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Advanced Photoporation: Micro-Nanostructures for Size-Specific Highly Efficient Biomolecular Delivery 先进的光穿孔:微纳米结构用于特定尺寸的高效生物分子传递
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202511843
Ashwini Surendra Shinde, Gayathri R., Nandhini Balasubramaniam, Athira Prasad, Donia Dominic, Moeto Nagai, Srabani Kar, Tuhin Subhra Santra
With the growing demand for precise and minimally invasive intracellular delivery, photoporation has emerged as a powerful non-viral strategy. This review presents a comprehensive analysis of photoporation as a versatile intracellular delivery platform, with particular emphasis on the role of micro- and nanostructured materials in enabling efficient transport across a wide range of biomolecular sizes. A key novelty of this review is its size-centric organizational framework, which systematically classifies photoporation strategies based on biomolecular cargo size, from small molecules and nucleic acids to ultralarge assemblies and bacteria, rather than conventional material- or laser-based categorizations. The review examines laser-induced mechanisms responsible for transient membrane permeabilization and highlights critical material parameters, including composition, size, shape, surface charge, and optical properties, that govern light–matter interactions and delivery efficiency. Comparative evaluation of micro- and nanostructured materials across different size regimes provides a practical framework for rational material selection and platform design. In addition, key challenges related to delivery precision, biocompatibility, scalability, and clinical translation are critically discussed alongside emerging optimization strategies. By integrating mechanistic insights with translational considerations, this review provides a structured roadmap for developing safe, efficient, and size-adaptive photoporation platforms for biological research and therapeutic applications.
随着对精确和微创细胞内递送的需求不断增长,光穿孔已成为一种强大的非病毒策略。这篇综述全面分析了光穿孔作为一种多功能的细胞内递送平台,特别强调了微纳米结构材料在实现广泛生物分子尺寸的有效运输中的作用。该综述的一个关键新颖之处在于其以尺寸为中心的组织框架,该框架基于生物分子货物大小(从小分子和核酸到超大组装体和细菌)系统地对光穿孔策略进行分类,而不是传统的基于材料或激光的分类。这篇综述研究了激光诱导瞬态膜渗透的机制,并强调了关键的材料参数,包括组成、尺寸、形状、表面电荷和光学性质,这些参数决定了光与物质的相互作用和传递效率。对不同尺寸的微纳米结构材料进行比较评估,为合理的材料选择和平台设计提供了一个实用的框架。此外,与递送精度、生物相容性、可扩展性和临床翻译相关的关键挑战与新兴的优化策略一起进行了批判性的讨论。通过将机制见解与翻译考虑相结合,本综述为开发用于生物学研究和治疗应用的安全,高效和尺寸自适应的光穿孔平台提供了结构化的路线图。
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引用次数: 0
Biocompatible Glue-Enabled Drug Localization and Mechanical Reinforcement of Lyophilized Microneedle Systems 冻干微针系统的生物相容性胶合药物定位和机械强化
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202512379
Seon Tae Kim, Eun Ji Kim, Yun Ji Jung, Jaehun Han, Minho Yang, Jong Seob Choi, Jae Hwan Jung
Clinical translation of dissolving microneedles (DMNs) is hindered by critical challenges such as drug diffusion into the backing layer during fabrication and slow dissolution rates, which compromise dose accuracy, delivery efficiency, and user compliance. Although lyophilization has emerged as a strategy to accelerate microneedle dissolution by inducing a porous, amorphous microstructure, the resulting mechanical fragility limits effective skin insertion. To overcome these issues, we developed a Lyophilized Microneedle System using Biocompatible Glue (LMS-BG), wherein a lyophilized, drug-loaded microneedle tip is coupled with a prefabricated backing via a biodegradable, ethanol-based glue (BC glue). This system enables tip-localized drug confinement, rapid dissolution, and mechanical reinforcement through partial interpenetration of BC glue into the porous tip. Using lidocaine hydrochloride (LiH) as a model drug, LMS-BG exhibited an 11-fold faster dissolution rate than conventional DMNs, with over 96% of the drug retained in the tip and a transdermal delivery efficiency exceeding 90% within 2 min. In vivo studies in rats confirmed superior local anesthetic efficacy and biocompatibility of LMS-BG compared to commercial lidocaine gel. Furthermore, the LMS-BG fabrication method was successfully extended to various microneedle platforms using soluble polymers, hydrogels, and PLGA nanoparticles, demonstrating its scalability and versatility. Overall, the LMS-BG platform addresses key translational barriers of conventional DMNs and presents a modular strategy for rapid, efficient, and clinically viable transdermal drug delivery.
