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Gas-Molecular-Shearing Carbon Vacancy Defect Networks on Ni-Doped Carbon Fibers for High-Efficiency Low-Concentration CO2 Enrichment and Electrocatalytic Reduction ni掺杂碳纤维上的气体-分子剪切碳空位缺陷网络用于高效低浓度CO2富集和电催化还原
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-02-11 DOI: 10.1021/acscatal.5c08111
Jinsheng Lai,Youpeng Xiong,Aerman Habadati,Meng Li,Mei Zhang,Tianwen Fang,Ke Yi,Yuzhu Ding,Xinghuan Liu,Xin Jia
Electrocatalytic systems for low-concentration CO2 reduction still face significant challenges in the mass transport and electronic modulation of catalyst active sites. This study developed a gas-molecular shear strategy for constructing nickel single atoms (Ni SAs) and nanocluster (NC)-doped carbon nanofiber catalysts (Ni/TCNFS-10CA; CA = cyanuric acid) featuring carbon vacancy defect engineering and hierarchical porous channels, which created a microenvironment that enhances CO2 adsorption and enrichment. Density functional theory (DFT) and experimental analysis revealed the effects of carbon vacancy defect-engineered Ni NCs on Ni SAs: (1) The introduction of carbon defects can regulate the local electronic structure and pore size, thereby achieving efficient enrichment and adsorption of CO2. (2) Carbon vacancy defects can optimize the key *COOH adsorption and reduce the desorption energy of *CO. The resulting catalyst achieved a near-unity Faradaic efficiency (FE) for CO (FECO ≈100%) over a broad potential window. Notably, it maintained a high FECO of 88.2% under a 20% CO2 atmosphere. The catalyst exhibited durability exceeding 306 h (1102 cycles) in a Zn-CO2 battery and over 80 h (288 cycles) in a Zn-CO2 (20% CO2) battery. This work proposes a high-activity carbon vacancy defect engineering strategy, delivering an innovative approach for efficient ECO2RR and the direct conversion of industrial flue gases.
用于低浓度CO2还原的电催化系统在催化剂活性位点的质量传输和电子调制方面仍然面临重大挑战。本研究开发了一种气体-分子剪切策略来构建镍单原子(Ni SAs)和纳米簇(NC)掺杂的碳纳米纤维催化剂(Ni/TCNFS-10CA; CA =氰脲酸),该策略具有碳空位缺陷工程和分层多孔通道,创造了一个增强CO2吸附和富集的微环境。密度泛函理论(DFT)和实验分析揭示了碳空位缺陷工程Ni NCs对Ni SAs的影响:(1)碳空位缺陷的引入可以调节局部电子结构和孔径,从而实现对CO2的高效富集和吸附。(2)碳空位缺陷可以优化*COOH的关键吸附,降低*CO的解吸能。所得到的催化剂在较宽的电位窗口内获得了CO的接近统一的法拉第效率(FE) (FECO≈100%)。值得注意的是,在20%的二氧化碳气氛下,它保持了88.2%的高FECO。该催化剂在Zn-CO2电池中表现出超过306小时(1102次循环)的耐久性,在Zn-CO2 (20% CO2)电池中表现出超过80小时(288次循环)的耐久性。这项工作提出了一种高活性碳空位缺陷工程策略,为高效的ECO2RR和工业烟气的直接转化提供了一种创新方法。
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引用次数: 0
Self-Assembled Chiral Nanochannel Arrays with Amplified Signal for Self-Powered Enantiomer Discrimination 具有放大信号的自组装手性纳米通道阵列用于自供电对映体识别
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c18501
Hua Yang,Yichen Hou,Chao Li,Lei Jiang
Molecular chirality is significantly important for drug synthesis, material design, and other life activities. Thus, developing an efficient, convenient, and rapid technique for chiral recognition is of great industrial and physiological significance. Here, we demonstrate an electrochemical method for the sensitive real-time recognition of chiral molecules by using high-density chiral nanochannels. The chiral porphyrins direct the self-assembly of porphyrin-cored star homopolymers (p-HP) into ordered helical porphyrin arrays, providing chiral-selective nanochannels with enantioselective recognition capabilities. This well-defined assembly enables dual functionality of osmotic energy conversion and chiral molecule recognition, which is combined with a self-powered nanosensor for chiral molecule recognition. This work bridges the gap between molecular chirality and macroscopic membrane engineering, offering a sustainable platform for convenient chiral molecule recognition.
