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

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

GIANT

Pub 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。

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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 : 2025-09-08 DOI: 10.1016/j.giant.2025.100372

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

引用次数: 0

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 : 2025-08-13 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 : 2025-08-08 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 : 2025-08-08 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

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 : 2025-08-05 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

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 : 2025-07-16 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

Nanotechnology-based theranostics for bone tumors 基于纳米技术的骨肿瘤治疗

IF 5.4 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-07-16 DOI: 10.1016/j.giant.2025.100365

Wenwen Zhan , Shuyan Zeng , Lin Yang , Ye-Zhong Zhang , Jing Zhang

Bone tumors, particularly osteosarcoma and metastatic lesions, present significant challenges in current diagnostic and therapeutic approaches, often failing to meet patients’ expectations for quality of life. Recent rapid advancements in nanotechnology have introduced diverse and more effective strategies for the management of bone tumors. This review comprehensively examines the applications of nanomedicine in bone oncology, with a focused discussion on emerging developments and future prospects in imaging modalities, image-guided therapies, and targeted therapeutics. Each section critically evaluates the strengths and limitations of existing diagnostic and treatment protocols, aiming to provide innovative perspectives and methodologies for clinical management of bone tumors. The synthesis of these insights seeks to bridge current technological gaps and advance precision medicine in musculoskeletal oncology.

骨肿瘤，特别是骨肉瘤和转移性病变，在目前的诊断和治疗方法中提出了重大挑战，往往不能满足患者对生活质量的期望。近年来，纳米技术的快速发展为骨肿瘤的治疗带来了多样化和更有效的策略。本文综述了纳米医学在骨肿瘤学中的应用，重点讨论了成像方式、图像引导治疗和靶向治疗的新兴发展和未来前景。每个部分都批判性地评估现有诊断和治疗方案的优势和局限性，旨在为骨肿瘤的临床管理提供创新的观点和方法。这些见解的综合旨在弥合目前的技术差距和推进精确医学在肌肉骨骼肿瘤学。

引用次数: 0

Low-field NMR for polymer science 聚合物科学的低场核磁共振

IF 5.4 1区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

GIANT

Pub Date : 2025-07-13 DOI: 10.1016/j.giant.2025.100364

Xiaojie Chen , Chengyan Li , Lei Wu , Shaojie Yan , Lingxun Qi , Junfei Chen , Wei Chen

Owing to its low-cost maintenance and easy adaptability, low-field NMR (LF-NMR), which is developed based on permanent magnets, has attracted increasing attention in recent decades. It shows great potential for fundamental research as well as quality assessment and control in the industry. In this review, we first present the key hardware features of LF-NMR, including magnets, radiofrequency (RF) coils, spectrometers, and hyphenated units. Subsequently, commonly used pulse sequences and basic theoretical treatments are summarized. The applications of LF-NMR in polymer science are discussed in detail, including chain dynamics, polymer networks, and hierarchical morphologies. The multiphase and multicomponent features of polymers make polymer science a suitable area for developing new LF-NMR techniques. A personal perspective on the further development of LF-NMR is also presented.

基于永磁体的低场核磁共振技术（low-field NMR，简称fl -NMR）由于其维护成本低、适应性强等优点，近年来受到越来越多的关注。它在基础研究和行业质量评估和控制方面显示出巨大的潜力。在这篇综述中，我们首先介绍了LF-NMR的主要硬件特征，包括磁体，射频（RF）线圈，光谱仪和连字符单元。总结了常用的脉冲序列和基本的理论处理方法。详细讨论了LF-NMR在聚合物科学中的应用，包括链动力学、聚合物网络和层次形貌。聚合物的多相和多组分特性使聚合物科学成为开发新型LF-NMR技术的合适领域。并对LF-NMR的进一步发展提出了个人的看法。

引用次数: 0

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