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Recent advances in catalytic asymmetric metalloid–hydrogen bond insertion of transition-metal carbenes 过渡金属碳烯催化不对称金属氢键插入的研究进展
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-09 DOI: 10.1039/D5CS00195A
Shuyue Zhang and Ming-Hua Xu

Over recent decades, transition-metal-catalyzed asymmetric carbene insertion into metalloid–hydrogen bonds (B–H/Si–H/Ge–H) has become a prominent research area. This review summarizes recent enantioselective strategies for constructing chiral organoboron, organosilicon, and organogermanium compounds through carbon–metalloid bond formation. Approaches are classified by chirality induction modes, with emphasis on transition-metal catalysts paired with precisely designed chiral ligands, including bisoxazolines, dienes, carboxylates, and diimines. Mechanistic correlations between ligand architectures and stereocontrol are discussed. Additionally, environmentally friendly biocatalytic approaches using engineered enzymes are also highlighted.

近几十年来,过渡金属催化的不对称碳插入金属氢键(B-H / Si-H / Ge-H)已成为一个重要的研究领域。本文综述了近年来通过碳-金属键形成手性有机硼、有机硅和有机锗化合物的对映选择性策略。方法按手性诱导模式分类,重点是过渡金属催化剂与精确设计的手性配体配对,包括双恶唑啉,二烯,羧酸盐和二亚胺。讨论了配体结构与立体控制之间的机理关系。此外,使用工程酶的环境友好型生物催化方法也得到了强调。
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引用次数: 0
When do molecular polaritons behave like optical filters?† 分子极化子什么时候表现得像光学滤光片?
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-06 DOI: 10.1039/D4CS01024H
Kai Schwennicke, Arghadip Koner, Juan B. Pérez-Sánchez, Wei Xiong, Noel C. Giebink, Marissa L. Weichman and Joel Yuen-Zhou

This review outlines several linear optical effects featured by molecular polaritons arising in the collective strong light–matter coupling regime. Under weak laser irradiation and when the single-molecule light–matter coupling can be neglected (often in the limit when the number of molecules per photon mode is large), we show that the excited-state molecular dynamics under collective strong coupling can be exactly replicated without the cavity using a shaped (or “filtered”) laser, whose field amplitude is enhanced by the cavity quality factor, shining on the bare molecules. As a consequence, the absorption within a cavity can be understood as the overlap between the polariton transmission and the bare molecular absorption, suggesting that polaritons act in part as optical filters. This framework demystifies and provides a straightforward explanation for a large class of experiments and theoretical models in molecular polaritonics, highlighting that the same effects can be achieved without the cavity with shaped laser pulses. With a few modifications, this simple conceptual picture can also be adapted to understand the incoherent nonlinear response of polaritonic systems. This review establishes a clear distinction between polaritonic phenomena that can be fully explained through classical linear optics and those that require a quantum electrodynamics approach. It also highlights the need to differentiate between effects that necessitate polaritons (i.e., hybrid light–matter states) and those that can occur in the weak coupling regime. We further discuss that certain quantum optical effects like fluorescence can be partially described as optical filtering, whereas some others like cavity-induced Raman scattering go beyond this. Further exploration in these areas is needed to uncover novel polaritonic phenomena beyond optical filtering.

本文概述了在集体强光-物质耦合状态下产生的分子极化子所具有的几种线性光学效应。在弱激光照射下,当单分子光-物质耦合可以忽略时(通常在每个光子模式的分子数很大的极限下),我们证明了在没有腔的情况下,使用形状(或“过滤”)激光可以精确地复制集体强耦合下的激发态分子动力学,其场振幅通过腔质量因子增强,照射在裸露的分子上。因此,腔内的吸收可以理解为极化子传输和裸分子吸收之间的重叠,这表明极化子在一定程度上起着光学滤光器的作用。这个框架揭开了分子极化电子学中大量实验和理论模型的神秘面纱,并为它们提供了一个直接的解释,强调了在没有形状激光脉冲的空腔的情况下也可以实现相同的效果。经过一些修改,这个简单的概念图也可以用来理解极化系统的非相干非线性响应。本综述明确区分了可以通过经典线性光学充分解释的极化现象和需要量子电动力学方法解释的极化现象。它还强调需要区分需要极化的效应(即,混合光物质状态)和那些可能在弱耦合状态下发生的效应。我们进一步讨论了某些量子光学效应,如荧光,可以部分地描述为光学滤波,而其他一些量子光学效应,如腔诱导拉曼散射,则超出了这一点。需要在这些领域进行进一步的探索,以发现超越光学滤波的新的极化现象。
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引用次数: 0
Intracellular aggregation of exogenous molecules for biomedical applications 生物医学应用中外源分子的细胞内聚集。
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-06 DOI: 10.1039/D5CS00141B
Da-Yong Hou, Haoran Wang, Yue-Ze Wang, Dong-Bing Cheng, Ben Zhong Tang and Wanhai Xu