分子手性在药物合成、材料设计和其他生命活动中具有重要意义。因此,开发一种高效、方便、快速的手性识别技术具有重要的工业和生理意义。在这里,我们展示了一种利用高密度手性纳米通道对手性分子进行敏感实时识别的电化学方法。手性卟啉引导卟啉核星型均聚物(p-HP)自组装成有序的螺旋状卟啉阵列,提供具有对映选择性识别能力的手性选择性纳米通道。这种定义良好的组件具有渗透能量转换和手性分子识别的双重功能,并与自供电的纳米传感器相结合,用于手性分子识别。本研究弥补了分子手性与宏观膜工程之间的差距,为方便的手性分子识别提供了一个可持续的平台。
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引用次数: 0
Chemist-Guided Human–AI Workflow for Covalent Organic Framework Synthesis 化学家引导的人工智能工作流程共价有机框架合成
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c20068
Lihan Chen,Zhen Lu,Lin Chen,Linxi Hou,Dong Zhang
The synthesis of covalent organic frameworks (COFs) is still largely driven by chemists’ literature-informed intuition and iterative trial-and-error, which can be difficult to scale and reproduce. Here we present a chemist-guided human–AI workflow that digitizes this reasoning loop─search, hypothesis formation, and iteration─by coupling a structured literature knowledge base with retrieval-augmented large language models and experiment-aware updates. We first construct a COF synthesis knowledge base containing 2709 protocols extracted from over 800 publications. Given an unseen linker combination, the workflow retrieves a Top-K neighborhood and assembles evidence through stratified sampling and context permutation, generating a range-type synthesis prior over solvent system, catalyst, temperature, time, and stoichiometry. A diagnosis module then interprets macroscopic observations together with powder X-ray diffraction (PXRD) files using a failure taxonomy and proposes targeted updates and next-round experiments. In leave-one-out benchmarks on 60 held-out COFs, the best context-assembly and self-consensus settings improve solvent–catalyst hit rates from baseline levels to up to 0.83, supporting robust transfer beyond individual case studies. We demonstrate the workflow by synthesizing two fluorinated COFs, TAPPy-4F and TAPPy-8F, both exhibiting crystallinity and permanent porosity. By simulating the chemist’s reasoning loop, this human-AI system integrates expert knowledge with model-driven exploration, offering a generalizable and scalable paradigm for the rational design of complex reticular materials.
共价有机框架(COFs)的合成在很大程度上仍然是由化学家的文献直觉和反复的试错来驱动的,这很难扩展和复制。在这里,我们提出了一个由化学家指导的人类-人工智能工作流,通过将结构化文献知识库与检索增强的大型语言模型和实验感知更新相结合,将这个推理循环──搜索、假设形成和迭代──数字化。我们首先构建了一个COF合成知识库,其中包含从800多篇出版物中提取的2709个协议。给定一个看不见的连接物组合,工作流程检索Top-K邻域,并通过分层采样和上下文排列收集证据,生成一个范围型合成,优先于溶剂系统、催化剂、温度、时间和化学计量学。然后,诊断模块使用故障分类法解释宏观观察结果以及粉末x射线衍射(PXRD)文件,并提出有针对性的更新和下一轮实验。在60个持有COFs的留一基准测试中,最佳情境组合和自我共识设置将溶剂催化剂的命中率从基线水平提高到0.83,支持超越个别案例研究的强大转移。我们通过合成两种氟化COFs, TAPPy-4F和TAPPy-8F来演示该工作流程,这两种COFs都具有结晶性和永久孔隙性。通过模拟化学家的推理循环,这个人类-人工智能系统将专家知识与模型驱动的探索相结合,为复杂网状材料的合理设计提供了一个可推广和可扩展的范例。
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引用次数: 0
Ultrafine Sub-1 nm One-Dimensional Coordination Polymer Nanowires for Boosting Photocatalytic Functionalization of Inert C(sp3)–H Bonds 超细亚1nm一维配位聚合物纳米线促进惰性C(sp3) -H键光催化功能化
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c21627
Songtao Liu,Guanfeng Ji,Yefei Wang,Liang Zhao,Cheng He,Chunhong Liu,Chunying Duan
The heterogenization of molecular catalysts to be compatible with industrialization demands still faces great challenges. In this work, we demonstrate for the first time that the activity of a molecular catalyst is unrestricted when installed in nanostructured coordination polymers (CPs). CPs that can be used to obtain ultrafine nanowires by ultrasound exfoliation are extremely limited. We illustrate that chain-like CPs can be designed using electrostatic ligand-capped low-coordination-number metal ions and electropositive ligands as building blocks. This guides the preparation of the three-dimensional (3D) chain-like CPs from chloride ion-capped Cu-based chromophores and 1,1’-(1,4-phenylenebis(methylene))bis(3-carboxy quinolin-1-ium) chloride; subsequently, ultrafine sub-1 nm nanowires were obtained via ultrasound exfoliation. The formed ultrafine sub-1 nm CP nanowires demonstrate high activity enhancement for functionalization of C(sp3)−H bonds with conversion being significantly increased for alkylation, thiolation, and oxidation of C(sp3)−H bonds after exposure to external surfaces of the flexible nanowires. Therefore, the observed activity increases in the order CuCl2 < bulk CP crystals < CP nanowires in functionalization of C(sp3)−H bonds. This work not only provides a strategy for constructing chain-like CPs and their ultrafine nanowires but also paves the way for expanding the diversity of the ultrafine 1D CP nanowires.
