GIANT最新文献 - Book学术

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

GIANT

Pub 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

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

GIANT

Pub 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 (T_In site) and NO metallizes the system, greatly increasing electrical conductivity; adsorption of Cl₂ (T_N site) and SO₂ increases the bandgap by approximately 47.3 % and 49.4 %, respectively; notably, NO₂ adsorption on the T_Te 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_Te 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。

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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

GIANT

Pub 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 α_c 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 α_c 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

Lanthanum-substituted CaMo-MOF via controlled metal nitrate ratios for Electrochemical Performance 镧取代CaMo-MOF的电化学性能研究

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-10-31 DOI: 10.1016/j.giant.2025.100380

P. Arularasan , Mohd Arif Dar , Mohammad Rezaul Karim , P Rajesh , M Pavithra , Sambasivam Sangaraju

In this study, a series of La_xCa_1-xMo-based metal-organic frameworks (MOFs), designated as CML1, CML2, CML3 and CML4, were synthesized via a controlled precipitation method. A comprehensive characterization was performed using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The XRD confirmed the formation of a single-phase tetragonal scheelite-type structure (I4₁/a), with no secondary phases detected. The average crystallite size is found to be 54, 52, 42 and 16 (nm) in CML1, CML2, CML3 and CML4 MOFs. The SEM reveals a morphological evolution from irregular granules in CML1 to well-faceted rods in CML4 MOFs. The electrochemical analysis revealed a clear performance hierarchy, with CML3 electrode exhibiting the highest the specific capacitance in a two-electrode system. The coulombic efficiency of 96 % is retained by the CML3 electrode even after 1000 GCD cycles in a two-electrode system.

本研究采用可控沉淀法合成了一系列基于laxca1 - xmo的金属有机骨架（mof），编号为CML1、CML2、CML3和CML4。利用x射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、拉曼光谱（Raman）和x射线光电子能谱（XPS）对其进行了综合表征。XRD证实形成了单相四方白钨矿型结构（I4 1 /a），未检测到二次相。CML1、CML2、CML3和CML4 MOFs的平均晶粒尺寸分别为54,52,42和16 nm。扫描电镜显示了CML1的不规则颗粒到CML4的光滑棒状mof的形态演变。电化学分析表明，CML3电极在两电极体系中表现出最高的比电容。在双电极系统中，CML3电极在1000 GCD循环后仍保持96%的库仑效率。

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

GIANT

Pub 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

Biosynthesis of CuO-nanoparticles using extracts of Mespilus germanica, Crataegus spp., and Wild barberry and their synergistic antibacterial activity 德国山楂、山楂和野小檗提取物合成纳米cuo的研究及其协同抗菌活性

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-10-24 DOI: 10.1016/j.giant.2025.100379

Hassan Koohestani , Ali Balooch , Hamid Staji

The green synthesis of nanoparticles is gaining attention as a sustainable and eco-friendly alternative to conventional chemical methods. In this study, copper oxide nanoparticles (CuONPs) were biosynthesized using leaf extracts of Mespilus germanica (M-CuO), Wild barberry (B-CuO), and Crataegus spp. (CCuO) as natural reducing and stabilizing agents. The synthesized nanoparticles were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and Field-emission scanning electron microscopy (FESEM). XRD results confirmed the formation of crystalline CuO with high purity. FESEM analysis revealed that the nanoparticles were nearly spherical with size ranges of 50–70 nm (M-CuO), 60–100 nm (B-CuO), and 50–80 nm (CCuO). FTIR spectra indicated the presence of functional groups such as hydroxyl (-OH) and carbon-oxygen (CO), along with characteristic Cu-O bond vibrations in the 500–700 cm-¹ range. The antibacterial activity of the CuONPs was tested against Gram-positive and Gram-negative bacteria, showing considerable inhibition. A synergistic effect was observed when combining the different types of CuONPs, resulting in enhanced antibacterial performance. These findings highlight the potential of plant-mediated CuONPs as promising candidates for biomedical and antibacterial applications.