溶解性微针(DMNs)的临床转化受到一些关键挑战的阻碍,例如在制造过程中药物扩散到衬底层和溶解速度缓慢,从而影响剂量准确性、给药效率和用户依从性。虽然冻干已成为一种通过诱导多孔、无定形微观结构来加速微针溶解的策略,但由此产生的机械脆弱性限制了有效的皮肤插入。为了克服这些问题,我们开发了一种使用生物相容性胶(LMS-BG)的冻干微针系统,其中冻干的载药微针尖端通过可生物降解的乙醇基胶(BC胶)与预制的背衬相结合。该系统通过BC胶在多孔尖端的部分渗透,实现了尖端局部药物约束、快速溶解和机械加固。以盐酸利多卡因(LiH)为模型药物,LMS-BG的溶出速度比传统DMNs快11倍,药物残留在针尖超过96%,2 min内透皮给药效率超过90%。大鼠体内研究证实LMS-BG比市售利多卡因凝胶具有更好的局部麻醉效果和生物相容性。此外,LMS-BG制造方法已成功扩展到使用可溶性聚合物、水凝胶和PLGA纳米颗粒的各种微针平台,证明了其可扩展性和通用性。总体而言,LMS-BG平台解决了传统dmn的关键翻译障碍,并提出了快速、高效和临床可行的透皮给药的模块化策略。
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引用次数: 0
A Metal-Free Phthalocyanine Additive for Defect Passivation and Processing Tolerance in High-Efficiency Perovskite Solar Cells 一种用于高效钙钛矿太阳能电池缺陷钝化和加工耐受的无金属酞菁添加剂
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202512151
Chuan-Hung Huang, Zhong-En Shi, Yi-Han Zheng, Yu-Cheng Chen, Chih-Ping Chen, Chih-Hsin Chen
Metal-free phthalocyanines (Pcs) have rarely been explored in perovskite solar cells (PSCs) due to poor solubility and limited processability. Here, we introduce CG-0, a fully substituted metal-free Pc bearing peripheral chlorine atoms and non-peripheral ethoxy chains that confer exceptional solubility, near-infrared absorption, and photochemical robustness. As an additive in wide-bandgap (WBG) PSCs, CG-0 promotes high-quality crystallization, passivates defects, and suppresses non-radiative recombination. Strikingly, ultra-high doping levels (1.75 mm) are tolerated without performance loss, yielding a PCE of 20.41% with an FF of 83.2% under AM 1.5G, and a PCE of 38.60% with an FF of 82.2% under 1000 lux white LED. At high loadings, CG-0 also imparts a vivid, tunable film color, enabling aesthetic and multifunctional device designs. This work establishes a rational molecular design paradigm in which solubility-driven processability, multi-point defect passivation, and interfacial stabilization are integrated into a single additive. The approach not only delivers record WBG PSC efficiencies under both solar and indoor light, but also breaks the constraint of fixed device appearance, opening avenues toward efficient, color-adaptive perovskite photovoltaics.
