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Design of a supersoft, ultra-stretchable, and 3D printable hydrogel electrical bioadhesive interface for electromyography monitoring 设计用于肌电图监测的超软、超拉伸和可 3D 打印的水凝胶电生物粘合界面
Pub Date : 2024-11-10 DOI: 10.1016/j.supmat.2024.100079
Junxiao Qiu , Hude Ma , Mutian Yao , Manting Song , Liping Zhang , Jingkun Xu , Ximei Liu , Baoyang Lu
Electromyography (EMG) monitoring has been extensively employed for critical applications in medicine, sports science, and rehabilitation. However, the mechanical mismatch between conventional EMG electrodes and the skin can lead to electrode detachment upon significant skin deformation. To address this limitation, we develop a PEDOT:PSS-based hydrogel electrical bioadhesive interface (EBI) that incorporates molecular doping and robust adhesion strategies to achieve excellent mechanical compatibility with biological tissues. This hydrogel EBI is fabricated using direct writing of printable inks followed by in-situ thermal initiation, enabling the creation of customizable patterns with high shape fidelity. The resultant 3D-printed PEDOT:PSS-based hydrogel EBI exhibits supersoft properties (Young's modulus 5–8.5 kPa), ultra-stretchability (1175 % strain), robust adhesion (>133 kPa), and outstanding electrochemical performance (CIC reduction by 0.45 % over 1,000,000 cycles). Additionally, we further develop a PEDOT:PSS-based hydrogel electrode specifically for stable EMG signal recording. This electrode outperforms superior signal-to-noise ratio (SNR) performance compared to commercial electrodes in EMG monitoring.
肌电图(EMG)监测已被广泛应用于医学、运动科学和康复领域的关键应用。然而,传统肌电图电极与皮肤之间的机械不匹配会导致电极在皮肤发生明显变形时脱落。为了解决这一局限性,我们开发了一种基于 PEDOT:PSS 的水凝胶生物电粘附界面(EBI),它结合了分子掺杂和强大的粘附策略,可与生物组织实现出色的机械兼容性。这种水凝胶 EBI 是通过直接写入可打印墨水,然后进行原位热引发来制造的,从而能够创建具有高形状保真度的可定制图案。最终制成的基于 PEDOT:PSS 的三维打印水凝胶 EBI 具有超软特性(杨氏模量 5-8.5 kPa)、超强拉伸性(1175 % 应变)、强大的粘附性(133 kPa)和出色的电化学性能(100 万次循环后 CIC 降低 0.45 %)。此外,我们还进一步开发了一种基于 PEDOT:PSS 的水凝胶电极,专门用于记录稳定的肌电信号。在 EMG 监测中,该电极的信噪比 (SNR) 性能优于商用电极。
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引用次数: 0
High-sensitivity and damage redundant detection capable gel-state [BMIM][BF4] electronic skin for aerospace applications 用于航空航天应用的高灵敏度和损伤冗余检测能力凝胶态 [BMIM][BF4]电子蒙皮
Pub Date : 2024-11-09 DOI: 10.1016/j.supmat.2024.100077
Kunpeng Ma , Hongyu Yi , Yifan Gao , Yang Cao , Kongyu Ge , Ting Kuang , Hongjun Ji , Mingyu Li , Huanhuan Feng
Electronic skin (e-skin) holds significant potential for applications in robotics, Internet-of-things, and health monitoring. However, conventional e-skins often exhibit decreased sensitivity and delayed response in ultra-low temperature environments due to the freezing of conductive materials. Moreover, an increased brittleness can cause substrate damage, limiting their application in cryogenic conditions. To address existing challenges, an ionic liquid [BMIM][BF4] is cross-linked with N,N'-Bis(2-hydroxyethyl)oxamide to form an ionic gel for this study. The gel exhibits excellent electrical performance at −71 °C, significantly expanding the operating temperature range of e-skins. Additionally, gelation decreases resistive drift and leakage inherent to ionic liquids. The prepared sensing units demonstrate high sensitivity to pressure loading across an ultra-wide temperature range of −50–50 °C, with linear sensing within the range of 48–32,000 Pa and a rapid response time of 0.05 s. Integration of the units into large-scaled e-skin enables precise recognition of static and dynamic pressure loads in ultra-low temperature environments (−50 °C). Furthermore, a space glove model assembled using the sensing units achieves accurate recognition of hand gestures in extreme conditions. The sensing units retain over 60 % of their pressure response even when damaged, and demonstrate resilience to environmental factors including low temperatures and vacuum conditions. Along with exceptional performance and environmental resilience under harsh conditions, the gel-state [BMIM][BF4] e-skin shows great potential in deep space exploration, polar expeditions, and other challenging environments.
