进展。因为温度波动伴随着各种病理状态,连续准确的监测已成为可穿戴生物医学设备开发的核心目标。许多研究已证明可穿戴温度传感器必须结合高灵敏度、机械稳定性和长期可靠性以在现实环境中有效运行[93,217]。为满足这些要求,研究人员越来越多地转向能够生产柔性、皮肤顺应和多功能传感平台的先进材料和制造策略。本章全面概述了支撑现代可穿戴温度传感器的原理、材料和新兴静电纺丝系统。

传感器通过将非电物理量转换为可被处理、量化和解释的电信号来工作。广泛的材料——包括半导体、陶瓷、金属和有机聚合物——可作为传感元件。这些材料的固有特性不仅决定设备的灵敏度和稳定性,还决定其在单一平台内集成多个传感功能的潜力[218]。触觉传感是一个密切相关的领域,涉及对压力、应变、剪切、温度和湿度等各种刺激的空间测量[219]。其中,温度仍然是实时监测生命体征的中心生理参数[220,221]。可穿戴系统中触觉和热感知的融合促使探索柔性、生物相容且能够多模式信号转导的材料。

静电纺丝已成为生产具有高比表面积与体积比、可调孔隙率和优异机械柔韧性的纳米纤维材料的强大技术。当碳纳米管(CNT)或石墨烯等导电纳米材料被掺入生物聚合物基质时,所得复合材料表现出适用于可穿戴传感应用的温度依赖性电行为[222]。这些静电纺丝导电复合材料通过电导率变化响应热变化,实现轻质、透气和皮肤相容的温度传感器。其结构多功能性还允许集成到纺织、贴片和连续生理监测所需的其他顺应格式中。

可穿戴系统中使用的温度传感器通常依赖三种主要机制之一:热敏机制、热阻机制和热电机制(图18)。热敏传感器通过活性层的电阻变化检测温度。这些电阻变化源于传感材料内电荷传输路径的温度诱导修改[223,224,225,226]。热阻传感器基于电阻随温度因材料电导率变化而变化的原理运行。电阻温度系数(TCR)是支配其性能的关键参数。例如,Shin等人在[227]中将NiO纳米颗粒油墨涂覆到PET上制造了基于NiO的热阻传感器,展示了快速响应和长期稳定性在可穿戴热敏电阻中的重要性。热电传感器利用塞贝克效应,其中温度梯度产生电压。这种机制使某些配置中的自供电传感成为可能,使热电器件对长期可穿戴应用具有吸引力[227]。

纳米复合系统由于聚合物基质和纳米填料之间的协同相互作用而提供增强的性能。Ben Shimon和Ya'akobovitz[104]使用碳纳米管(CNT PDMS)复合材料开发了柔性、生物相容的温度传感器。CNT和PDMS之间的热失配在导电网络内引起应变,改变电路径并实现温度依赖性电阻变化。这些传感器在反复机械加载下表现出优异的柔韧性、低重量和高重现性,使其适合皮肤上部署。材料选择在传感器舒适性和耐久性中起关键作用。天然聚合物(纤维素、丝绸、壳聚糖)提供可生物降解性和皮肤友好性。合成聚合物(聚氨酯、聚丙烯腈)提供机械强度、弹性和在恶劣条件下的长期稳定性[228,229]。

静电纺丝和电喷涂是用于功能化热纺织品的通用技术。静电纺丝相变纤维提供几种优势,包括消除封装步骤、可控的纤维尺寸和具有成本效益的加工[230]。除CNT外,石墨烯、氮化硼和氮化硅纳米颗粒以及相变材料是热管理系统中非常受欢迎的组件[231]。PCM广泛用于热管理系统,可按化学性质分类为有机PCM(oPCM)、无机PCM(ioPCM)和共晶PCM(euPCM)。按物理行为分类为固-固、固-液、固-气和液-气PCM[192,232,233,234]。PCM由于其能够在无显著温度变化的情况下调节热流而对智能纺织品特别有吸引力。基于生物聚合物的PCM已整合到医疗产品如绷带中,其中它们吸收和储存身体或外部热量并随后逐渐释放[235]。尽管有优势,PCM面临诸如熔化期间的泄漏和流动性的挑战。静电纺丝提供了一种有效的策略将PCM限制在形状稳定的纳米纤维内,改善可靠性并扩展适用性[192]。掺入CNT或石墨烯等导电填料进一步增强热导率,实现被动散热和主动温度控制[232]。静电纺丝PCM增强纳米纤维及其添加剂的全面概述列于表5。

可穿戴传感器可组织为四大类[218]:单多功能传感器、平面集成传感器、三维组装传感器、堆叠或混合集成传感器。对于温度传感,碳基纳米材料——包括CNT、石墨烯、氮化硼、氮化硅纳米颗粒和碳纳米纤维——由于其优异的电学和热学性能常被集成到静电纺丝生物聚合物基质中[246,247]。堆叠或混合架构在单一分层设备内集成多个传感模式——如温度、压力和湿度。这些系统使用电阻、热电或其他机制实现同时、紧凑和抗干扰的检测。作为堆叠或混合结构多功能温度传感器的例子,Yu X等人在[219]中展示了能够同时检测压力、温度和材料类型的多功能触觉传感器,说明了实时健康监测的分层集成潜力。静电纺丝导电材料,特别是掺入CNT或石墨烯的材料,由于其高电导率和结构可调性而对热管理非常有前景。当集成到堆叠或混合系统中时,它们实现被动散热和主动温度调节,支持下一代可穿戴电子学中的复杂传感任务[218]。