Most biomolecules play important roles in aggregated states, as exemplified by proteins and DNA. Inspired by biomacromolecule formation, the exploration of intracellular bioactive materials derived from exogenous molecules has drawn considerable interest. In cells, exogenous molecules may assemble into macromolecules and supermolecules and thus help monitor disease processes or regulate the cell fate, which provides a new approach to disease treatment. The diverse cellular microenvironments (reductive in the cytoplasm, oxidative in mitochondria, and acidic in lysosomes) can be exploited to achieve controllable and precise intracellular aggregation using intelligent molecular design. Moreover, the intracellular polymerization and organelle targeting–triggered aggregation of exogenous molecules can be used for cell fate manipulation. This review deals with the intracellular aggregation of exogenous molecules activated by intracellular stimuli, exogenous stimuli, and organelle targeting and discusses the related molecular mechanisms and biomedical applications, providing guidance for the design of bioactive materials and discovery of theranostic agents.

大多数生物分子在聚集状态下发挥重要作用,例如蛋白质和DNA。受生物大分子形成的启发,从外源分子衍生的细胞内生物活性物质的探索引起了相当大的兴趣。在细胞中,外源分子可以组装成大分子和超分子,从而帮助监测疾病过程或调节细胞命运,这为疾病治疗提供了新的途径。不同的细胞微环境(细胞质中的还原性,线粒体中的氧化性和溶酶体中的酸性)可以利用智能分子设计来实现可控和精确的细胞内聚集。此外,细胞内聚合和细胞器靶向触发的外源分子聚集可用于细胞命运操纵。本文综述了细胞内刺激、外源刺激和细胞器靶向作用下外源分子的细胞内聚集,并讨论了相关的分子机制和生物医学应用,为生物活性材料的设计和治疗药物的发现提供指导。
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引用次数: 0
Supramolecular engineering in hybrid perovskite optoelectronics† 混合钙钛矿光电子学中的超分子工程。
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-06 DOI: 10.1039/D4CS00924J
Tzu-Sen Su, Anurag Krishna, Chenxu Zhao, Junhao Chu and Hong Zhang

This review explores the emerging field of supramolecular engineering in hybrid organic–inorganic perovskite optoelectronics. The incorporation of supramolecular agents has shown transformative effects on the crystallization, morphology, stability, and performance of perovskite-based materials and devices. We systematically review the types of supramolecular interactions, mechanisms of supramolecular engineering crystallization, synthesis of perovskite quantum dots, and interface engineering advancements for device stability. This comprehensive evaluation discusses the latest progress, challenges, and promising future directions, highlighting supramolecular engineering's potential in advancing hybrid organic–inorganic perovskite optoelectronic technologies.

本文综述了有机-无机钙钛矿杂化光电子学的超分子工程研究进展。超分子试剂的掺入对钙钛矿基材料和器件的结晶、形态、稳定性和性能产生了变革性的影响。我们系统地回顾了超分子相互作用的类型、超分子工程结晶的机制、钙钛矿量子点的合成以及用于器件稳定性的界面工程进展。这篇综合评价讨论了最新的进展、挑战和有希望的未来方向,突出了超分子工程在推进有机-无机钙钛矿混合光电技术方面的潜力。
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引用次数: 0
Computational insights on the role of structure-directing agents (SDAs) in the synthesis of zeolites. 结构导向剂(SDAs)在沸石合成中的作用的计算见解。
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-04 DOI: 10.1039/d5cs00306g
Xiaomin Tang, Omer F Altundal, Frits Daeyaert, Zhiqiang Liu, German Sastre

Most of the zeolites synthesised in the last 3 or 4 decades employ organic structure-directing agents (OSDAs) in their synthesis. The synthesis or test of new OSDAs is a major driving force in order to achieve the goal of synthesising a new zeolite. Despite this, predicting which zeolite phase will form when a specific OSDA is used remains a complex challenge. Moreover, even knowing the zeolite phase that will be obtained using a given OSDA, it is not easy to always rationalise or fully explain the result obtained. Computational simulations have occasionally been employed, and in a number of cases they are limited to calculate the van der Waals contribution between zeolite and the OSDA molecules (zeo-OSDA). Strongly negative values indicate an increasing viability of the synthesis, but it is only by comparison between competing zeolite phases that some insight can be gained, and this has been done in a limited number of cases. Other, less simple, approaches consider the total energy of the zeolite formed, of which the van der Waals zeo-OSDA contribution is not always the dominant contribution. These and other similar procedures need to be analysed and summarised in order to clarify the pros and cons of each approach. The recent advent of big data has allowed to construct databases that make it possible to analyse a large number of results. With the help of new descriptors and algorithms (some of them making use of artificial intelligence) further advances have been made. In spite of the large pool of data available, it becomes difficult to systematise and obtain general rules. A recent burst to this topic comes from the possibility to (at least partially) control the Al distributions by selecting appropriate OSDAs. These Al distributions influence the location and strength of Brønsted acid sites which in turn are directly responsible for the catalytic activity of the material.