纳米颗粒的绿色合成作为一种可持续和环保的传统化学方法的替代品正在引起人们的关注。以德国墨斯皮乌斯（M-CuO）、野杨梅（B-CuO）和山楂（CCuO）叶提取物为天然还原剂和稳定剂，合成了氧化铜纳米颗粒（CuONPs）。采用x射线衍射（XRD）、傅里叶变换红外光谱（FTIR）和场发射扫描电镜（FESEM）对合成的纳米颗粒进行了表征。XRD结果证实形成了高纯度的CuO晶体。FESEM分析表明，纳米颗粒呈近球形，粒径范围为50 ~ 70 nm （M-CuO）、60 ~ 100 nm （B-CuO）和50 ~ 80 nm （CCuO）。FTIR光谱表明，在500-700 cm-¹范围内存在羟基（- oh）和碳氧（CO）等官能团，并伴有特征性的Cu-O键振动。CuONPs对革兰氏阳性菌和革兰氏阴性菌的抑菌活性均有明显的抑制作用。不同类型的CuONPs联合使用可产生协同效应，增强抗菌性能。这些发现突出了植物介导的CuONPs作为生物医学和抗菌应用的有希望的候选者的潜力。

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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

GIANT

Pub 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。

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

GIANT

Pub 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

GIANT

Pub 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

GSH-triggered CD44/FRβ dual-targeting nanoprodrug for acute myeloid leukemia eradication via cascade DNA damage and mitochondrial oxidative storm gsh触发CD44/FRβ双靶向纳米前药通过级联DNA损伤和线粒体氧化风暴根除急性髓系白血病

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-09-21 DOI: 10.1016/j.giant.2025.100374

Yanrong Shuai , Xiaojuan Miao , Yan Wang , Chaozheng Zhang , Yu Liu , Yuening Cao , Tingting Zhang , Jun Lu , Yilan Liu

Conventional DNA double-strand breaks (DSBs)-inducing chemotherapeutics for acute myeloid leukemia (AML) are often limited by poor solubility, non-selectivity, and drug resistance stemming from robust tumor DNA repair mechanisms. Here, we report a glutathione (GSH)-responsive, dual-targeting nano-prodrug, designated HA-FA@Etp-Olp, for efficient AML cell eradication. The HA-FA@Etp-Olp system was constructed through the conjugation of the PARP inhibitor Olaparib (Olp) with etoposide (Etoposide) via a disulfide linkage, forming an Etp-Olp heterodimeric prodrug. This hydrophobic conjugate was encapsulated within a polymeric carrier composed of poly (ethylene glycol)-modified hyaluronic acid (HA) functionalized with folic acid (FA), self-assembling into well-refined nanoparticles. Exhibiting excellent circulatory stability, HA-FA@Etp-Olp achieved efficient accumulation within AML cells leveraging CD44/FR dual-receptor-mediated active targeting, followed by GSH-triggered disassembly and specific drug release in response to elevated intracellular GSH levels. Furthermore, HA-FA@Etp-Olp elicited a synergistic cytotoxic effect against AML through a dual-pronged mechanism: "DNA damage-repair blockade" cascade and significant augmentation of mitochondrial oxidative stress, effectively inducing apoptotic cell death. This strategy provides a promising targeted nanotherapeutic approach with enhanced efficacy and reduced systemic toxicity, demonstrating significant potential for the precise treatment of AML.

传统的DNA双链断裂（DSBs）诱导的急性髓性白血病（AML）化疗药物通常受到溶解度差、非选择性和来自强大的肿瘤DNA修复机制的耐药性的限制。在这里，我们报告谷胱甘肽（GSH）反应，双靶向纳米前药，指定HA-FA@Etp-Olp，用于有效的AML细胞根除。通过二硫键将PARP抑制剂Olaparib （Olp）与依托泊苷（etoposide）偶联，构建了HA-FA@Etp-Olp体系，形成Etp-Olp异二聚体前药。这种疏水共轭物被封装在由聚乙二醇修饰透明质酸（HA）和叶酸（FA）组成的聚合物载体中，自组装成精细的纳米颗粒。HA-FA@Etp-Olp表现出优异的循环稳定性，利用CD44/FR双受体介导的活性靶向，在AML细胞内实现了高效的积累，随后是GSH触发的分解和特异性药物释放，以响应细胞内GSH水平的升高。此外，HA-FA@Etp-Olp通过双管齐下的机制引发了抗AML的协同细胞毒性作用：“DNA损伤-修复阻断”级联和线粒体氧化应激的显著增强，有效诱导凋亡细胞死亡。该策略提供了一种有前景的靶向纳米治疗方法，具有增强的疗效和降低的全身毒性，显示出精确治疗AML的巨大潜力。

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引用次数: 0