电子皮肤(e-skin)在机器人、物联网和健康监测领域的应用潜力巨大。然而,由于导电材料的冻结,传统的电子皮肤在超低温环境中通常会表现出灵敏度降低和响应延迟的问题。此外,脆性增加会导致基板损坏,从而限制了其在低温条件下的应用。为应对现有挑战,本研究采用离子液体 [BMIM][BF4]与 N,N'-双(2-羟乙基)草酰胺交联形成离子凝胶。这种凝胶在-71 °C时表现出优异的电气性能,极大地扩展了电子皮肤的工作温度范围。此外,凝胶化还能减少离子液体固有的电阻漂移和泄漏。所制备的传感单元在-50-50 °C的超宽温度范围内表现出对压力负荷的高灵敏度,在48-32,000帕范围内具有线性传感能力,响应时间仅为0.05秒。将这些单元集成到大型电子皮肤中,可在超低温环境(-50 °C)下精确识别静态和动态压力负荷。此外,使用传感单元组装的太空手套模型可在极端条件下准确识别手势。即使在损坏的情况下,传感单元仍能保持 60% 以上的压力响应,并能适应包括低温和真空条件在内的各种环境因素。凝胶态[BMIM][BF4]电子皮肤在恶劣条件下具有卓越的性能和环境适应能力,在深空探测、极地探险和其他具有挑战性的环境中显示出巨大的潜力。
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引用次数: 0
Poly[2]catenanes-based hydrogels prepared by hydroxyl-yne click chemistry 通过羟基炔点击化学制备聚[2]卡替烷基水凝胶
Pub Date : 2024-11-08 DOI: 10.1016/j.supmat.2024.100076
Jinsa Li, Ziqing Hu, Hanwei Zhang, Xiaofan Ji
Polycatenanes as a typical type of mechanically interlocked polymers (MIP), composing of some interlocked cycles through topology bonding has been extensively investigated. However, the comprehension regarding polycatenanes-based materials still lags behind other kinds of MIP. Therein, polyrotaxanes and slide-ring gels were able to fabricate in water to produce hydrogel. Hydrogel materials play an important role in tissue engineering, cell culture, flexible devices and other fields because of their softness and good biocompatibility. However, there was rare reports concerning polycatenanes-based hydrogels. Here, we prepared poly[2]catenanes-based hydrogel G12 incorporating hydrogen bonds through hydroxyl‑yne click reactions from M1 and M2. Comparative tests of substituting M2 with M3 involving mechanical bonds only, hydrophobic alkyl diols M4 and hydrophilic ethylene glycol M5 demonstrated that the mechanical bonds and hydrogen bonds could significantly enhance the hydrogel properties. Besides, temperature and acid responsiveness of G12 was elucidated.