与工业化要求相适应的分子催化剂的多相化仍面临着很大的挑战。在这项工作中,我们首次证明了当分子催化剂安装在纳米结构配位聚合物(CPs)中时,其活性是不受限制的。可通过超声剥离获得超细纳米线的CPs非常有限。我们证明了可以使用静电配体覆盖的低配位数金属离子和正电配体作为构建块来设计链状CPs。这指导了由氯离子覆盖的cu基发色团和1,1 ' -(1,4-苯基双(亚甲基))双(3-羧基喹啉-1-ium)氯制备三维(3D)链状CPs;随后,通过超声剥离获得超细的亚1 nm纳米线。形成的超细亚1nm CP纳米线对C(sp3)−H键的功能化表现出很高的活性增强,暴露在柔性纳米线的外表面后,C(sp3)−H键的烷基化、硫代化和氧化转化显著增加。因此,在C(sp3)−H键的功能化过程中,观察到的活性按照CuCl2 <块状CP晶体< CP纳米线的顺序增加。这项工作不仅为构建链状CP及其超细纳米线提供了一种策略,而且为扩大超细1D CP纳米线的多样性铺平了道路。
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引用次数: 0
Construction of Heterocyclic-Triazolopyrimidine Framework for Energetic Compounds: High-Energy, Low-Sensitivity Explosives 高能、低灵敏度炸药含能化合物杂环-三唑嘧啶骨架的构建
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-11 DOI: 10.1021/acs.orglett.6c00128
Lei Zhao,Chungui Xue,Caijin Lei,Jie Tang,Wei Hu,Mengya Wan,Chuan Xiao,Guangbin Cheng,Hongwei Yang
This study reports the synthesis of three novel heterocycle triazolopyrimidine compounds with vicinal amino-nitro groups by introducing dinitropyrazole, nitrooxadiazole, and trinitromethyl groups into the fused-ring framework, respectively. Target compounds 3, 6, and 9 were obtained by subjecting substrates 1, 4, and 7, respectively, to a nucleophilic substitution cyclization reaction with 3,3-diethoxypropionitrile, followed by a nitration step. Among them, 2-(4,5-dinitro-1H-pyrazol-3-yl)-6-nitro-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (3) and 6-nitro-2-(4-nitro-1,2,5-oxadiazol-3-yl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (6) exhibited moderate detonation performance (Dv = 7769 m·s–1and P = 25.1 GPa ; Dv = 8258 m·s–1 and P = 29.4 GPa), low sensitivity (IS = 30 and 24 J; FS = 288 and 240 N) and high thermal stability (Td = 277 and 263 °C). Even more outstanding is 6-nitro-2-(trinitromethyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (9), which exhibits detonation performance (Dv = 8716 m·s–1) close to that of the classic explosive cyclotrimethylenetrinitramine (RDX: Dv = 8795 m·s–1, IS = 7.5 J, FS = 120 N), but exhibiting lower sensitivity (IS = 16 J, FS = 168 N), making it highly promising as a novel high-energy, low-sensitivity energetic material. This work expands their potential applications as high-energy, low-sensitivity explosives.
