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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
NaturIL Gels: Gels Formed from the Synergy of Alginates and Bioderived Ions. Tunable Gels from Seaweed 天然凝胶:海藻酸盐和生物衍生离子协同作用形成的凝胶。海藻可调凝胶
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/acssuschemeng.5c11739
Patrick A. Bailie,Pamela J. Walsh,Andrew C. Marr,Patricia C. Marr
A class of NaturIL gels was prepared from alginate and ionic liquids containing ions that can be derived from nature. Aqueous Cholinium Amino Acid Ionic Liquids (ChAAILs) solutions with sodium alginate derived from Laminaria digitata were cross-linked by calcium ions and the variation of rheological properties investigated relative to the parent hydrogel. Viscoelastic gels were formed for the four amino acid anions [Pro], [Gly], [Lys] and [Val] and their rheological properties were compared to those of an analogous hydrogel. All four were found to be stiffer and more viscoelastic than the hydrogel and have properties that varied as the amino acid anion was changed.
以海藻酸盐和含有天然离子的离子液体为原料制备了一类天然凝胶。研究了从海带中提取的胆碱氨基酸离子液体(ChAAILs)溶液与海藻酸钠的交联,并研究了其相对于母体水凝胶的流变性能变化。将四个氨基酸阴离子[Pro], [Gly], [Lys]和[Val]形成粘弹性凝胶,并将其流变性能与类似的水凝胶进行比较。所有四种都被发现比水凝胶更硬,更粘弹性,并且随着氨基酸阴离子的改变而具有不同的性质。
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引用次数: 0
Stereochemical and Structural Characterization of Methionine Oxidation in the IgG1 Fc Region by Integrated NMR and LC-MS Analysis 综合NMR和LC-MS分析IgG1 Fc区蛋氨酸氧化的立体化学和结构表征
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-11 DOI: 10.1021/acs.analchem.5c06092
Maho Yagi-Utsumi,Saeko Yanaka,Noritaka Hashii,Kohei Tomita,Takashi Misawa,Yosuke Demizu,Akiko Ishii-Watabe,Koichi Kato
Monoclonal antibodies are widely used biotherapeutics, whose efficacy and pharmacokinetics critically depend on their structural integrity. Among chemical degradation pathways, methionine oxidation is a particularly important post-translational modification that compromises antibody stability, Fc receptor binding, and thereby FcRn-mediated recycling and FcγR-mediated effector functions. However, the structural consequences of oxidation remain poorly understood, largely due to the subtle and localized nature of the modification. Here, we present an integrated analytical framework combining methyl-based NMR spectroscopy, selective enzymatic reduction, and peptide mapping to resolve methionine oxidation in the Fc region of human IgG1 antibodies at residue- and stereochemical-level resolution. By selectively labeling methionine methyl groups, we monitored oxidation-induced spectral changes in conserved Fc residues Met252 and Met428. Site-directed mutagenesis revealed a mutual influence between these residues, consistent with their spatial proximity at the CH2–CH3 domain interface. Stereospecific reduction with methionine sulfoxide reductase A enabled the assignment of R- and S-isomers, while peptide mapping by liquid chromatography–mass spectrometry corroborated the NMR findings. This combined approach demonstrated that Met252, which is solvent-exposed, is more susceptible to oxidation than buried Met428 and that both residues display stereochemical heterogeneity that modulates local structure. By bridging chemical modifications and higher-order structural perturbations, this integrated framework provides mechanistic insights into how methionine oxidation impairs antibody function. More broadly, it establishes a basis for quality assurance and rational design of therapeutic antibodies with improved stability.
