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Temperature-induced fibrillogenesis and gelation of fibrinogen mediated by calcium salts 钙盐介导的温度诱导纤维形成和纤维蛋白原凝胶化
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-01 Epub Date: 2026-01-14 DOI: 10.1016/j.giant.2026.100383
Dominik Hense , Lana Molnar , Andreas Bernkop-Schnürch , Oliver I. Strube
The blood clotting protein fibrinogen is known for its excellent biocompatibility and cell adhesion. The usual strategy to use its full potential is to create fibers and/or hydrogels out of it, most commonly enzymatically in form of fibrin. There are, however, many pathways to create fibrinogen-based materials via enzyme-free approaches. In this study, we investigate these possibilities even further and present a temperature-induced method to obtain enzyme-free fibrous hydrogels from a precursor within 30 min. The keys to create these gels are the addition of calcium salts and a defined temperature program. Successful gelation first requires an incubation period at 37 °C for approximately 10 h. This leads to the formation of a ready-to-gel precursor, which remains stable for 2.5 days when the temperature is unchanged. When lowering the temperature to 25 – 10 °C, the mixture irreversibly gels within 30 min. If the incubation period is, however, canceled earlier, the precursor will not gel at all. Additionally, this process succeeds only with Ca2+ ions; if Mg2+ is used instead, the solution remains unchanged while the addition of Sr2+ leads to amorphous precipitation over time. In this study, this remarkable process is characterized regarding optimal reaction conditions by means of scanning electron microscopy, rheology, and dynamic light scattering.
凝血蛋白纤维蛋白原以其优异的生物相容性和细胞粘附性而闻名。利用其全部潜力的通常策略是用它制造纤维和/或水凝胶,最常见的是酶促纤维蛋白的形式。然而,有许多途径可以通过无酶的方法来制造基于纤维蛋白原的材料。在这项研究中,我们进一步研究了这些可能性,并提出了一种温度诱导的方法,可以在30分钟内从前体中获得无酶纤维水凝胶。制造这些凝胶的关键是钙盐的添加和确定的温度程序。成功凝胶化首先需要在37°C下孵育约10小时。这导致形成可凝胶前体,在温度不变的情况下,该前体可保持2.5天的稳定。当温度降低到25 - 10°C时,混合物在30分钟内不可逆地凝胶化。但是,如果提前取消潜伏期,则前体根本不会凝结。此外,该过程仅在Ca2+离子中成功;如果用Mg2+代替,溶液保持不变,而Sr2+的加入会随着时间的推移导致非晶析出。在本研究中,通过扫描电镜、流变学和动态光散射等手段,对这一显著的过程进行了最佳反应条件的表征。
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引用次数: 0
Phosphorus-containing resveratrol-based flame retardants derived from esterification reactions for flame-retardant epoxy resins 含磷白藜芦醇系阻燃剂,由阻燃环氧树脂的酯化反应衍生
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-01 Epub Date: 2026-02-09 DOI: 10.1016/j.giant.2026.100385
Yong Liu , Shi Hao Zheng , Fang Zhou , Hao Yuan
With an increasing focus worldwide on protecting the environment and developing in a sustainable way. Developing halogen-free, environmentally benign flame retardants is of critical relevance. To enhance the fire-safety performance of epoxy resins while simultaneously mitigating their environmental impacts. The bio-derived flame retardant DOPR was prepared in a single-step, one-pot process using resveratrol and DOPO as the key starting materials. The resulting product was subsequently incorporated into an epoxy matrix to obtain EP/DOPR composites. Despite encompassing only 0.35 wt % phosphorus, the EP/5DOPR composite exhibited an increased LOI of 28.19 % and secured the top-tier V-0 grade in the UL-94 flammability evaluation. Compared with neat EP, its pHRR, THR and TSP were lowered by nearly 15.65 %, 33.13 % and 9.62 %, respectively. Furthermore, the residual char yield of the composite was improved from 14.78 % to 17.88 %. The mechanical properties of the composite material were enhanced following the addition of 3wt % and 5wt % flame retardant, indicating a more favourable balance between flame retardancy efficiency and additive loading. The relevant research findings may provide a potential fundamental approach for the application of bio-based flame retardants to enhance the high performance of epoxy resins.