由于钙钛矿太阳能电池(PSCs)溶解度差和加工能力有限,无金属酞菁(Pcs)在钙钛矿太阳能电池(PSCs)中很少被研究。在这里,我们介绍CG-0,一种完全取代的不含金属的Pc,具有外周氯原子和非外周乙氧基链,具有优异的溶解度,近红外吸收和光化学稳健性。作为宽带隙(WBG) psc的添加剂,CG-0可以促进高质量的结晶,钝化缺陷,抑制非辐射复合。引人注目的是,在没有性能损失的情况下,可以容忍超高掺杂水平(1.75 mm),在AM 1.5G下,PCE为20.41%,FF为83.2%,在1000勒克斯白光LED下,PCE为38.60%,FF为82.2%。在高负载下,CG-0还赋予生动,可调的薄膜颜色,使美学和多功能设备设计成为可能。这项工作建立了一个合理的分子设计范例,其中溶解度驱动的可加工性、多点缺陷钝化和界面稳定被集成到一个单一的添加剂中。该方法不仅在太阳能和室内光线下提供了创纪录的WBG PSC效率,而且打破了固定设备外观的限制,为高效,自适应颜色的钙钛矿光伏开辟了道路。
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引用次数: 0
NBD Integrated and Vitamin B6-Driven Charge-Reversible Peptide-Based Nanocarriers for Targeted Therapeutic Delivery 靶向治疗递送的NBD集成和维生素b6驱动电荷可逆肽基纳米载体
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202513436
Suman Nayak, Anushree Lye, Subhabrata Guha, Nanjundan Raghul, Adele Stewart, Gaurav Das, Biswanath Maity, Priyadip Das
Peptide-based self-assembled nanostructures offer great promise for targeted drug delivery due to their intrinsic biocompatibility, biodegradability, and structural tunability. However, their limited optical properties and lack of functional sites for selective targeting restrict their use in theranostics. Here, we report a fluorophore-integrated, pH-responsive dipeptide nanocarrier engineered from phenylalanine–tryptophan (F–W) conjugated with 4-chloro-7-nitrobenzofurazan (NBD) as a fluorescent probe and vitamin B6 (VitB6) as a pH-sensitive unit. The resulting vitamin B6-modified nanoparticles (PS-Dox) exhibited charge reversal from negative to positive under mildly acidic conditions (pH 5.0), promoting doxorubicin (Dox) release, endosomal escape, and nuclear localization. PS-Dox demonstrated enhanced cytotoxicity, DNA damage, and apoptosis induction in multiple cancer cell lines, while showing negligible toxicity toward non-malignant cardiomyocytes (AC-16 and H9C2). In vivo biodistribution and pharmacokinetic studies revealed increased tumour accumulation and superior tumour growth inhibition compared with Dox. Importantly, PS-mediated encapsulation effectively mitigated Dox-associated cardiotoxicity, a major limitation of conventional chemotherapy. Overall, this study establishes a vitamin B6-mediated, charge-reversible peptide nanocarrier as a biocompatible and efficient platform for targeted anticancer drug delivery, combining tumour-specific therapeutic efficacy with improved cardiac safety.
