IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-12-01 Epub 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

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 : 2025-12-01 Epub 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

Corrigendum to “Mesomorphic phases of the electrostatic complexes of amphiphilic surfactants with low-generation dendrimers” [Giant, 25 (2025) 100369] “具有低代树突状分子的两亲表面活性剂静电络合物的介形相”的勘误表[巨人，25 (2025)100369]

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-12-01 Epub Date: 2025-09-08 DOI: 10.1016/j.giant.2025.100372

Yi-Cheng Lai , Chun-Yu Chen , Chun-Jen Su , Hsin-Lung Chen

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 : 2025-12-01 Epub 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

Controlled orientation of polystyrene-b-poly(L-lactide) nanostructured thin films by air plasma treatment via thermal annealing 热退火空气等离子体处理聚苯乙烯-b-聚（l -丙交酯）纳米薄膜的取向控制

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-10-01 Epub Date: 2025-08-05 DOI: 10.1016/j.giant.2025.100367

Wen-Chi Huang , Thanmayee Shastry , Pin-Chia Chen, Ashika A P, Kang-Ping Liu, Rong-Ming Ho

This work aims to develop a new approach for controlling the orientation of nanostructured block copolymer (BCP) thin films via thermal annealing. A thin layer of polystyrene-block-poly(L-lactide) (PS-b-PLLA) thin film is prepared by spin coating followed by air plasma treatment, giving a layer with randomly crosslinked PS and PLLA. This layer will serve as a neutral substrate for the second layer of PS-b-PLLA thin film to develop perpendicular PLLA cylinder in PS matrix from the bottom of the thin film by thermal annealing. Subsequently, the second air plasma treatment is carried on the second layer of PS-b-PLLA thin film to give a topcoat neutral layer for the development of perpendicular PLLA cylinders from the top of the thin film after thermal annealing, giving film-spanning perpendicular PLLA cylinders through self-alignment process. With the degeneration of the PLLA in the PS-b-PLLA monolith, it is possible to create PS film with prolonged cylindrical nanochannels that is appealing for applications such as NanoMEMS manufacturing, membrane fabrication and templated synthesis.

本工作旨在开发一种通过热退火来控制纳米结构嵌段共聚物（BCP）薄膜取向的新方法。采用自旋镀膜和空气等离子体处理法制备了一层聚苯乙烯-嵌段聚（l -丙交酯）（PS-b-PLLA）薄膜，得到了一层随机交联的PS和PLLA。该层将作为PS-b-PLLA薄膜第二层的中性衬底，通过热退火从薄膜底部在PS矩阵中形成垂直的PLLA圆柱体。随后，对PS-b-PLLA薄膜的第二层进行二次空气等离子体处理，使热退火后的PS-b-PLLA薄膜顶部形成垂直PLLA圆柱体的面涂中性层，通过自对准过程形成跨膜垂直PLLA圆柱体。随着PS-b-PLLA单体中PLLA的退化，有可能产生具有长圆柱形纳米通道的PS膜，这对NanoMEMS制造、膜制造和模板合成等应用具有吸引力。

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引用次数: 0

Gradient hydrogels based on photo-initiated polymerization-induced self-assembly 基于光引发聚合诱导自组装的梯度水凝胶

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-10-01 Epub Date: 2025-08-13 DOI: 10.1016/j.giant.2025.100371

Yingchu Zhou , Ziqi Liu , Yi Zeng , Li Luo , Jie Chen , Diyuan Zheng , Zhao Wu , Chao Lang

Gradient materials enable performance optimization by adjusting composition or structure across one or more dimensions while minimizing interfacial incompatibility. However, current preparation procedures are often complicated, requiring multiple steps and complex post-processing. In this study, we report the fabrication of a unidirectional mechanical gradient hydrogel via a one-pot synthesis enabled by reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly (PISA). Through concurrent photo-initiated RAFT polymerization and macro-CTA end-group cleavage, compositional and structural gradients were simultaneously created based on the distance from the light source. The near-light region displays a structure of disordered spheres primarily composed of triblock copolymer, while the far-light region features bicontinuous structure with a higher homopolymer content. This gradient design results in significantly different mechanical properties such as strength, resilience, modulus, and loss factors across the hydrogel. Moreover, gradient hydrogel demonstrates exceptional impact resistance, where the soft region efficiently absorbs and dissipates energy while the hard region provides structural support. This study highlights the potential of PISA in developing high-performance gradient materials with tailored mechanical properties, offering promising applications in protective sports equipment, energy absorption systems, soft robotics, and biomedical implants.