随着世界范围内对环境保护和可持续发展的日益关注。开发无卤、环保的阻燃剂至关重要。提高环氧树脂的防火性能,同时减轻其对环境的影响。以白藜芦醇和DOPO为主要原料,采用一步一锅法制备了生物源阻燃剂DOPR。所得产物随后加入到环氧基中,得到EP/DOPR复合材料。尽管EP/5DOPR复合材料的含磷量仅为0.35 wt %,但LOI增加了28.19%,并在UL-94可燃性评估中获得了顶级的V-0级。与纯EP相比,其pHRR、THR和TSP分别降低了近15.65%、33.13%和9.62%。此外,复合材料的残炭收率由14.78%提高到17.88%。添加3wt %和5wt %的阻燃剂后,复合材料的力学性能得到了提高,表明阻燃效率和添加剂负荷之间的平衡更为有利。相关研究结果可能为应用生物基阻燃剂提高环氧树脂的高性能提供潜在的基础途径。
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引用次数: 0
Why is the temperature rating of biaxially oriented polypropylene film capacitors limited to 85°C? 为什么双轴定向聚丙烯薄膜电容器的额定温度限制在85°C?
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-01 Epub Date: 2025-12-24 DOI: 10.1016/j.giant.2025.100381
Tianke Chen , Yue Li , Guanchun Rui , Yuta Makita , Toshikazu Miyoshi , Eric Baer , Lei Zhu
Biaxially oriented polypropylene (BOPP) film capacitors have become the benchmark technology for DC-link and power electronic applications in electric vehicles due to their ultralow loss, high ripple current, high dielectric breakdown strength, and long operational lifetime. However, their maximum operating temperature is restricted to 85°C, a limitation that constrains performance in demanding power electronic environments (∼140°C). The origin of this temperature ceiling has remained insufficiently understood. In this work, we investigate the structure-property relationships that govern the breakdown strength and lifetime of BOPP films at elevated temperatures. Comprehensive analyses, including both structure and dielectric insulation characterizations, were performed to correlate microstructural transitions with dielectric performance. The results revealed that the αc relaxation of isotactic polypropylene around 90°C was the critical factor responsible for the deterioration of breakdown strength (and thus reduced lifetime). Because of 120° helical jumps at crystalline-amorphous interfaces, the αc relaxation lowered modulus, diminished the rigid fraction, and enhanced homocharge injection. Consequently, breakdown strength decreased sharply above 85°C. These findings provide a mechanistic explanation for the long-recognized 85°C rating of BOPP film capacitors. The insights gained not only clarify the intrinsic thermal limitation of BOPP but also point toward rational design strategies for high-temperature polymer dielectrics, such as advanced polyolefins, capable of extending the dielectric performance toward 150°C operation in next-generation electric vehicle power electronics.