可穿戴温度传感技术已通过材料科学、纳米复合材料和静电纺丝的创新显著进步。导电纳米材料、生物聚合物和相变材料的整合已实现柔性、轻量和多功能传感平台,能够进行实时生理监测。

### 6.2. 同时具备抗菌、透气性和热性能

静电纺丝已成为生产具有受控形态和组成的微纳纤维结构的多功能、成本效益高且高效的技术[213,248,249,250]。由于其薄、轻质的特性,静电纺丝纳米纤维毡可无缝集成到可穿戴系统中,包括纺织面料。这些纳米纤维平台特别适用于传感器应用,实现对运动、温度和湿度等物理参数的检测[73]。这种基础能力使静电纺丝成为工程化结合热调节、透气性和抗菌性能的多功能材料的理想方法。

富含功能性添加剂的生物聚合物为同时展现热调节和抗菌性能的材料提供了有前景的途径。这种多功能性通常通过掺入相变材料(PCM)以管理热流和抗菌剂——如金属纳米颗粒或生物活性化合物——以抑制细菌生长来实现。这种双功能设计能够开发适用于医疗、环境和可穿戴应用的高级智能纺织品。

多项研究已证明将PCM和导电或增强添加剂集成到静电纺丝纤维中的有效性。Wu等人在[244]中通过绿色静电纺丝制造了PEG/PVA复合膜,实现出色的柔韧性、透气性和热调节。碳纳米管(CNT)的掺入显著增强了机械强度,并在仅1.5 wt%的CNT负载下将热导率提高了40.4%。膜表现出实用的相变温度范围(26.9-38.9°C)和高潜热值,确认了其对可穿戴热管理的适用性。类似地,Qin等人在[158]中使用同轴静电纺丝开发了抗菌热调节纺织品,其中PAN/姜黄素形成鞘,n-十八烷作为PCM核。这些材料展示了在服装、食品保鲜和生物医学产品中的应用的强大潜力。Wang等人在[159]中通过合成具有出色抗菌活性的基于姜黄素的聚氨酯(Cur-PU)膜并系统表征其热学、机械和生物相容性性能进一步推进了该领域。姜黄素已被广泛探索作为静电纺丝系统中的天然抗菌剂。Leng等人在[251]中将姜黄素封装在PCEC纳米颗粒中并将其掺入PVA/胶原蛋白复合膜,展示了强大的抗菌性能。额外的研究已生产姜黄素负载的PLA/PVP纳米纤维[252]和壳聚糖-胶原蛋白纳米纤维毡[253],两者均显示出伤口愈合和生物医学应用的显著潜力。Lin等人在[254]中制造了有效减少细菌粘附(特别是针对金黄色葡萄球菌)的亲水性HCP和HCPG纳米纤维膜。同样,Khanzada等人在[255]中开发了具有固有抗菌活性的芦荟/PVA纳米纤维,突出了天然生物活性化合物在静电纺丝系统中的多功能性。

纳米颗粒也已用于赋予静电纺丝膜多功能性。Costa等人在[256]中生产了用Ag、TiO₂和MgO纳米颗粒功能化的可生物降解PCL膜,实现高过滤效率和强大抗菌效果。值得注意的是,将PCL/MgO膜集成在棉层内改善了热舒适,展示了纳米颗粒整合的协同益处(见图19)。Peng等人在[27]中通过开发包含Ag纳米线的柔性、透气、可生物降解纳米纤维基摩擦电系统将这些概念扩展到电子皮肤(e-skin)应用。这项工作说明了多功能纳米纤维在下一代可穿戴电子学中的潜力。

进一步创新聚焦于增强UV保护、防水和透气性以及热调节。Wang等人在[257]中通过在同轴静电纺丝十八烷/PAN纤维中使用ZnO纳米颗粒创造了抗UV、热调节膜。额外的工作证明了PEG/PA6/TiO₂复合材料中强大的热能储存[247,257]。Yi等人在[258]中生产了阻挡液态水同时允许汗蒸气逸出的防水透气CNT负载膜,改善穿戴者舒适性。Xu等人在[259]中开发了结合n-二十烷/PVDF/Cu₇S₄膜与静电纺丝PAN层的双模式织物,实现热管理和透气性(见图20)。Feng等人在[160]中制造了具有温度响应性湿气渗透性的同轴PU/PEG膜,实现汗液蒸发和热缓冲。Zhang等人在[260]中生产了具有出色防水性(见图21)和透气性的PBSe/PO3G-BPU膜,进一步扩展了高性能可穿戴材料的范围。Qiao等人在[261]中通过离心静电纺丝制备了PEG/PEO/CNT相变复合纤维,展示了出色的柔韧性、热导率和储能能力(见图22)。这些结果突出了PCM集成纳米纤维对柔性可穿戴热管理的强大潜力。

总体而言,这些研究突出了静电纺丝领域的快速进步。