单克隆抗体是广泛应用的生物治疗药物,其疗效和药代动力学关键取决于其结构完整性。在化学降解途径中,甲硫氨酸氧化是一种特别重要的翻译后修饰,它会影响抗体的稳定性、Fc受体的结合,从而影响fcrn介导的再循环和Fcγ r介导的效应物功能。然而,氧化的结构后果仍然知之甚少,很大程度上是由于修饰的微妙和局部性质。在这里,我们提出了一个综合的分析框架,结合甲基核磁共振光谱,选择性酶还原和肽定位,以残基和立体化学水平分辨率解决人IgG1抗体Fc区域的甲硫氨酸氧化。通过选择性标记蛋氨酸甲基,我们监测了氧化诱导的保守Fc残基Met252和Met428的光谱变化。位点定向诱变揭示了这些残基之间的相互影响,这与它们在CH2-CH3结构域界面上的空间接近一致。蛋氨酸亚砜还原酶A的立体特异性还原使R-和s -异构体的分配成为可能,而液相色谱-质谱法的肽图谱证实了核磁共振的发现。这种综合方法表明,暴露于溶剂中的Met252比埋藏的Met428更容易被氧化,并且两种残留物都显示出调节局部结构的立体化学异质性。通过桥接化学修饰和高阶结构扰动,这个集成框架提供了蛋氨酸氧化如何损害抗体功能的机制见解。更广泛地说,它为质量保证和合理设计具有更高稳定性的治疗性抗体奠定了基础。
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引用次数: 0
Cu-Catalyzed Atroposelective Protoboration of Allenes to Access Stereodefined Tetrasubstituted Axially Chiral Alkenylboronates 铜催化的炔基硼酸酯的亲硼化反应制备立体四取代轴向手性硼烯酸酯
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-11 DOI: 10.1021/acs.orglett.6c00026
Baoli Li,Zhan Huang,Shichao Hong,Liangzhi Pang,Yan Wu,Xuechen Li,Hao Li,Hua-Jie Jiang,Jie Yu,Xue Zhang,Qiankun Li
Alkenylboronates represent a cornerstone functional group in modern organic synthesis owing to their versatile reactivity in Suzuki–Miyaura cross-coupling reactions and other key transformations. However, catalytic asymmetric methods for producing stereodefined tetrasubstituted axially chiral alkenylboronates remain underdeveloped. Here, we report a copper-catalyzed atroposelective protoboration of allenes, providing a facile strategy to access tetrasubstituted axially chiral Z-alkenylboronates with excellent regio- and atroposelectivities. The enantiomerically enriched axially chiral alkenylboronates could be further transformed into diverse stereodefined tetrasubstituted axially chiral olefins via the cross-coupling reaction of the C–B bond. This methodology also provides a new avenue to construct C–C or C–N axially chiral alkene–phosphine frameworks.
烯基硼酸盐由于其在Suzuki-Miyaura交叉偶联反应和其他关键转化中的多用途反应性而成为现代有机合成中的基石官能团。然而,不对称催化合成立体四取代轴手性硼烯酸酯的方法尚不发达。在这里,我们报道了一种铜催化的烯丙烯的芳香选择原硼酸盐,提供了一种简单的策略来获得具有优异的区域和芳香选择性的轴手性四取代z -烯基硼酸盐。对映体富集的轴手性硼烯酸酯可通过C-B键的交叉偶联反应进一步转化为各种立体四取代轴手性烯烃。该方法也为构造C-C或C-N轴向手性烯烃-膦骨架提供了新的途径。
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引用次数: 0
Pr3+-Doped WO3 1D Yoga-Pillar-Shaped Nanorod Gas Sensor: A High-Performance Ppb-Level Triethylamine Gas Sensor for Fish Freshness Monitoring Pr3+掺杂wo31d瑜伽柱状纳米棒气体传感器:用于鱼类新鲜度监测的高性能ppb级三乙胺气体传感器
IF 8.9 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-11 DOI: 10.1021/acssensors.5c03942
Jiale Wang,Xiang Zhao,Xiang Li,Rundong Xue,Dan Li,Feng Li,Ying Yang,Tianqi Wang,Duanduan Yin,Xiangting Dong
Traditional triethylamine (TEA) gas sensors suffer from the drawback of high detection limits due to the low charge-transfer ability of materials. Herein, the Pr3+-doped WO3 one-dimensional (1D) yoga-pillar-shaped nanorods have been successfully synthesized via electrostatic spinning and oxidative calcination. The gas sensor based on WO3:1%Pr3+ 1D yoga-pillar-shaped nanorods exhibits excellent performance in terms of rapid response (3-fold), higher response (3.75-fold), and lower detection limits compared with the WO3 gas sensor. Furthermore, the sensor features excellent repeatability and long-term stability, indicating the potential commercial value. The findings reveal that doping Pr3+ is one of the effective strategies to improve the gas-sensing performance of WO3. Based on the above analysis, as well as literature reports, the gas-sensing mechanism is explored systematically. The enhancement can be attributed to the formation of impurity energy levels, which can effectively optimize the band structure and facilitate electron transfer. The recombination between electrons in the conduction band and holes in the valence band is partly suppressed, providing more opportunities for electron exchange between WO3 and oxygen molecules. The content of chemically adsorbed oxygen on the WO3 surface has significantly increased, which is one of the fundamental reasons for the improvement in gas sensitivity. In addition, the practical value of the WO3:1%Pr3+ 1D yoga-pillar-shaped nanorod gas sensor is demonstrated by testing the freshness of fish stored under various conditions. This work presents a high-performance ppb-level TEA detection method and broadens the application scope of WO3 gas sensors.