基于肽的自组装纳米结构由于其内在的生物相容性、生物可降解性和结构可调性,为靶向药物递送提供了巨大的希望。然而,它们有限的光学性质和缺乏选择性靶向的功能位点限制了它们在治疗学中的应用。在这里,我们报道了一种荧光团集成,ph响应的二肽纳米载体,由苯丙氨酸-色氨酸(F-W)与4-氯-7-硝基苯并呋喃唑(NBD)偶联作为荧光探针,维生素B6 (VitB6)作为ph敏感单元。得到的维生素b6修饰纳米粒子(PS-Dox)在温和酸性条件下(pH 5.0)表现出由负向正的电荷反转,促进阿霉素(Dox)释放、内体逃逸和核定位。PS-Dox在多种癌细胞系中表现出增强的细胞毒性、DNA损伤和细胞凋亡诱导,而对非恶性心肌细胞的毒性可以忽略不计(AC-16和H9C2)。体内生物分布和药代动力学研究显示,与Dox相比,肿瘤积累增加,肿瘤生长抑制效果更好。重要的是,ps介导的包封有效地减轻了dox相关的心脏毒性,这是传统化疗的一个主要限制。总的来说,本研究建立了一种维生素b6介导的电荷可逆肽纳米载体,作为靶向抗癌药物递送的生物相容性和高效平台,将肿瘤特异性治疗效果与提高心脏安全性结合起来。
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引用次数: 0
Microstructure-Interface Modulation Boosts Sodium Storage Capacity and Stability of Hard Carbon 微观结构-界面调制提高硬碳的钠储存能力和稳定性
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202513954
Zhe Wang, Yutian Yang, Hang Li, Yuying Zhang, Feng Ouyang, Wenjing Dong, Quan Zong, Shuang Zhou, Anqiang Pan
The development of hard carbon (HC) anode is severely hindered by limited Na+ storage capacity and poor cycling stability, which are closely related to its microstructure and interface. In this work, a synergistic microstructure-interface modulation strategy is demonstrated to regulate the Na+ storage active sites and structural stability of resin-based HC. The introduced C═O enables reversible Na+ adsorption, while carboxyl and neighboring phenolic hydroxyl functional groups anchor the template metal ions (Zn2+), thereby constructing a hierarchical pore structure with abundant sites for reversible Na+ storage. Additionally, expanded interlayer spacing promotes the kinetics of reversible Na+ intercalation/deintercalation. Based on this strategy, the optimized HC material (ZGB-HC) exhibits an extra-high capacity of 406 mAh g−1 at 50 mA g−1 and maintains exceptional cycling stability of over 1000 cycles for 1 A g−1. More surprisingly, the assembled Na3V2(PO4)3||ZGB-HC full cell delivers a superior rate capability of 96.4 mAh g−1 at 4 C and maintains excellent cycling stability for over 250 cycles at 2C. This work develops an innovative strategy for designing HC anodes with advanced microstructure-interface and new insights into their structural evolution during cycling.
硬碳(HC)阳极的发展受到Na+存储容量有限和循环稳定性差的严重阻碍,这与它的微观结构和界面密切相关。在这项工作中,证明了一种协同微结构-界面调制策略可以调节树脂基HC的Na+存储活性位点和结构稳定性。引入的C = O实现了可逆的Na+吸附,而羧基和邻近的酚羟基官能团锚定了模板金属离子(Zn2+),从而构建了具有丰富可逆Na+存储位点的分层孔结构。此外,层间距的扩大促进了可逆的Na+插/脱插动力学。基于该策略,优化的HC材料(ZGB-HC)在50 mA g - 1下具有406 mAh g - 1的超高容量,并且在1 A g - 1下保持超过1000次循环的优异稳定性。更令人惊讶的是,组装的Na3V2(PO4)3||ZGB-HC全电池在4℃下提供了96.4 mAh g−1的卓越倍率能力,并在2C下保持了250多次循环的优异稳定性。这项工作开发了一种创新的策略来设计具有先进微观结构界面的HC阳极,并对其在循环过程中的结构演变有了新的见解。
{"title":"Microstructure-Interface Modulation Boosts Sodium Storage Capacity and Stability of Hard Carbon","authors":"Zhe Wang, Yutian Yang, Hang Li, Yuying Zhang, Feng Ouyang, Wenjing Dong, Quan Zong, Shuang Zhou, Anqiang Pan","doi":"10.1002/smll.202513954","DOIUrl":"https://doi.org/10.1002/smll.202513954","url":null,"abstract":"The development of hard carbon (HC) anode is severely hindered by limited Na<sup>+</sup> storage capacity and poor cycling stability, which are closely related to its microstructure and interface. In this work, a synergistic