聚卡丁烷作为一种典型的机械互锁聚合物(MIP),通过拓扑键合组成一些互锁循环,已被广泛研究。然而,人们对聚卡特烯烷基材料的理解仍然落后于其他类型的 MIP。因此,聚卡他烷和滑环凝胶能够在水中制造出水凝胶。水凝胶材料因其柔软性和良好的生物相容性,在组织工程、细胞培养、柔性设备等领域发挥着重要作用。然而,有关聚卡他烯烃基水凝胶的报道却很少见。在此,我们以 M1 和 M2 为原料,通过羟炔点击反应制备了含有氢键的聚[2]卡替烷基水凝胶 G12。用仅涉及机械键的 M3、疏水性烷基二元醇 M4 和亲水性乙二醇 M5 替代 M2 进行的对比试验表明,机械键和氢键能显著提高水凝胶的性能。此外,还阐明了 G12 对温度和酸的响应性。
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引用次数: 0
Dynamic covalent epoxy network of hyperbranched-synergistic-supramolecular: Catalyst-free reprocessing, and application in carbon fiber composites recycling 超支化-协同-超分子的动态共价环氧网络:无催化剂再加工及在碳纤维复合材料回收中的应用
Pub Date : 2024-10-30 DOI: 10.1016/j.supmat.2024.100078
Yueran He, Yanlin Liu, Zhen Yu, Xiangyu Zhou, Jin Zhu, Zhaobin Tang
Plastic recycling, especially the recycling of thermosets, is a crucial step towards improving waste management and achieving economic recycling. Here, a method utilizing non-covalent supramolecular interactions and synergistic hyperbranched structures is reported to endow transesterification-based thermosetting materials with recyclability in the absence of a catalyst. A hyperbranched epoxy resin curing agent (HPCA) containing amide bonds, terminated by amine and ester, was designed and synthesized, and further cured with bisphenol A epoxy resin. The hyperbranched topological structure and its abundant amide bonds contribute to the formation of a dense hydrogen bonding network, enhancing the reprocessability, thermal, and mechanical properties of the material. As a result, the resin can be reprocessed by hot pressing at 190 °C and 10 MPa for 40 min without catalyst. Moreover, amide and ester bonds endow resin materials with excellent degradation performance in alkaline solutions, laying the foundation for the recycling and utilization of carbon fibers in composite materials.
塑料回收,尤其是热固性塑料的回收,是改善废物管理和实现经济回收的关键一步。本文报告了一种利用非共价超分子相互作用和协同超支化结构的方法,在没有催化剂的情况下赋予基于酯交换反应的热固性材料以可回收性。研究人员设计并合成了一种超支化环氧树脂固化剂(HPCA),该固化剂含有酰胺键,以胺和酯为端基,并与双酚 A 环氧树脂进一步固化。超支化拓扑结构及其丰富的酰胺键有助于形成致密的氢键网络,从而提高了材料的再加工性、热性能和机械性能。因此,这种树脂可以在不使用催化剂的情况下,通过在 190 °C 和 10 兆帕下热压 40 分钟进行再加工。此外,酰胺键和酯键赋予了树脂材料在碱性溶液中优异的降解性能,为碳纤维在复合材料中的回收和利用奠定了基础。
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引用次数: 0
Optical absorption of supramolecular aggregates of vanadyl etioporphyrin-III in solutions and thin films 溶液和薄膜中香草醛基乙二卟啉-III 超分子聚合体的光学吸收
Pub Date : 2024-10-10 DOI: 10.1016/j.supmat.2024.100075
Andrey I. Koptyaev , Ekaterina D. Rychikhina , Yury A. Zhabanov , Vlad V. Travkin , Georgy L. Pakhomov
Relative abundance of vanadyl etio-porphyrin-III, VO-EtioP-III, a typical geoporphyrin, reaches its maximum in solid fossil fuels (coals). This determines the interest in studying supramolecular structure and solid-state properties of this compound. Unlike planar etio-type porphyrins, the visible absorption spectra of VO-EtioP-III undergo significant transformation in transition from a solution to solid films, which is associated with formation of supramolecular aggregates. In this work, we compare the spectra of VO-EtioP-III films deposited by thermal evaporation of powder in vacuum (VTE) or by spin-coating of dissolved compound (SC) to prove that they are similar to those observed for binary solutions in which adding water to methanol also initiates aggregation. The absorption spectra of VTE-films are very sensitive to the film thickness and deposition conditions. The spectral studies are supplemented with analysis of the microscopic morphology and conducting properties of the films. While the photoconductivity of solution-processed VO-EtioP-III films suffers due to the inhomogeneity of their structure, the VTE-films behave as good photoconductors with a lateral current response to sunlight up to 105.