双轴取向聚丙烯(BOPP)薄膜电容器因其超低损耗、高纹波电流、高介电击穿强度和长使用寿命,已成为电动汽车直流链路和电力电子应用的基准技术。然而,它们的最高工作温度限制在85°C,这一限制限制了在苛刻的电力电子环境(~ 140°C)中的性能。这个温度上限的起源仍然没有得到充分的了解。在这项工作中,我们研究了在高温下控制BOPP薄膜击穿强度和寿命的结构-性能关系。综合分析,包括结构和介电绝缘特性,进行了微观结构转变与介电性能的关联。结果表明,等规聚丙烯在90℃左右αc弛豫是导致其击穿强度下降的关键因素。由于αc弛豫在晶态-非晶态界面处发生了120°的螺旋跃变,使得模量降低,刚性分数降低,同电荷注入增强。因此,在85°C以上,击穿强度急剧下降。这些发现为长期以来公认的BOPP薄膜电容器的85°C额定值提供了机制解释。这些发现不仅阐明了BOPP固有的热限制,还为高温聚合物介电材料(如先进的聚烯烃)的合理设计策略指明了方向,这些材料能够将下一代电动汽车电力电子设备的介电性能扩展到150°C。
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引用次数: 0
Closed-Loop green precipitation polymerization for kinetically controlled multifunctional polymer microspheres 动力学控制多功能聚合物微球的闭环绿色沉淀聚合
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-01 Epub Date: 2026-01-29 DOI: 10.1016/j.giant.2026.100384
Xuechun Cui , Wei Liu , Zonglin Yang , Jinman Zhou , Xianyong Lu
Multifunctional polymer microspheres are indispensable in catalysis, separation, and drug delivery, yet their scalable fabrication is often hampered by low solvent recovery, narrow synthetic scope, and poor kinetic control. These limitations not only lead to solvent wastage and environmental burdens, but also cause undesirable outcomes such as uncontrolled polymerization and broadened particle size distributions. Herein, we report a green, sustainable, and kinetically controllable precipitation polymerization strategy that couples rotary evaporation with a closed-loop solvent management system. This platform enables the efficient synthesis of polymer microspheres bearing diverse functional groups, thereby broadening their applicability across multiple application scenarios. The process achieves a solvent recovery rate of up to 95.2%, affords precise regulation of crosslinking density (0.05–0.80), and simultaneously improves both monodispersity and yield (up to 68.7% at high crosslinking degrees). Notably, the recovered acetonitrile can be directly reused without additional purification, underscoring the robustness of the solvent recycling scheme. Overall, this scalable approach integrates kinetic control, functional versatility, and solvent circularity into a unified process, providing a practical route to high-quality multifunctional polymer microspheres while minimizing solvent waste and obviating complex post-treatment steps.
多功能聚合物微球在催化、分离和药物传递中是不可或缺的,但其可扩展性制造往往受到溶剂回收率低、合成范围窄和动力学控制差的阻碍。这些限制不仅会导致溶剂浪费和环境负担,而且还会导致不受控制的聚合和扩大的粒径分布等不良后果。在此,我们报告了一种绿色、可持续、动态可控的沉淀聚合策略,该策略将旋转蒸发与闭环溶剂管理系统相结合。该平台能够高效合成具有多种官能团的聚合物微球,从而扩大其在多种应用场景中的适用性。该工艺溶剂回收率可达95.2%,可精确调节交联密度(0.05 ~ 0.80),同时提高单分散性和收率(高交联度时可达68.7%)。值得注意的是,回收的乙腈可以直接重复使用,而无需额外的净化,强调了溶剂回收方案的稳健性。总的来说,这种可扩展的方法将动力学控制、功能通用性和溶剂循环性集成到一个统一的过程中,为高质量的多功能聚合物微球提供了一条实用的途径,同时最大限度地减少了溶剂浪费,避免了复杂的后处理步骤。
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引用次数: 0
MoTeSe/InN heterostructures for gas sensors: a first-principles study 气体传感器的moese /InN异质结构:第一性原理研究
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-01 Epub Date: 2025-12-31 DOI: 10.1016/j.giant.2025.100382
Hangyu Wen , Yifei Zhong , Jianhua Pang , Kuanyi Wang , Guang Wei , Zhenming Yang , Songrui Wei