microstructure-interface modulation strategy is demonstrated to regulate the Na<sup>+</sup> storage active sites and structural stability of resin-based HC. The introduced C═O enables reversible Na<sup>+</sup> adsorption, while carboxyl and neighboring phenolic hydroxyl functional groups anchor the template metal ions (Zn<sup>2+</sup>), thereby constructing a hierarchical pore structure with abundant sites for reversible Na<sup>+</sup> storage. Additionally, expanded interlayer spacing promotes the kinetics of reversible Na<sup>+</sup> intercalation/deintercalation. Based on this strategy, the optimized HC material (ZGB-HC) exhibits an extra-high capacity of 406 mAh g<sup>−1</sup> at 50 mA g<sup>−1</sup> and maintains exceptional cycling stability of over 1000 cycles for 1 A g<sup>−1</sup>. More surprisingly, the assembled Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>||ZGB-HC full cell delivers a superior rate capability of 96.4 mAh g<sup>−1</sup> at 4 C and maintains excellent cycling stability for over 250 cycles at 2C. This work develops an innovative strategy for designing HC anodes with advanced microstructure-interface and new insights into their structural evolution during cycling.","PeriodicalId":228,"journal":{"name":"Small","volume":"11 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146134320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Self-Lubricating Nanofiber/Hollow Microsphere All-Ceramic Architecture for Robust Flexible Thermal Insulation 自润滑纳米纤维/空心微球全陶瓷结构坚固的柔性保温
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202514094
Kehan Qu, Yujie You, Qiangyu Xue, Sanyu Yi, Yinsong Si
The integration of ultrahigh thermal stability, minimal thermal conductivity, and robust mechanical flexibility into a single thermal insulation material remains a critical challenge, especially for safeguarding against transient thermal extremes like lithium battery thermal runaway. This study presents an all-inorganic flexible membrane fabricated via a facile electrospinning technique, which strategically embeds hollow silica (SiO2) microspheres (HSMs) within a scaffold of SiO2 nanofibers (SNF). This design yields a 3D self-lubricating architecture that confers extraordinary mechanical durability, withstanding over 100 000 bending cycles under 99% strain and 72 h of vibration without significant weight loss—a performance that surpasses conventional ceramics by orders of magnitude. Simultaneously, the composite membrane exhibits an ultralow and stable thermal conductivity of 31.39 mW m−1 K−1, together with a high specific airflow resistance of 122.11 (kPa S m−1) mm−1, synergistically inhibiting heat conduction and convection. The SNF/HSMs composite membrane demonstrates exceptional thermal resilience, enduring long-term exposure at 1100°C and surviving drastic thermal shocks from 1300°C to −196°C. When evaluated in a practical flame test at 700°C, a mere 5-mm-thick membrane effectively maintains a low backside temperature of ≈160°C. This work establishes a groundbreaking design principle for high-performance, flexible thermal protection systems.