本研究报道了通过在融合环框架中分别引入二硝基吡唑、硝基恶二唑和三硝基甲基,合成了三种新型的邻氨基硝基杂环三唑嘧啶化合物。底物1、4和7分别与3,3-二氧基丙腈进行亲核取代环化反应,然后进行硝化反应,得到目标化合物3、6和9。其中,2 - (4 5-dinitro-1H-pyrazol-3-yl) 6-nitro -(1、2、4)triazolo(1、5)pyrimidin-7-amine(3)和6-nitro-2——(4-nitro-1 2 5-oxadiazol-3-yl) -(1、2、4)triazolo(1、5)pyrimidin-7-amine(6)表现出温和的爆轰性能(Dv = 7769 m·s-1and P = 25.1的绩点,Dv = 8258 m·s - 1, P = 29.4 GPa),低灵敏度(24 J = 30, FS = 288和240 N)和高的热稳定性(Td = 277和263°C)。更为突出的是6-硝基-2-(三硝基甲基)-[1,2,4]三唑[1,5-a]嘧啶-7-胺(9),其爆轰性能(Dv = 8716 m·s-1)接近经典炸药环三甲基三硝胺(RDX: Dv = 8795 m·s-1, is = 7.5 J, FS = 120 N),但灵敏度较低(is = 16 J, FS = 168 N),是一种很有前景的新型高能量、低灵敏度能材料。这项工作扩大了它们作为高能量、低灵敏度炸药的潜在应用。
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引用次数: 0
Unlabeled NMR Approach with Site-Specific Methyl Assignments for Structural Evaluation of the IgG1 Fc Region IgG1 Fc区结构评价的位点特异性甲基分配的无标记核磁共振方法
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c18997
Saeko Yanaka,Yuuki Koseki,Yohei Miyanoiri,Toshio Yamazaki,Tsutomu Terauchi,Daichi Kaneko,Yukiko Isono,Kohei Tomita,Sachiko Kondo,Masayoshi Onitsuka,Maho Yagi-Utsumi,Hirokazu Yagi,Akiko Ishii-Watabe,Koichi Kato
Monoclonal antibodies are the cornerstone biopharmaceuticals whose safety and efficacy critically depend on their higher-order structure (HOS). Nuclear magnetic resonance (NMR) spectroscopy has emerged as a promising tool for HOS evaluation, yet its application has largely relied on fingerprinting approaches without residue-level interpretation. Here, we report site-specific assignments of methyl resonances in the Fc region of human IgG1, established through amino acid-selective labeling and correlation with backbone resonances using scalar coupling and NOE connectivities, further supported by mutagenesis. These assignments allowed us to identify glycoform-dependent spectral variations, including distinct signatures of core fucosylation and terminal galactosylation, as well as an Fc-specific amino acid substitution. Importantly, these spectral probes were detectable even in antibodies at natural isotopic abundance, enabling practical applications to therapeutic products without isotopic labeling. Furthermore, dynamic filtering highlighted methyl resonances from hinge and receptor-binding residues with elevated mobility, providing localized insights into functional sites. Collectively, our results establish unlabeled methyl NMR as a robust platform for sensitive and practical HOS assessment of therapeutic antibodies. This approach is broadly applicable to monitor glycosylation heterogeneity, chemical modifications, and batch-to-batch consistency, thereby offering a valuable framework for development and quality control of both innovative biopharmaceuticals and biosimilars.