Two-dimensional van der Waals heterojunctions can significantly boost gas-sensing performance through interfacial synergy, surpassing the limits of individual constituents. Based on first-principles calculations, this study systematically explores the potential of a vertical heterojunction composed of novel Janus MoTeSe and InN for gas-sensing applications. Binding-energy calculations and AIMD simulations identify AB-MoIn-stacked MoTeSe/InN as the most stable configuration, and the adsorption behavior and sensing mechanism of the heterojunction toward Cl₂, NO₂, NH₃, NO, SO₂, and H₂S are investigated comprehensively. The results reveal that the heterojunction markedly enhances adsorption of Cl₂, NO₂, NO, and H₂S, with adsorption energies of -0.880 eV and -0.961 eV for Cl₂ and NO₂, respectively, accompanied by substantial charge transfer. Electronic-structure analysis elucidates the key sensing mechanisms: adsorption of NO₂ (TIn site) and NO metallizes the system, greatly increasing electrical conductivity; adsorption of Cl₂ (TN site) and SO₂ increases the bandgap by approximately 47.3 % and 49.4 %, respectively; notably, NO₂ adsorption on the TTe site also induces magnetism. Further evaluation of sensitivity and recovery time indicates that the heterojunction exhibits both high sensitivity and good reversibility toward NO₂ and Cl₂—for example, the room-temperature recovery time for NO₂ on the TTe site is only 0.36 ms. This work clarifies the atomic-scale gas-sensing mechanism of MoTeSe/InN heterostructures, especially for Cl₂ and NO₂, and provides a solid theoretical basis for their application as high-performance, recyclable gas-sensor candidates.
二维范德华异质结可以通过界面协同作用显著提高气敏性能,超越单个成分的限制。基于第一性原理计算,本研究系统地探索了由新型Janus MoTeSe和InN组成的垂直异质结在气敏应用中的潜力。结合结合能计算和AIMD模拟,确定了AB-MoIn-stacked moese /InN是最稳定的构型,并对异质结对Cl₂、NO₂、NH₃、NO、SO₂和H₂S的吸附行为和传感机理进行了全面研究。结果表明,异质结对Cl₂、NO₂、NO和H₂S的吸附能力显著增强,Cl₂和NO₂的吸附能分别为-0.880 eV和-0.961 eV,并伴有大量电荷转移。电子结构分析阐明了关键的传感机制:吸附NO₂(TIn位点)和NO金属化系统,大大提高了电导率;Cl₂(TN位)和SO₂的吸附使带隙分别增大约47.3%和49.4%;值得注意的是,TTe位点上的NO₂吸附也会产生磁性。对灵敏度和恢复时间的进一步评价表明,异质结对NO₂和Cl₂具有较高的灵敏度和良好的可逆性,例如,TTe位点上NO₂的室温恢复时间仅为0.36 ms。本研究阐明了MoTeSe/InN异质结构的原子尺度气敏机理,特别是对Cl₂和NO₂的气敏机理,为其作为高性能、可回收的候选气敏材料的应用提供了坚实的理论基础。
{"title":"MoTeSe/InN heterostructures for gas sensors: a first-principles study","authors":"Hangyu Wen ,&nbsp;Yifei Zhong ,&nbsp;Jianhua Pang ,&nbsp;Kuanyi Wang ,&nbsp;Guang Wei ,&nbsp;Zhenming Yang ,&nbsp;Songrui Wei","doi":"10.1016/j.giant.2025.100382","DOIUrl":"10.1016/j.giant.2025.100382","url":null,"abstract":"<div><div>Two-dimensional van der Waals heterojunctions can significantly boost gas-sensing performance through interfacial synergy, surpassing the limits of individual constituents. Based on first-principles calculations, this study systematically explores the potential of a vertical heterojunction composed of novel Janus MoTeSe and InN for gas-sensing applications. Binding-energy calculations and AIMD simulations identify AB-MoIn-stacked MoTeSe/InN as the most stable configuration, and the adsorption behavior and sensing mechanism of the heterojunction toward Cl₂, NO₂, NH₃, NO, SO₂, and H₂S are investigated