梯度材料通过在一个或多个维度上调整成分或结构来实现性能优化，同时最大限度地减少界面不兼容性。然而，目前的制备程序往往很复杂，需要多个步骤和复杂的后处理。在这项研究中，我们报告了通过可逆加成-碎片链转移（RAFT）介导的聚合诱导自组装（PISA）一锅合成制备单向机械梯度水凝胶的方法。通过同时光引发RAFT聚合和宏观cta端基裂解，根据与光源的距离同时产生成分梯度和结构梯度。近光区表现为主要由三嵌段共聚物组成的无序球结构，远光区表现为双连续结构，均聚物含量较高。这种梯度设计导致水凝胶的力学性能显著不同，如强度、回弹性、模量和损失系数。此外，梯度水凝胶表现出优异的抗冲击性，其中软区有效地吸收和耗散能量，而硬区提供结构支撑。这项研究强调了PISA在开发具有定制机械性能的高性能梯度材料方面的潜力，在保护性运动装备、能量吸收系统、软机器人和生物医学植入物方面提供了有前途的应用。

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引用次数: 0

Mesomorphic phases of the electrostatic complexes of amphiphilic surfactants with low-generation dendrimers 低代树状大分子两亲表面活性剂静电配合物的介晶相

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-10-01 Epub Date: 2025-08-08 DOI: 10.1016/j.giant.2025.100369

Yi-Cheng Lai , Chun-Yu Chen , Chun-Jen Su , Hsin-Lung Chen

Through the microphase separation between the polar and nonpolar components, the complexation of macromolecule with an amphiphilic surfactant has the potential to construct a broad spectrum of mesomorphic phase with long-range order. This study explores the self-assembly behavior of the electrostatic complexes formed between poly(amidoamine) (PAMAM) dendrimers of generation two (G2) and generation three (G3) with two surfactants: dodecylbenzenesulfonic acid (DBSA) and sodium dodecyl sulfate (SDS). Long-range ordered lamellar structures formed in the complexes of DBSA with both PAMAM G2 and G3 dendrimers via acid-base interaction. A detailed analysis of the lamellar structure revealed that the thickness of the polar layer containing the dendrimer was virtually independent of the dendrimer generation number. This phenomenon even extended to the complexes of DBSA with PAMAM G4 and G6 dendrimers, indicating that the dendrimer molecules were in general highly compressed along the lamellar interface due to the electrostatic attraction. The complexations of protonated dendrimer systems with SDS driven by the entropic gain from counterion release yielded a higher-curvature structure, where the SDS formed cylindrical micelles packed in a 2D hexagonal lattice, as the original spherical SDS micelles merged into cylinders to enhance the charge matching with the dendrimers. The subtle variation of the relative intensities of the diffraction peaks in the small angle X-ray scattering pattern suggested that, as the binding density of the surfactant to the dendrimer increased, the cross section of the cylindrical micelle progressively deformed from nearly circular to elliptical shape to facilitate the charge matching under the hexagonal packing symmetry.

通过极性和非极性组分的微相分离，大分子与两亲性表面活性剂的络合有可能形成广谱、长阶的介晶相。本研究探讨了第二代（G2）和第三代（G3）聚氨基胺（PAMAM）树状大分子与十二烷基苯磺酸（DBSA）和十二烷基硫酸钠（SDS）两种表面活性剂之间形成的静电配合物的自组装行为。DBSA与PAMAM G2和G3树状大分子通过酸碱相互作用形成了长时间有序的层状结构。对层状结构的详细分析表明，含有树枝状分子的极层厚度实际上与枝状分子的世代数无关。这种现象甚至延伸到DBSA与PAMAM G4和G6树状大分子的配合物中，表明由于静电吸引，树状大分子沿着片层界面普遍受到高度压缩。在反离子释放的熵增益的驱动下，质子化的枝状大分子体系与SDS的络合产生了更高曲率的结构，其中SDS形成了堆积在二维六边形晶格中的圆柱形胶束，而原始的球形SDS胶束合并成圆柱形以增强与枝状大分子的电荷匹配。小角度x射线散射图中衍射峰相对强度的细微变化表明，随着表面活性剂与树状大分子结合密度的增加，柱状胶束的横截面由近圆形逐渐变形为椭圆形，有利于六边形堆积对称下的电荷匹配。

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引用次数: 0

Development of a mechanically tunable triblock copolyester with partial chemical recyclability 具有部分化学可回收性的机械可调三嵌段共聚聚酯的研制

IF 4.9 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-10-01 Epub Date: 2025-08-08 DOI: 10.1016/j.giant.2025.100370

Jiawei Wang, Hao Chen, Chenlin Pan, Jinlin He, Peihong Ni

Triblock copolymers can significantly enhance material properties due to their unique microphase separation structures and have become important candidates for the development of sustainable polymers. However, research reports on recyclable block copolyesters remain relatively limited. 3,4-Dihydro-2H-benzo [b][1,4]dioxepin-2-one (BDXO) is a renewable monomer derived from lactones, and its homopolymer exhibits excellent thermal properties and tensile strength but low flexibility. Copolymerizing various cyclic esters and leveraging their respective advantages for modification has emerged as a highly promising strategy to address this issue. In this study, a partially chemically recyclable triblock copolyesters was designed and synthesized using poly(trimethylene carbonate) (PTMC) as the soft chain and poly(3,4-dihydro-2H-benzo[b][1,4]dioxepin-2-one) (PBDXO) as the hard segment. The synthesized triblock copolyesters were characterized for their chemical structure, molecular weight, and thermal properties using proton nuclear magnetic resonance (¹H NMR), size exclusive chromatography (SEC), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Mechanical tests revealed that the mechanical strength the copolyesters can be tuned by the proportion of the soft and hard segments as well as the total molecular weight. Leveraging the disparity in ceiling temperature (T_c) between the hard and soft segments enables efficient selective chemical recycling of the PBDXO hard segment, with the PTMC soft segment being substantially remained. This offers a facile and sustainable approach to the design of recyclable block copolyesters.