单克隆抗体是生物制药的基石,其安全性和有效性主要取决于其高阶结构。核磁共振(NMR)波谱已成为一种很有前途的HOS评估工具,但其应用在很大程度上依赖于没有残留物水平解释的指纹识别方法。在这里,我们报告了人类IgG1 Fc区域甲基共振的位点特异性分配,通过氨基酸选择性标记和使用标量耦合和NOE连通性与骨干共振的相关性建立,并进一步得到突变的支持。这些分配使我们能够识别糖形依赖的光谱变化,包括核心聚焦化和末端半乳糖基化的不同特征,以及fc特异性氨基酸取代。重要的是,这些光谱探针甚至可以在天然同位素丰度的抗体中检测到,从而使实际应用于没有同位素标记的治疗产品。此外,动态过滤突出了铰链和受体结合残基的甲基共振,具有更高的迁移率,提供了对功能位点的局部见解。总的来说,我们的结果建立了未标记的甲基核磁共振作为敏感和实用的治疗性抗体HOS评估的强大平台。该方法广泛适用于监测糖基化异质性、化学修饰和批次间一致性,从而为创新生物制药和生物仿制药的开发和质量控制提供了有价值的框架。
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引用次数: 0
Determination of selected gadolinium-based contrast agents in soil: method validation and application. 土壤中选定钆基造影剂的测定:方法验证和应用。
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-02-11 DOI: 10.1007/s00216-026-06389-2
A F Roig-Navarro, F Soria-Prieto, E Pitarch, R García-Cubedo

The increasing use of reclaimed water for agricultural irrigation raises concerns about the environmental accumulation of persistent contaminants, including gadolinium-based contrast agents (GBCAs). These compounds, widely used in medical imaging, are excreted unmetabolized and poorly removed by conventional wastewater treatment plants, leading to their release into aquatic environments and potential accumulation in soils and crops. In this study, a method was developed, validated, and applied-for the first time-for the determination of three commonly used GBCAs-gadoteric acid, gadoteridol, and gadobutrol-in clay soil. Quantification was achieved by ion chromatography coupled to inductively coupled plasma mass spectrometry (IC-ICP-MS). Suitable separation was accurately optimized using a mobile phase containing 30 mM EDTA and 20 mM NH4NO3 at pH 9.8. Elution of all target species was achieved within 7.5 min. The method was evaluated using real clay soil samples from an agricultural field in Castelló (Spain) fortified with selected GBCAs at various concentrations. Mild extraction with NH4NO3 yielded recoveries below 50%, which allows assessment of the bioavailable fraction. To achieve quantitative recovery, a more severe alkaline extraction protocol using KOH was subsequently developed. The optimized procedure demonstrated excellent analytical performance, with LOD and LOQ below 2 and 5 ng g-1, respectively. This methodology enabled the first quantitative determination of GBCAs in soil samples collected from municipal parks irrigated with reclaimed water. Furthermore, the KOH-based extraction was extended to the quantification of gadoteric acid in peat substrates from greenhouse-scale cultivation trials, yielding a mean recovery of 80% with a relative standard deviation (RSD) of 12%. The application of this method confirmed the accumulation of the contrast agent in peat irrigated with fortified tap water. These findings underscore the necessity for robust, matrix-specific analytical workflows to monitor the environmental fate of GBCAs and to accurately assess their potential transfer into the food chain.

越来越多地使用再生水用于农业灌溉,引起了人们对持久性污染物(包括钆基造影剂(gbca))在环境中积累的担忧。这些广泛用于医学成像的化合物未经代谢就被排出体外,传统的废水处理厂也很难去除它们,导致它们释放到水生环境中,并可能在土壤和作物中积累。在这项研究中,首次开发、验证并应用了一种方法来测定粘土中常用的三种gbcas——gadoteracid, gadoteridol和gadobutrol。定量采用离子色谱-电感耦合等离子体质谱法(IC-ICP-MS)。采用含30 mM EDTA和20 mM NH4NO3的流动相,pH为9.8,精确优化了最佳分离条件。所有目标物种的洗脱在7.5 min内完成。该方法使用来自Castelló(西班牙)农田的真实粘土样品进行了评估,这些样品中添加了不同浓度的选定的gbca。用NH4NO3进行温和萃取,回收率低于50%,从而可以评估生物可利用部分。为了实现定量回收,随后开发了一种使用KOH的更严格的碱性提取方案。优化后的方法具有良好的分析性能,LOD和LOQ分别小于2和5 ng g-1。该方法首次实现了再生水灌溉市政公园土壤样品中gbca的定量测定。此外,将该方法扩展到温室栽培试验中泥炭基质中钆的定量提取,平均回收率为80%,相对标准偏差(RSD)为12%。该方法的应用证实了用强化自来水灌溉泥炭时造影剂的积累。这些发现强调了建立强大的、针对特定基质的分析工作流程的必要性,以监测gbca的环境命运,并准确评估它们进入食物链的可能性。
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引用次数: 0
Hybrid membrane-camouflaged nanomedicines for precision oncology: rational design, mechanism innovation, and diversified applications 用于精准肿瘤的混合膜伪装纳米药物:合理设计、机制创新、多样化应用
IF 20.6 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-11 DOI: 10.1016/j.ccr.2026.217681
Shuyao Cai, Zhenghui Chen, Yaoyao Lv, Dongdong Xu, Yang Li, Shouchun Yin
The clinical translation of cancer nanomedicine is significantly impeded by biological barriers, including rapid immune clearance, the heterogeneous tumor microenvironment (TME), and the limited efficacy of passive targeting. While single-source cell membrane coatings offer partial solutions, they are often constrained by functional incompleteness. The emergence of hybrid membrane-camouflaged nanomedicines (HMCNs), fabricated by fusing membranes from distinct cell types, represents a paradigm shift. This biomimetic strategy ingeniously engineers bio-interfaces that synergistically integrate multifunctional properties, such as prolonged circulation, active targeting, and TME modulation, thereby overcoming the limitations of single-membrane systems. This review systematically deconstructs the rational design principles governing HMCNs, emphasizing source cell selection based on functional complementarity to avoid signal conflict. We further delve into mechanism-driven engineering, exploring advanced fusion methodologies and characterization techniques essential for ensuring structural and functional fidelity. The functional diversification of HMCNs is highlighted through their application in multimodal synergistic therapies (e.g., photothermal-immunotherapy, chemo-gene therapy) and intelligent theranostic platforms. Finally, we critically discuss prevailing challenges in batch consistency and scalable production, and envision future directions, including smart stimulus-responsive systems, AI-aided design, and patient-specific nanoplatforms. By bridging biology, chemistry, and materials science, HMCNs establish a versatile and potent paradigm for next-generation cancer therapeutics.