comprehensively. The results reveal that the heterojunction markedly enhances adsorption of Cl₂, NO₂, NO, and H₂S, with adsorption energies of -0.880 eV and -0.961 eV for Cl₂ and NO₂, respectively, accompanied by substantial charge transfer. Electronic-structure analysis elucidates the key sensing mechanisms: adsorption of NO₂ (T<sub>In</sub> site) and NO metallizes the system, greatly increasing electrical conductivity; adsorption of Cl₂ (T<sub>N</sub> site) and SO₂ increases the bandgap by approximately 47.3 % and 49.4 %, respectively; notably, NO₂ adsorption on the T<sub>Te</sub> site also induces magnetism. Further evaluation of sensitivity and recovery time indicates that the heterojunction exhibits both high sensitivity and good reversibility toward NO₂ and Cl₂—for example, the room-temperature recovery time for NO₂ on the T<sub>Te</sub> site is only 0.36 ms. This work clarifies the atomic-scale gas-sensing mechanism of MoTeSe/InN heterostructures, especially for Cl₂ and NO₂, and provides a solid theoretical basis for their application as high-performance, recyclable gas-sensor candidates.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"27 ","pages":"Article 100382"},"PeriodicalIF":4.9,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Elucidating the solvent-modulated self-assembly nanostructures of high ion exchange capacity short-side-chain perfluorosulfonic acid dispersions 高离子交换容量短侧链全氟磺酸分散体的溶剂调制自组装纳米结构研究
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2025-09-12 DOI: 10.1016/j.giant.2025.100373
Jingnan Song , Suyan Wang , Wutong Zhao , Bonan Hao , Yecheng Zou , Xing Li , Xuefei Wu , Feng Liu , Yongming Zhang
The self-assembly behavior of short-side-chain perfluorosulfonic acid (SSC-PFSA) dispersions plays a pivotal role in governing the morphology and performance of proton exchange membranes (PEMs). We explored solvent-modulated structural transitions of SSC-PFSA dispersions using combinatory characterization techniques. It is seen that in high-dielectric environment (25 wt% ethanol), the SSC-PFSA chain adopts rigid rod-like assemblies with locally ordered alignment due to electrostatic repulsion and surface polarization. Lowering the dielectric constant (50 wt% ethanol) induces a semi-flexible configuration with approximately 20 % axial compression, and dispersing heterogeneity is observed due to inter-particle association. Upon reaching 75 wt% ethanol conditions, the rod-like assembly is elongated, loosened, and more disordered. The solvent environment plays an important role in determining the dispersion heterogeneity. More ethanol content lowers the dielectric constant, which reduces acidic dissociation and leads to localized assembly association. This work elucidates a fundamental understanding of the dynamic interplay between backbone solubility and electrostatic interactions in governing the PFSA assembly under different solvent environment. These detailed multi-length-scale nanostructures are key in determining the morphology and performance of PEM, which needs to clearly investigated before PEM fabrication.