三嵌段共聚物由于其独特的微相分离结构，可以显著提高材料的性能，已成为发展可持续聚合物的重要候选者。然而，关于可回收的嵌段共聚聚酯的研究报告仍然相对有限。3,4-二氢- 2h -苯并[b][1,4]二氧杂平-2- 1 （BDXO）是由内酯衍生而来的可再生单体，其均聚物具有优异的热性能和拉伸强度，但柔韧性较低。共聚各种环酯并利用其各自的优势进行改性已成为解决这一问题的一种非常有前途的策略。本研究以聚碳酸三亚甲基（PTMC）为软链，聚（3,4-二氢- 2h -苯并[b][1,4]二奥塞宾-2- 1）（PBDXO）为硬链，设计并合成了一种部分化学可回收的三嵌段共聚物。利用质子核磁共振（1H NMR）、尺寸专用色谱（SEC）、基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF MS）、热重分析（TGA）和差示扫描量热法（DSC）对合成的三嵌段共聚聚酯的化学结构、分子量和热性能进行了表征。力学试验结果表明，软段和硬段的比例以及总分子量可以调节共聚酯的机械强度。利用硬段和软段之间的上限温度（Tc）差异，PBDXO硬段可以有效地进行选择性化学回收，而PTMC软段基本上可以保留下来。这为设计可回收的块状共聚聚酯提供了一种方便和可持续的方法。

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引用次数: 0

Characterizing bound rubber of additively manufactured silicone rubber at an expanded scale: A contrast variation spin-echo small-angle neutron scattering investigation 增材制造硅橡胶粘结橡胶的扩展尺度表征：对比变化自旋回波小角中子散射研究

1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-08-05 DOI: 10.1016/j.giant.2025.100368

Jingjing Han, Xiaoqing Tu, Z. H. Qu, Kun Song, Yue Yin, Xiang Luo, A. Lu, Guangai Sun, Chengzhen Geng, Dong Liu

引用次数: 1

Stimuli-responsive antimicrobial polymer systems: From structural design to biomedical applications 刺激反应抗菌聚合物系统：从结构设计到生物医学应用

IF 5.4 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-08-01 Epub Date: 2025-07-16 DOI: 10.1016/j.giant.2025.100366

Jia Guo , Yaqi Tao , Zhen Du , Siqi Zhang , Wei Zheng , Zhibo Wang , Zhuomin Yi , Yangqing Gou , Wen Tang

Bacterial infections and drug-resistant evolution have seriously threatened public health. Stimuli-responsive antimicrobial materials have been rapidly developed to address the evolving challenges posed by multi-drug-resistant bacteria. Among various materials, polymer-based stimuli-responsive systems stand out thanks to their structural design flexibility, functional diversity, decreased systemic toxicity, and enhanced therapeutic effects compared with free drugs. In this review, we present the latest advances in stimuli-responsive antimicrobial polymer systems, summarizing their molecular structures and design principles across exogenous and endogenous stimulus types. Exogenous stimuli offer precise spatiotemporal control triggered by temperature, light, magnetic, salt, etc. Endogenous stimuli are in-situ biomarkers in the infection environment, such as pH, redox, bacterial secretions, etc. In the aim of developing antimicrobial material with high selectivity, we also summarize antimicrobial recognition strategies that enhance drug targeting efficiency. Finally, the challenges in current stimuli-responsive antimicrobial polymeric systems are discussed, opening up prospects for next-generation intelligent antimicrobial materials with enhanced efficacy, biosafety and pathogen-targeting precision.

细菌感染和耐药性演变严重威胁着公众健康。刺激反应性抗菌材料已迅速发展，以解决多重耐药细菌带来的不断变化的挑战。在各种各样的材料中，基于聚合物的刺激反应系统因其结构设计的灵活性、功能的多样性、降低全身毒性和与游离药物相比增强的治疗效果而脱颖而出。本文综述了刺激响应型抗菌聚合物系统的最新进展，总结了它们的分子结构和设计原理，涵盖了外源性和内源性刺激类型。外源刺激提供精确的时空控制，由温度、光、磁、盐等触发。内源性刺激是感染环境中的原位生物标志物，如pH、氧化还原、细菌分泌物等。为了开发具有高选择性的抗菌材料，我们还总结了提高药物靶向效率的抗菌识别策略。最后，讨论了当前刺激响应型抗菌聚合物系统面临的挑战，为下一代具有更高功效、生物安全性和病原体靶向精度的智能抗菌材料开辟了前景。

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引用次数: 0

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