将超高的热稳定性、最小的热导率和强大的机械灵活性整合到单一的隔热材料中仍然是一个关键的挑战,特别是在防止锂电池热失控等瞬态极端热的情况下。本研究提出了一种通过静电纺丝技术制备的全无机柔性膜,该膜将空心二氧化硅(SiO2)微球(hsm)策略性地嵌入二氧化硅纳米纤维(SNF)支架中。这种设计产生了一种3D自润滑结构,赋予了非凡的机械耐久性,在99%的应变和72小时的振动下承受了超过10万次的弯曲循环,而没有明显的重量减轻,这一性能超过了传统陶瓷的数量级。同时,复合膜具有31.39 mW m−1 K−1的超低稳定导热系数,以及122.11 (kPa S m−1)mm−1的高比气流阻力,协同抑制热传导和对流。SNF/ hsm复合膜具有优异的热弹性,可承受1100°C的长期暴露,并可承受1300°C至- 196°C的剧烈热冲击。当在700°C的实际火焰测试中进行评估时,仅仅5毫米厚的薄膜就能有效地保持约160°C的低背面温度。这项工作为高性能、灵活的热保护系统建立了开创性的设计原则。
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引用次数: 0
Exposure to Grilled Lamb-Borne Carbon Quantum Dots Induces Intrahepatic Cholestasis by Activating the Intestinal Microbial-Derived Lipopolysaccharide-TLR4 Pathway 暴露于烤羊肉碳量子点通过激活肠道微生物来源的脂多糖- tlr4途径诱导肝内胆汁淤积
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202512173
Jingwen Xu, Kaiqiang Lv, Sijuan Wang, Guangwen Luo, Shasha Chen, Ning Guo, Yijie Li, Guoliang Li
The by-products of thermally processed foods, carbon quantum dots (CQDs), pose unpredictable risks to human health due to their nanoscale size and abundant surface functional groups that can readily accumulate in organs. Herein, mice were oral-exposed to grilled lamb-derived CQDs (25 mg kg−1) for 9 weeks. The results indicated that CQDs exposure resulted in liver and intestinal barrier injury, as well as an increase in intestinal microbiota-derived lipopolysaccharide (LPS). CQDs exposure directly and indirectly upregulated the expression of bile acid (BA) synthesis genes (Cyp7a1, Cyp8b1, and Cyp27a1) by activating MyD88 in the intestinal LPS-TLR4 pathway, as well as MyD88 and NFκB, downstream molecules of LPS-TLR4 pathway in the liver, leading to increased BA synthesis. Concurrently, the expression of BA excretion genes Bsep and Mrp2 was downregulated, contributing to cholestasis. With prolonged exposure, the levels of the farnesoid X receptor (FXR) inhibitor tauro-β-muricholic acid increased, while that of agonists chenodeoxycholic acid and taurochenodeoxycholic acid decreased, further exacerbating cholestasis. Supplementation with Lactiplantibacillus plantarum ATCC8014 mitigated cholestasis by reducing the relative abundance of g_Flexispira, increasing the relative abundance of g_Adlercreutzia, and remodeling the intestinal barrier. This study provides substantial evidence for the comprehensive assessment, control, and intervention regarding the hepatotoxicity of foodborne CQDs.
热加工食品的副产品碳量子点(CQDs)由于其纳米级尺寸和丰富的表面官能团易于在器官中积累,对人类健康构成不可预测的风险。在本研究中,小鼠口服暴露于烤羊肉来源的CQDs (25 mg kg - 1) 9周。结果表明,CQDs暴露导致肝脏和肠道屏障损伤,以及肠道微生物源性脂多糖(LPS)的增加。CQDs暴露通过激活肠道LPS-TLR4通路MyD88以及肝脏LPS-TLR4通路下游分子MyD88和NFκB,直接或间接上调胆汁酸(BA)合成基因Cyp7a1、Cyp8b1和Cyp27a1的表达,导致BA合成增加。同时,BA排泄基因Bsep和Mrp2表达下调,导致胆汁淤积。随着暴露时间的延长,法脂类X受体(FXR)抑制剂牛磺酸-β-胆酸的水平升高,而激动剂鹅去氧胆酸和牛磺酸去氧胆酸的水平下降,进一步加剧了胆汁淤积。补充植物乳杆菌ATCC8014可以通过降低g_Flexispira的相对丰度、增加g_Adlercreutzia的相对丰度和重塑肠道屏障来减轻胆汁淤积。本研究为食源性CQDs肝毒性的综合评估、控制和干预提供了有力证据。
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引用次数: 0
Fluorescently Labeled Gradient Hydrogels Reveal Matrix-Dependent Cell Responses to Substrate Stiffness 荧光标记梯度水凝胶揭示基质依赖性细胞对基质刚度的反应
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202512198
Shin Wei Chong, Li Liu, Daryan Kempe, Yingqi Zhang, Kourosh Kalantar-Zadeh, Marcela M. M. Bilek, Lining Arnold Ju, Maté Biro, Daniele Vigolo