短侧链全氟磺酸(SSC-PFSA)分散体的自组装行为对质子交换膜(PEMs)的形态和性能起着关键作用。我们利用组合表征技术探索了SSC-PFSA分散体的溶剂调制结构转变。可见,在高介电环境(25%乙醇)下,由于静电斥力和表面极化,SSC-PFSA链采用刚性棒状组件,具有局部有序排列。降低介电常数(50 wt%乙醇)可产生约20%轴向压缩的半柔性结构,并且由于颗粒间关联而分散非均质性。在达到75%乙醇条件下,棒状组装被拉长,松动,更混乱。溶剂环境对分散不均一性有重要影响。更多的乙醇含量降低介电常数,这减少了酸性解离和导致局部组装联想。这项工作阐明了在不同溶剂环境下控制PFSA组装的主链溶解度和静电相互作用之间的动态相互作用的基本理解。这些详细的多长度尺度纳米结构是决定PEM形态和性能的关键,需要在PEM制造之前进行清楚的研究。
{"title":"Elucidating the solvent-modulated self-assembly nanostructures of high ion exchange capacity short-side-chain perfluorosulfonic acid dispersions","authors":"Jingnan Song ,&nbsp;Suyan Wang ,&nbsp;Wutong Zhao ,&nbsp;Bonan Hao ,&nbsp;Yecheng Zou ,&nbsp;Xing Li ,&nbsp;Xuefei Wu ,&nbsp;Feng Liu ,&nbsp;Yongming Zhang","doi":"10.1016/j.giant.2025.100373","DOIUrl":"10.1016/j.giant.2025.100373","url":null,"abstract":"<div><div>The self-assembly behavior of short-side-chain perfluorosulfonic acid (SSC-PFSA) dispersions plays a pivotal role in governing the morphology and performance of proton exchange membranes (PEMs). We explored solvent-modulated structural transitions of SSC-PFSA dispersions using combinatory characterization techniques. It is seen that in high-dielectric environment (25 wt% ethanol), the SSC-PFSA chain adopts rigid rod-like assemblies with locally ordered alignment due to electrostatic repulsion and surface polarization. Lowering the dielectric constant (50 wt% ethanol) induces a semi-flexible configuration with approximately 20 % axial compression, and dispersing heterogeneity is observed due to inter-particle association. Upon reaching 75 wt% ethanol conditions, the rod-like assembly is elongated, loosened, and more disordered. The solvent environment plays an important role in determining the dispersion heterogeneity. More ethanol content lowers the dielectric constant, which reduces acidic dissociation and leads to localized assembly association. This work elucidates a fundamental understanding of the dynamic interplay between backbone solubility and electrostatic interactions in governing the PFSA assembly under different solvent environment. These detailed multi-length-scale nanostructures are key in determining the morphology and performance of PEM, which needs to clearly investigated before PEM fabrication.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"26 ","pages":"Article 100373"},"PeriodicalIF":4.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145158982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Single-molecule junctions for ultrasensitive detection: fundamental mechanisms and cross-field applications 用于超灵敏检测的单分子结:基本机制和跨领域应用
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2025-10-16 DOI: 10.1016/j.giant.2025.100377
Lin Wang, Zitai Jiang
Ultrasensitive detection at the single-molecule level is crucial for advancing biomedical diagnostics, environmental monitoring, and chemical synthesis. Among various strategies, single-molecule junctions (SMJs) stand out as they convert molecular-scale events into detectable electrical signals, offering a versatile and sensitive platform for real-time, label-free, and non-destructive sensing with single-molecule resolution. This review provides an overview of the primary SMJ measurement techniques, with a particular focus on the fundamental mechanisms driving SMJ-based sensing, including the molecular chemical structure influenced by the local environment, supramolecular interactions and molecule-electrode interface. We also highlight recent progress in utilizing SMJs for monitoring chemical reactions, chiral recognition, and biomedical diagnostics. Finally, we have analyzed the current challenges in single-molecule electrical detection in terms of signal reliability, sensitivity, and selectivity, offering corresponding solutions for each to provide valuable insights for designing more effective detection systems.