肿瘤纳米药物的临床转化受到生物屏障的严重阻碍,包括快速免疫清除、异质性肿瘤微环境(TME)和被动靶向的有限疗效。虽然单源细胞膜涂层提供了部分解决方案,但它们往往受到功能不完整的限制。混合膜伪装纳米药物(HMCNs)的出现,通过融合不同细胞类型的膜来制造,代表了一种范式转变。这种仿生策略巧妙地设计了生物界面,协同集成了多功能特性,如延长循环,主动靶向和TME调制,从而克服了单膜系统的局限性。本文系统地解构了控制hmcn的合理设计原则,强调基于功能互补性的源细胞选择以避免信号冲突。我们进一步深入研究机制驱动工程,探索先进的融合方法和表征技术,以确保结构和功能的保真度。通过在多模式协同治疗(如光热-免疫治疗、化学-基因治疗)和智能治疗平台中的应用,hmcn的功能多样化得到了强调。最后,我们批判性地讨论了批量一致性和可扩展生产中普遍存在的挑战,并展望了未来的方向,包括智能刺激响应系统,人工智能辅助设计和患者特定的纳米平台。通过连接生物学,化学和材料科学,hmcn为下一代癌症治疗建立了一个多功能和有效的范例。
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引用次数: 0
Nanozyme fabrication based on magnetic COFs and gold nanorods and its SERS detection of zearalenone 基于磁性COFs和金纳米棒的纳米酶制备及其对赤霉烯酮的SERS检测
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-11 DOI: 10.1016/j.aca.2026.345229
Xiaoyuan Ma, Xi Ma, Muxi Zhang, Jinchi Han, Zhouping Wang

Background

As one of the most common mycotoxins, Zearalenone (ZEN) not only contaminates cereal crops but also exists in processed grain products for its chemical stability. After entering human body through the food chain, ZEN exhibits remarkable bioaccumulation properties, which poses varying degrees of harmful effects to human health. The traditional chromatography instrumental methods require expensive equipment and complex experimental procedures. The aim of this manuscript is to develop a facile and accurate method for ZEN detection in food samples.

Results

Here, a SERS platform was developed for ZEN detection using COF and noble metal nanomaterial with nitroreductase (NTR)-like activity. First, magnetic COF loaded with gold nanoparticles (MCOF-Au) were synthesized as SERS enhancement substrates with partial NTR activity. Simultaneously, palladium-loaded dumbbell-shaped gold nanorods (AuNR/Pd) were prepared and served as the primary NTR in the 4-NTP/NaBH4 system, significantly enhancing both catalytic activity and SERS signal. After nucleic acid functionalization, the two components assembled. The addition of ZEN regulated the assemble of AuNR/Pd on MCOF-Au. Following magnetic separation, the catalytic and SERS activities changed in the precipitate. Using the Raman peak of the output product 4-ATP at 390 cm-1 as the quantitative marker, the method showed a linear range in 0.001 μg/kg-1000 μg/kg. The LOD was calculated as 1.88×10-4 μg/kg, and spiked recoveries in wheat flour and corn ranged from 88.91% to 115.78%, demonstrating high sensitivity and reliability for real-sample detection.