Microfabricated stiffness gradient hydrogels hold significant value for advancing mechanobiology, tissue engineering, and in vitro tissue models. However, it remains challenging to design these materials given their broad processing parameter space. The continuum of stiffness values also makes it difficult to precisely correlate the local substrate properties and observed biological responses, often relying on cumbersome characterization methods such as atomic force microscopy. To address these bottlenecks, we present a straightforward thermophoresis-based fabrication strategy to pattern stiffness gradients in a fluorescein isothiocyanate-labeled hydrogel network, which displays a polymer concentration-dependent fluorescence readout. This approach enables quantitative assessment of the gradient formation process and contactless stiffness mapping via standard microscopy imaging. Using gelatin methacryloyl and Gellan gum as model systems, it is shown that substrate stiffness and extracellular matrix protein composition work together to affect 3T3-L1 fibroblast cell morphology and migration, with the underlying hydrogel type also affecting the outcome. By offering a simple and reliable approach for characterizing stiffness gradient hydrogels, this work advances the thermophoretic fabrication platform, opening avenues for new biomaterial systems for understanding and controlling the cell-material interplay.
微制造刚度梯度水凝胶对于推进机械生物学、组织工程和体外组织模型具有重要价值。然而,由于这些材料具有广泛的加工参数空间,因此设计这些材料仍然具有挑战性。连续的刚度值也使得很难精确地将局部衬底特性和观察到的生物反应联系起来,通常依赖于繁琐的表征方法,如原子力显微镜。为了解决这些瓶颈,我们提出了一种直接的基于热致电阻的制造策略,以在异硫氰酸荧光素标记的水凝胶网络中绘制刚度梯度,该网络显示聚合物浓度依赖的荧光读数。这种方法可以通过标准显微镜成像对梯度形成过程和非接触刚度映射进行定量评估。以明胶甲基丙烯酰和结冷胶为模型体系,研究表明底物刚度和细胞外基质蛋白组成共同影响3T3-L1成纤维细胞的形态和迁移,而底层水凝胶类型也影响结果。通过提供一种简单可靠的方法来表征刚度梯度水凝胶,这项工作推进了热泳制备平台,为理解和控制细胞-材料相互作用的新生物材料系统开辟了道路。
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引用次数: 0
Cu–O–In Bridge Engineering in Cu2O/In2O3 Nanowires for Efficient CO2-to-CO Electroreduction 用于CO2-to-CO电还原的Cu2O/In2O3纳米线的Cu-O-In桥接工程
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202513217
Jiaomei Xiao, Guanfa Wang, Yan Chen, Gaixiu Yang, Jianlin Huang
Although modulating the d-band center (εd) is an effective strategy to improve electrocatalytic activity, precise regulation of εd for CO2 electroreduction to CO remains a substantial challenge. Here, we report a heterostructured catalyst consisting of In2O3-incorporated 3D nanowire copper foam (Cu2O/In2O3@CF), with tunable εd via Cu–O–In bridges for efficient electrocatalytic CO2 reduction (eCO2R) to CO. The optimized Cu2O/In2O3@CF delivers impressive CO Faradaic efficiency (FECO) exceeding 90% over a broad potential range from −0.47 to −0.87 V (vs. reversible hydrogen electrode, RHE), with a peak FECO of 95.8% at −0.67 V (vs. RHE), and a high production rate of 1035.3 µmol cm−2 h−1, along with stable operation for over 130 h. In situ Raman and Fourier transform infrared spectroscopy (FTIR) analyses combined with density functional theory (DFT) calculations reveal that the formation of Cu2O/In2O3 heterointerface with Cu–O–In bridge facilitates charge redistribution, upshifting the εd of Cu sites and downshifting that of In sites, thereby optimizing the adsorption-desorption energies of reaction intermediates during eCO2R. This synergistic design of oxide-oxide heterointerface with an interconnected 1D nanowires architecture offers an innovative strategy for enhancing eCO2R performance.