钒基乙撑卟啉-III(VO-EtioP-III)是一种典型的地卟啉,其相对丰度在固体化石燃料(煤)中达到最高。这就决定了研究这种化合物的超分子结构和固态特性的兴趣。与平面蚀变型卟啉不同,VO-EtioP-III 的可见吸收光谱在从溶液转变为固态薄膜的过程中会发生显著变化,这与超分子聚集体的形成有关。在这项工作中,我们比较了通过真空中粉末热蒸发(VTE)或溶解化合物旋涂(SC)沉积的 VO-EtioP-III 薄膜的光谱,证明它们与二元溶液中观察到的光谱相似,在二元溶液中,向甲醇中加水也会引发聚集。VTE 薄膜的吸收光谱对薄膜厚度和沉积条件非常敏感。光谱研究还辅以对薄膜微观形态和导电特性的分析。溶液加工的 VO-EtioP-III 薄膜的光电导性因其结构的不均匀性而受到影响,而 VTE 薄膜则表现为良好的光电导体,对阳光的横向电流响应高达 105。
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引用次数: 0
Erratum for previously published articles 对以前发表的文章的勘误
Pub Date : 2024-07-17 DOI: 10.1016/j.supmat.2024.100074
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引用次数: 0
Versatile preparation of jellyfish-inspired color transition hydrogels via polymerization induced supramolecular geletion (PISG) 通过聚合诱导超分子发生(PISG)多功能制备水母启发的颜色转换水凝胶
Pub Date : 2024-05-10 DOI: 10.1016/j.supmat.2024.100072
Xiaowei Wang , Boyu Wu , Chen He , Yifan Bai , Chao Gao , Anchao Feng , San H. Thang

Supramolecular hydrogels based on host–guest interactions constitute a class of intriguing soft matter and have attracted great attention due to their unique properties, etc. In this study, we successfully synthesized 4-methylene-7-diethylaminocoumarin methacrylate (DEACMMA) monomer and carried out reversible addition-fragmentation chain transfer (RAFT) polymerization using methylated β-cyclodextrin via a host-guest encapsulation mechanism. This process led to the formation of ternary copolymer hydrogel supramolecular photoresponsive hydrogels through polymerization induced supramolecular gelation (PISG). The encapsulation of coumarin monomers by methylated cyclodextrins was confirmed using 2D ROESY NMR and fluorescence spectroscopy. We have carefully analyzed the microstructure of these supramolecular hydrogels by rheological profiles and scanning electron microscopy (SEM). Stimulated by UV light, the copolymers transition from non-luminescence to a bright fluorescent blue color, which is reminiscent of the self-transforming colors observed in jellyfish. The development of photostimuli-responsive hydrogels based on methylated β-cyclodextrin-coated coumarin esters opens new avenues in the fields of smart materials and clinical medicine.