单分子水平的超灵敏检测对于推进生物医学诊断、环境监测和化学合成至关重要。在各种策略中,单分子结(smj)脱颖而出,因为它们将分子尺度的事件转换为可检测的电信号,为实时、无标签和非破坏性的单分子分辨率传感提供了一个多功能和敏感的平台。本文综述了主要的SMJ测量技术,重点介绍了SMJ传感的基本机制,包括受局部环境影响的分子化学结构、超分子相互作用和分子-电极界面。我们还强调了利用smj监测化学反应、手性识别和生物医学诊断的最新进展。最后,我们分析了当前单分子电检测在信号可靠性、灵敏度和选择性方面面临的挑战,并针对每个挑战提出了相应的解决方案,为设计更有效的检测系统提供了有价值的见解。
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引用次数: 0
Microstructure modulated dynamics of main-chain giant molecules with exact chain-length and tunable chemical interaction 具有精确链长和可调化学相互作用的主链大分子的微结构调制动力学
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2025-10-15 DOI: 10.1016/j.giant.2025.100376
Hengzhi You, Weiwei Wu, Chengyang Hong, Gengxin Liu, Hao Liu
The field of polymer science has witnessed a paradigm shift from traditional polymers to giant molecules, which possess well-defined structures and discrete molecular weights. These giant molecules, constructed from precisely synthesized building blocks, offer unique opportunities to explore the relationship between molecular architecture and macroscopic properties. This study investigates the microstructure-modulated dynamics of main-chain giant molecules constructed from double-decker silsesquioxane (DDSQ) and polyhedral oligomeric silsesquioxane (POSS) building blocks. A series of giant molecules with exact chain lengths and tunable chain ends were synthesized using thiol-maleimide Michael addition reactions and an iterative "deprotection-addition" strategy. Structural and thermal analysis revealed that homopolymers and vinyl-terminated molecules exhibited amorphous features in their melt states, while carboxylic acid-terminated molecules showed evidence of microphase separation. Rheological characterization demonstrated that homopolymers and vinyl-terminated molecules exhibited unentangled, liquid-like dynamics, whereas carboxylic acid-terminated molecules displayed Zimm-like melt characteristics or pronounced elastic plateau modulus at low frequencies, indicating the formation of physically cross-linked network structures stabilized by intermolecular interactions. This research highlights that chain length and chain-end chemistry significantly govern the hierarchical assembly and viscoelastic behavior of main-chain giant molecules, offering a powerful strategy for engineering novel nanomaterials with tailored mechanical properties through precise molecular design and chain-end functionalization.
聚合物科学领域见证了从传统聚合物到具有明确结构和离散分子量的大分子的范式转变。这些巨大的分子,由精确合成的积木构成,为探索分子结构和宏观性质之间的关系提供了独特的机会。本文研究了双层硅氧烷(DDSQ)和多面体低聚硅氧烷(POSS)构建的主链大分子的微观结构调控动力学。采用巯基-马来酰亚胺Michael加成反应和迭代“脱保护加成”策略合成了一系列链长精确、链端可调的大分子。结构和热分析表明,均聚物和端乙烯基分子在熔融状态下表现出无定形特征,而端羧酸分子则表现出微相分离的特征。流变学表征表明,均聚物和端为乙烯基的分子表现出不纠缠的、类似液体的动力学特性,而端为羧酸的分子在低频时表现出类似齐姆的熔融特性或明显的弹性平台模量,表明分子间相互作用稳定了物理交联网络结构的形成。本研究强调了链长和链端化学对主链大分子的分层组装和粘弹性行为有重要影响,为通过精确的分子设计和链端功能化来设计具有定制力学性能的新型纳米材料提供了强有力的策略。
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引用次数: 0
Air purification and disinfection by biosynthesized Cu-doped TiO2 nanoparticles with Aloe vera extract 芦荟提取物生物合成cu掺杂TiO2纳米颗粒净化消毒空气
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2025-09-24 DOI: 10.1016/j.giant.2025.100375
Niloofar Arefipour , Hassan Koohestani , Hedayat Gholami
The use of plant extracts for synthesizing nanoparticles has garnered significant attention due to their simplicity, environmental friendliness, and cost-effectiveness. This study synthesized titanium dioxide (titania, TiO2) nanoparticles using Aloe vera extract. Its doping with copper was also investigated to reduce the electron/hole pair recombination rate and improve the photocatalytic activity of titania. Biosynthesized titania nanoparticles were characterized by X-ray diffraction (XRD), Diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). XRD reported the formation of crystals with sizes of 4–7 nm by the Scherrer method and 5–27 nm by the Williamson-Hall method. FE-SEM and TEM analysis showed the formation of spherical particles. Spectroscopic results showed that the addition of the copper ion reduced the band gap energy from 3.10 eV to 2.89 eV. It was observed that, under light, increasing the dopant concentration from 1 % to 3 % resulted in an increase in the bacterial removal rate from 93 % to 96 % and the particulate matter removal rate from 91 % to 94 %. Therefore, Cu-TiO2 nanoparticles biosynthesized with Aloe vera extract exhibited increased photocatalytic and antibacterial activity, which can be utilized for air purification.