虽然调节d波段中心(εd)是提高电催化活性的有效策略,但精确调节CO2电还原为CO的εd仍然是一个重大挑战。在这里,我们报告一个用In2O3-incorporated 3 d纳米线组成的催化剂铜泡沫(Cu2O / In2O3@CF),通过高效electrocatalytic Cu-O-In桥梁与可调εd减少二氧化碳(eCO2R)有限公司优化Cu2O / In2O3@CF提供令人印象深刻的公司感应电流的效率(摘要)超过90%在一个广泛的潜在范围从0.47−−0.87 V (vs可逆氢电极,流值),所以峰值的95.8%−0.67 V(和流值)和高产量的1035.3µ摩尔厘米−2 h−1,原位拉曼和傅里叶变换红外光谱(FTIR)分析结合密度泛函理论(DFT)计算表明,Cu2O/In2O3异质界面与Cu - o - In桥的形成促进了电荷的重新分配,提高了Cu位的εd,降低了In位的εd,从而优化了反应中间体在eCO2R过程中的吸附-解吸能。这种氧化物-氧化物异质界面与相互连接的一维纳米线结构的协同设计为提高eCO2R性能提供了一种创新策略。
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引用次数: 0
Regioisomeric Engineering of Covalent Organic Frameworks toward Enhanced Photocatalytic Performance 共价有机框架的区域异构体工程增强光催化性能
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202512472
Guoye Yu, Guangchao Han, Xin Zhao, Jialin Cui, Yingjie Zhao, Yuancheng Wang
The photocatalytic performance of covalent organic frameworks (COFs) is often restricted by the inefficient utilization of photogenerated charge carriers. Achieving precise regulation of their electronic structures to facilitate charge separation and transport remains a great challenge. Herein, two regioisomeric COFs bearing pyrene units substituted at the 1,6- or 2,7-positions were rationally designed and synthesized to elucidate the influence of isomerism on electron distribution and photocatalytic behavior. Despite their comparable chemical composition and framework topology, the two regioisomeric COFs exhibited distinct photocatalytic activities. The 2,7-substituted P-COF exhibited a remarkable hydrogen evolution rate of 12.3 mmol h−1 g−1, whereas the 1,6-substituted D-COF displayed only negligible activity of 0.42 mmol h−1 g−1. Furthermore, P-COF achieved a H2O2 generation rate of 4.25 mmol h−1 g−1 using benzyl alcohol as sacrificial agent, much higher than that of D-COF (0.64 mmol h−1 g−1). A combination of experimental characterization and theoretical analysis revealed that regioisomerism exerts a decisive effect on the electronic structures as well as charge separation and transport dynamics, thereby substantially enhancing photocatalytic performance of pyrene-based COFs.
共价有机骨架(COFs)的光催化性能经常受到光生成载流子利用率低的限制。实现它们的电子结构的精确调节以促进电荷分离和传输仍然是一个巨大的挑战。本文合理设计和合成了两个在1,6-或2,7位取代芘单元的区域异构体COFs,以阐明异构体对电子分布和光催化行为的影响。尽管两种区域异构体COFs具有相似的化学成分和结构拓扑结构,但它们表现出不同的光催化活性。2,7取代的P-COF的析氢速率为12.3 mmol h−1 g−1,而1,6取代的D-COF的析氢速率为0.42 mmol h−1 g−1,可以忽略。以苯甲醇为牺牲剂,P-COF的H2O2生成速率为4.25 mmol h−1 g−1,远高于D-COF的0.64 mmol h−1 g−1。实验表征和理论分析相结合表明,区域异构对电子结构、电荷分离和输运动力学具有决定性影响,从而大大提高了芘基COFs的光催化性能。
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