Significance

This aptasensor integrates the high sensitivity of Raman signals with the selectivity of aptamers, providing a robust and efficient tool for accurate ZEN detection in food. COF based nanocomposites are proved to have remarkable NTR activity and the catalytic product 4-ATP exhibits prominent Raman signal, making it suitable for quantitative detection. This design offers a versatile platform for food safety monitoring and public health protection.
玉米赤霉烯酮(ZEN)作为最常见的真菌毒素之一,不仅污染谷类作物,而且因其化学稳定性而存在于谷类加工产品中。ZEN通过食物链进入人体后,表现出显著的生物蓄积特性,对人体健康造成不同程度的有害影响。传统的色谱仪器方法需要昂贵的设备和复杂的实验程序。本文的目的是开发一种简便、准确的食品样品中ZEN检测方法。结果利用COF和具有类似硝基还原酶(NTR)活性的贵金属纳米材料,建立了一种检测ZEN的SERS平台。首先,合成了负载金纳米颗粒的磁性碳纳米管(MCOF-Au)作为具有部分NTR活性的SERS增强底物。同时,制备了负载钯的哑铃形金纳米棒(AuNR/Pd),作为4-NTP/NaBH4体系中的一级NTR,显著增强了催化活性和SERS信号。核酸功能化后,两个组分组装。ZEN的加入调节了unr /Pd在MCOF-Au上的组装。磁分离后,沉淀中的催化活性和SERS活性发生了变化。以输出产物4-ATP在390 cm-1处的拉曼峰为定量标记,该方法在0.001 μg/kg ~ 1000 μg/kg范围内呈线性关系。LOD为1.88×10-4 μg/kg,在小麦粉和玉米中加标回收率为88.91% ~ 115.78%,具有较高的检测灵敏度和可靠性。该适体传感器将拉曼信号的高灵敏度与适体的选择性相结合,为食品中ZEN的精确检测提供了一种强大而高效的工具。COF基纳米复合材料具有显著的NTR活性,催化产物4-ATP表现出显著的拉曼信号,适合于定量检测。本设计为食品安全监测和公共卫生保护提供了一个多功能平台。
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引用次数: 0
Enhancing Photocatalytic Propane Dehydrogenation via Electronic Structure Modulation of Platinum Sites Over Platinum-Based Alloys 通过铂基合金上铂位的电子结构调制增强光催化丙烷脱氢
IF 16.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1002/anie.202524711
Chi Duan, Jiaqi Zhao, Run Shi, Jinjia Liu, Li-Ping Zhang, Li-Zhu Wu, Zhenhua Li, Tierui Zhang
Photocatalytic propane dehydrogenation (PDH) offers a promising route for propylene production under mild conditions despite the unsatisfactory propylene yield at present. Herein, we have introduced several second metals into Pt/ZnO catalyst to modulate the electronic structure of Pt by forming PtM alloys. Among all these catalysts, PtPb alloys/ZnO catalyst (PtPb/ZnO) exhibits the optimum photocatalytic PDH activity. Both experiments and density functional theory calculations reveals that PtPb alloys significantly increases the electron density of Pt, weakening the interaction between Pt and propylene. This facilitates the desorption of the produced propylene during photocatalytic PDH, thus helping to release Pt active sites for reactant conversion. A 3.6-fold increase on propylene yield of photocatalytic PDH has been achieved over PtPb/ZnO with a propylene production rate of 5.4 mmol g−1 h−1. Our findings highlight the critical relationship between the electronic structure of Pt active sites and performance, marking product desorption modulation an effective strategy to boost photocatalytic PDH.
光催化丙烷脱氢(PDH)在温和条件下生产丙烯是一条很有前途的途径,但目前丙烯收率并不理想。在此,我们在Pt/ZnO催化剂中引入了几种第二金属,通过形成PtM合金来调节Pt的电子结构。其中,PtPb合金/ZnO催化剂(PtPb/ZnO)具有最佳的光催化PDH活性。实验和密度泛函理论计算均表明,PtPb合金显著提高了Pt的电子密度,减弱了Pt与丙烯的相互作用。这有利于在光催化PDH过程中产生的丙烯的解吸,从而有助于释放Pt活性位点进行反应物转化。光催化PDH的丙烯产率为5.4 mmol g−1 h−1,比PtPb/ZnO的丙烯产率提高了3.6倍。我们的发现强调了Pt活性位点的电子结构与性能之间的关键关系,标志着产物解吸调制是促进光催化PDH的有效策略。
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