利用植物提取物合成纳米颗粒因其简单、环保和成本效益而受到广泛关注。本研究以芦荟提取物为原料合成二氧化钛纳米粒子。此外,还研究了其与铜的掺杂,以降低电子/空穴对复合速率,提高二氧化钛的光催化活性。采用x射线衍射(XRD)、漫反射光谱(DRS)、透射电子显微镜(TEM)和场发射扫描电子显微镜(FE-SEM)对生物合成的纳米二氧化钛进行了表征。XRD报告了Scherrer法和Williamson-Hall法形成的尺寸分别为4-7 nm和5-27 nm的晶体。FE-SEM和TEM分析表明,颗粒呈球形。光谱结果表明,铜离子的加入使带隙能量从3.10 eV降低到2.89 eV。结果表明,在光照条件下,将掺杂剂浓度从1%提高到3%,细菌去除率从93%提高到96%,颗粒物去除率从91%提高到94%。因此,用芦荟提取物生物合成的Cu-TiO2纳米颗粒具有更高的光催化和抗菌活性,可用于空气净化。
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引用次数: 0
A non-helical supramolecular chiral catalyst for the asymmetric diels-alder reaction 一种用于不对称diols -alder反应的非螺旋超分子手性催化剂
IF 4.9 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2025-10-24 DOI: 10.1016/j.giant.2025.100378
Jinmiao Ma , Mengmeng Han , Xusen Li , Haoying Liu , Cong Gao , Shipeng Chen , Jie Han
The research of supramolecular chiral catalyst morphology is critically important in asymmetric catalysis, yet current research predominantly focuses on helical architectures, with non-helical systems remaining underexplored. Herein, we present a new type of nanosheet (NS)-like supramolecular chiral catalyst self-assembled from l-threonine-based amphiphilie (L-ThrC16) and Cu(II), which achieves obvious asymmetric catalysis in the Diels-Alder reaction between aza-chalcone and cyclopentadiene (91% yield and 45% ee) despite its non-helical nanostructure. Compared with monomeric counterpart of l-ThrC16Cu(II) catalyst displaying racemic product, the stronger interaction between aza-chalcone and l-ThrC16NS-Cu(II) have been confirmed, which facilitates the chirality transfer from the supramolecular scaffold to aza-chalcone and thereby leading to enantioselectivity. This work not only challenges the conventional paradigm of helical dominance in chiral induction but also establishes a foundation for developing scalable, high-performance non-helical catalysts, thereby expanding the design principles for supramolecular asymmetric synthesis.
超分子手性催化剂的形态研究在不对称催化中至关重要,但目前的研究主要集中在螺旋结构上,对非螺旋体系的探索还很不足。本文提出了一种由l-苏氨酸基两亲化合物(L-ThrC16)和Cu(II)自组装的新型纳米片(NS)类超分子手性催化剂,尽管其具有非螺旋纳米结构,但在偶氮查尔酮与环戊二烯的Diels-Alder反应中具有明显的不对称催化作用(产率91%,ee 45%)。与l-ThrC16Cu(II)单体催化剂相比,证实了偶氮查尔酮与l-ThrC16NS-Cu(II)之间的相互作用更强,这有利于手性从超分子支架转移到偶氮查尔酮,从而导致对映选择性。这项工作不仅挑战了传统的手性诱导中螺旋优势的范式,而且为开发可扩展的、高性能的非螺旋催化剂奠定了基础,从而扩展了超分子不对称合成的设计原则。
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引用次数: 0
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