基于主客体相互作用的超分子水凝胶是一类引人入胜的软物质,因其独特的性质等而备受关注。在这项研究中,我们成功合成了 4-亚甲基-7-二乙氨基香豆素甲基丙烯酸酯(DEACMMA)单体,并利用甲基化的 β-环糊精通过主客体包封机制进行了可逆加成-断裂链转移(RAFT)聚合。这一过程通过聚合诱导超分子凝胶化(PISG)形成了三元共聚物水凝胶超分子光致伸缩性水凝胶。利用二维 ROESY NMR 和荧光光谱证实了甲基化环糊精对香豆素单体的包裹作用。我们通过流变曲线和扫描电子显微镜(SEM)仔细分析了这些超分子水凝胶的微观结构。在紫外线的刺激下,共聚物从不发光转变为明亮的荧光蓝色,这让人联想到在水母中观察到的自转化颜色。基于甲基化β-环糊精包覆香豆素酯的光刺激响应水凝胶的开发为智能材料和临床医学领域开辟了新的途径。
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引用次数: 0
Phosphatidylserine-targeting bis(zinc-dipicolylamine) farnesol inhibits ATP production in cancer cells to overcome multidrug resistance 磷脂酰丝氨酸靶向双(锌-二羟基胺)法尼醇抑制癌细胞产生 ATP,克服多药耐药性
Pub Date : 2024-04-24 DOI: 10.1016/j.supmat.2024.100068
Wei Huang , Xuan Nie , Xiao-Hong Zhou , Lei Qiao , Hong-Jie Gao , Jing Zang , Long-Kang Yu , Long-Hai Wang , Ye-Zi You

Multidrug resistance significantly impedes the efficacy of cancer chemotherapy. Resistance often arises from the reduced cellular uptake of chemotherapeutic drugs, a process crucial for their cytotoxic effects. This reduction is frequently due to transmembrane efflux pumps powered by ATP from mitochondria and the cytoplasmic matrix, leading to lower intracellular concentrations of these drugs. This study introduces an amphiphilic molecule, bis(zinc-dipicolylamine) farnesol (Bis-ZnDPA), which targets phosphatidylserine (PS) – a negatively charged phospholipid prominently displayed on the outer leaflet of cancer cell plasma membranes. Integrating the hydrophobic segment of Bis-ZnDPA into the plasma membrane disrupts its integrity, potentially leading to hole formation and facilitating the uptake of chemotherapeutic drugs. Furthermore, the binding of Bis-ZnDPA to phosphatidylserine inhibits ATP production caused by Ca2+ influx and deregulation of the phosphoinositide 3-kinase/protein kinase B (PI3K/AKT) signaling pathway, reducing the efflux of drugs from cells. The results indicate the potent synergistic effect of Bis-ZnDPA with chemotherapeutic agents, suggesting that targeting PS is a viable strategy for overcoming multidrug resistance in cancer chemotherapy.

多药耐药性严重影响了癌症化疗的疗效。产生耐药性的原因通常是细胞对化疗药物的吸收减少,而这一过程对化疗药物的细胞毒性作用至关重要。这种减少往往是由于线粒体和细胞质基质的 ATP 驱动跨膜外排泵,导致这些药物的细胞内浓度降低。本研究引入了一种两亲分子--双(锌-二二乙醇胺)法尼索尔(Bis-ZnDPA),它以磷脂酰丝氨酸(PS)为靶标--PS 是一种带负电荷的磷脂,在癌细胞质膜的外叶上表现突出。将 Bis-ZnDPA 的疏水片段整合到质膜中会破坏质膜的完整性,从而可能导致孔洞的形成并促进化疗药物的吸收。此外,Bis-ZnDPA 与磷脂酰丝氨酸的结合还能抑制因 Ca2+ 流入和磷脂酰肌醇 3 激酶/蛋白激酶 B(PI3K/AKT)信号通路失调而产生的 ATP,从而减少药物从细胞中的外流。研究结果表明,Bis-ZnDPA 与化疗药物有很强的协同作用,这表明以 PS 为靶点是克服癌症化疗中多药耐药性的一种可行策略。
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引用次数: 0
Stretchable and self-healable lithium-ion batteries with all-in-one configuration 一体化配置的可拉伸、自修复锂离子电池
Pub Date : 2024-04-22 DOI: 10.1016/j.supmat.2024.100073
Zhen Li, Yue Guo, Xiaokong Liu

Stretchable lithium-ion batteries (LIBs) are highly desirable to serve as the power sources of stretchable and wearable electronic devices. Furthermore, endowing stretchable LIBs with self-healability can prolong their life-time and enhance their reliability. However, previously reported self-healable LIBs were flexible rather than stretchable, while the stretchable LIBs were unable to self-heal. Herein, we present a novel strategy to fabricate stretchable and self-healable LIBs with all-in-one configuration, by exploiting dynamic covalent polymers as both the electrolyte and the binder of electrodes. The developed polymer electrolyte exhibits a room-temperature ionic conductivity as high as 3.6 × 10−4 S cm−1 and possesses an elongation-at-break of 250 ± 30 %. Moreover, the stretchable electrolyte is highly resilient and its ionic conductivity shows minimal changes at different strains. The electrolyte exhibits an autonomous self-healing property at room temperature, making the cut sample easily recover its original performance. Importantly, the electrolyte and electrodes can be fused together at the interface to construct a healable LIB with all-in-one configuration, through the exchange of the dynamic imine bonds that exist in both the electrolyte and electrodes. As a result, the as-developed LIB possesses an elongation-at-break of 220 ± 20 % and can supply power in the course of stretching and releasing. Furthermore, the cut and then healed LIB can still deliver an average discharge capacity of 126.4 mAh g 1 and steadily provide power for LED. This work offers a new avenue for the development of stretchable and self-healable LIBs for the stretchable and wearable electronic devices.