传统的三乙胺(TEA)气体传感器由于材料的电荷转移能力低,存在检测限高的缺点。本文通过静电纺丝和氧化煅烧,成功合成了Pr3+掺杂的WO3一维瑜伽柱状纳米棒。基于WO3:1% pr3 + 1D瑜伽柱状纳米棒的气体传感器与WO3气体传感器相比,具有快速响应(3倍)、高响应(3.75倍)和低检出限的优异性能。此外,该传感器具有出色的可重复性和长期稳定性,表明潜在的商业价值。研究结果表明,掺杂Pr3+是提高WO3气敏性能的有效策略之一。在上述分析的基础上,结合文献报道,对气敏机理进行了系统探讨。这种增强可以归因于杂质能级的形成,这可以有效地优化能带结构并促进电子转移。导带电子与价带空穴之间的复合被部分抑制,为WO3与氧分子之间的电子交换提供了更多的机会。WO3表面化学吸附氧的含量明显增加,这是气敏性提高的根本原因之一。此外,通过对不同条件下储存鱼的新鲜度测试,验证了WO3:1%Pr3+ 1D瑜伽柱状纳米棒气体传感器的实用价值。提出了一种高性能的ppb级TEA检测方法,拓宽了WO3气体传感器的应用范围。
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引用次数: 0
Spatially Resolved Sequential Activation of Allosteric DNA for In Vivo Dual-Target Detection within Mitochondria: A Strategy to Visualize of Drug-Resistant Neuroblastoma 空间分辨序列激活变构DNA用于线粒体内的体内双靶标检测:一种可视化耐药神经母细胞瘤的策略
IF 8.9 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-11 DOI: 10.1021/acssensors.5c04083
Jingzhe Zang,Yingyu Zhang,Kangbo Liu,Yuyin Xu,Liang Zhao,Wentao Wang,Mengxin Zhang,Xueyi Qin,Qionglin Wang,Xianwei Zhang,Wancun Zhang
Our previous study demonstrated that apurinic/apyrimidinic endonuclease 1 (APE1) and miR-514a are significantly overexpressed in the cytoplasm of drug-resistant neuroblastoma (NB) cells. Furthermore, we have developed a novel strategy for monitoring drug resistance in NB by targeting cytoplasmic APE1 and miR-514a. The overexpression of key enzymes in the mitochondrial base excision repair pathway, along with dysregulated miRNAs, is closely associated with chemotherapy resistance in tumors. Therefore, this study leverages cytochrome c (cyt c), located in the inner mitochondrial membrane as a targeting agent and the mitochondria-specific expression of 16S rRNA as a response switch to develop a spatially resolved, sequential activation system for an allosteric DNA nanomachine (AP-miR-tFNA), enabling in vivo detection of APE1 and miR-514a within mitochondria and facilitating molecular imaging of NB. AP-miR-tFNA sequentially responds to cyt c, 16S rRNA, miR-514a, and APE1, thereby undergoing a conformational change that efficiently achieves progressive dissociation of the fluorophore from the quencher through a sequential mechanism, ultimately generating a detectable fluorescence signal. Experimental results demonstrate that AP-miR-tFNA enables in vivo monitoring of drug resistance in NB, providing an innovative and dependable approach for monitoring therapeutic resistance in NB. In particular, AP-miR-tFNA enables in situ detection of APE1 and miR-514a within NB plasma exosomes, thereby allowing non-invasive differentiation between high-risk and low-to-intermediate-risk NB, as well as between drug-resistant NB and non-drug-resistant NB.
我们之前的研究表明,无尿嘧啶/无嘧啶内切酶1 (APE1)和miR-514a在耐药神经母细胞瘤(NB)细胞的细胞质中显著过表达。此外,我们开发了一种通过靶向细胞质APE1和miR-514a来监测NB耐药的新策略。线粒体碱基切除修复通路中关键酶的过表达,以及mirna的失调,与肿瘤化疗耐药密切相关。因此,本研究利用位于线粒体内膜的细胞色素c (cyt c)作为靶向剂,16S rRNA的线粒体特异性表达作为响应开关,开发了一种空间分辨、顺序激活的变构DNA纳米机器(AP-miR-tFNA)系统,实现线粒体内APE1和miR-514a的体内检测,促进NB的分子成像。AP-miR-tFNA依次响应cyt c、16S rRNA、miR-514a和APE1,从而发生构象变化,通过顺序机制有效地实现荧光团与猝灭剂的递进解离,最终产生可检测的荧光信号。实验结果表明,AP-miR-tFNA能够在体内监测NB的耐药性,为监测NB的治疗性耐药性提供了一种创新和可靠的方法。特别是,AP-miR-tFNA能够原位检测NB血浆外泌体中的APE1和miR-514a,从而实现高风险NB和中低风险NB以及耐药NB和非耐药NB的无创区分。
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