可拉伸锂离子电池(LIBs)非常适合作为可拉伸和可穿戴电子设备的电源。此外,赋予可拉伸锂离子电池自愈能力可延长其使用寿命并提高其可靠性。然而,以前报道的可自愈锂离子电池是柔性的而不是可拉伸的,而可拉伸锂离子电池则无法自愈。在此,我们提出了一种新策略,利用动态共价聚合物作为电极的电解质和粘合剂,制造出具有一体化配置的可拉伸和自修复 LIB。所开发的聚合物电解质具有高达 3.6 × 10-4 S cm-1 的室温离子电导率和 250 ± 30 % 的断裂伸长率。此外,这种可拉伸电解质还具有很强的弹性,其离子电导率在不同应变下的变化极小。电解质在室温下具有自主自愈特性,使切割后的样品很容易恢复其原有性能。重要的是,通过交换电解质和电极中存在的动态亚胺键,电解质和电极可在界面处融合在一起,从而构建出具有一体化结构的可愈合 LIB。因此,所开发的 LIB 具有 220 ± 20 % 的断裂伸长率,并能在拉伸和释放过程中供电。此外,切割后愈合的 LIB 仍能提供 126.4 mAh g - 1 的平均放电容量,并能稳定地为 LED 供电。这项研究为开发用于可拉伸和可穿戴电子设备的可拉伸和自愈合 LIB 提供了一条新途径。
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引用次数: 0
Dynamic covalent bond-based materials: From construction to biomedical applications 动态共价键基材料:从构造到生物医学应用
Pub Date : 2024-04-18 DOI: 10.1016/j.supmat.2024.100070
Banruo Xianyu, Huaping Xu

Dynamic covalent bonds (DCBs) have received significant interest due to their unique reversibility and stimuli-responsiveness. The introduction of DCBs provides materials with self-healing and controllable load and release properties, which result in the emergence of widespread applications in biomedical disciplines. In this minireview, we first introduce the chemistry nature and reaction characteristics of different types of DCBs followed by discussing the design strategies of DCB materials. Finally, we summarize the latest progress about the biomedical applications, including drug delivery, enzyme regulation, molecule recognition and detection, wound healing, biosensing and cell culture, and propose some challenges in the future development of DCB biomaterials.

动态共价键(DCB)因其独特的可逆性和刺激响应性而备受关注。动态共价键的引入为材料提供了自愈合、可控载荷和释放特性,因而在生物医学领域得到了广泛的应用。在本综述中,我们首先介绍了不同类型 DCB 的化学性质和反应特点,然后讨论了 DCB 材料的设计策略。最后,我们总结了药物递送、酶调控、分子识别与检测、伤口愈合、生物传感和细胞培养等生物医学应用的最新进展,并提出了 DCB 生物材料未来发展的一些挑战。
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引用次数: 0
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Supramolecular Materials
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