近三四十年来合成的沸石大多采用有机定向结构剂(OSDAs)合成。为了达到合成新型沸石的目的,新的osda的合成或测试是一个主要的推动力。尽管如此,当使用特定的OSDA时,预测哪种沸石相将形成仍然是一个复杂的挑战。此外,即使知道使用给定的OSDA将获得的沸石相,也不容易总是合理化或完全解释所获得的结果。计算模拟偶尔被采用,在许多情况下,它们仅限于计算沸石和OSDA分子之间的范德华贡献(zeo-OSDA)。强烈的负值表明合成的活力在增加,但只有通过比较相互竞争的沸石相才能获得一些见解,这在有限的情况下已经完成。其他不太简单的方法考虑形成的沸石的总能量,其中范德华零osda贡献并不总是占主导地位。需要对这些和其他类似的程序进行分析和总结,以便澄清每种方法的利弊。最近大数据的出现使得构建数据库成为可能,从而分析大量结果。在新的描述符和算法(其中一些使用人工智能)的帮助下,已经取得了进一步的进展。尽管有大量可用的数据,但很难将其系统化并获得一般规则。通过选择合适的osda来(至少部分地)控制ai分布的可能性是这个主题的最新热点。这些Al的分布影响了Brønsted酸位的位置和强度,这反过来又直接影响了材料的催化活性。
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引用次数: 0
Correction: DNA-mediated precise regulation of SERS hotspots for biosensing and bioimaging 更正:dna介导的SERS热点精确调控用于生物传感和生物成像
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-02 DOI: 10.1039/D5CS90048D
Jingjing Zhang, Chunyuan Song, Xiyu He, Jian Liu, Jie Chao and Lianhui Wang

Correction for ‘DNA-mediated precise regulation of SERS hotspots for biosensing and bioimaging’ by Jingjing Zhang et al., Chem. Soc. Rev., 2025, https://doi.org/10.1039/d5cs00124b.

张晶晶等人对“dna介导的生物传感和生物成像SERS热点的精确调控”的修正。Soc。Rev., 2025, https://doi.org/10.1039/d5cs00124b。
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引用次数: 0
Nitrogen-centered radicals driving unusual enzyme reactions in biosynthetic pathways 以氮为中心的自由基驱动生物合成途径中不寻常的酶反应
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-06-02 DOI: 10.1039/D5CS00342C
Richiro Ushimaru and Ikuro Abe

Nitrogen-centered radicals have emerged as versatile intermediates in natural product biosynthesis, playing pivotal roles in complex bond-forming and rearrangement reactions—including fragmentations, cyclizations, and dimerizations. These transformations enable the efficient construction of structurally intricate alkaloids, amino acids, cofactors, and other scaffolds that are often inaccessible via classical polar mechanisms. This review provides an overview of the enzymatic systems discovered and characterized over the past decade that harness nitrogen-centered radicals to mediate diverse biological transformations. Emphasis is placed on the enzymatic strategies for generating and precisely controlling these reactive species, with detailed discussions of their underlying mechanisms. These insights underscore the expanding role of nitrogen radical chemistry in biology and highlight its potential in the development of new biocatalytic platforms for synthetically challenging transformations.

氮中心自由基已成为天然产物生物合成中的多功能中间体,在复杂的键形成和重排反应中起着关键作用,包括断裂、环化和二聚化。这些转化可以有效地构建结构复杂的生物碱、氨基酸、辅因子和其他通过经典极性机制通常无法获得的支架。本文综述了在过去十年中发现和表征的利用氮中心自由基介导多种生物转化的酶系统。重点放在产生和精确控制这些活性物种的酶策略上,并详细讨论了它们的潜在机制。这些见解强调了氮自由基化学在生物学中不断扩大的作用,并强调了它在开发新的生物催化平台以进行综合挑战转化方面的潜力。
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引用次数: 0
Chemical engineering of zeolites: alleviating transport limitations through hierarchical design and shaping 沸石的化学工程:通过分层设计和成型减轻运输限制
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-05-29 DOI: 10.1039/D5CS00169B
Nibras Hijazi, Anastasiya Bavykina, Irina Yarulina, Tuiana Shoinkhorova, Enrique V. Ramos-Fernandez and Jorge Gascon

Zeolites are indispensable catalysts in a wide range of industrial applications due to their well-defined microporous structures and exceptional shape-selective properties. However, their practical use is often constrained by diffusion limitations, which can hinder reactant accessibility, influence product selectivity, and accelerate catalyst deactivation. This review critically examines strategies to alleviate these diffusion constraints, focusing on hierarchical structuring, nanozeolite synthesis, and advanced shaping techniques. We discuss fundamental diffusion theories, experimental characterization methods, and emerging methodologies that enhance mass transport in zeolites. By bridging fundamental principles with industrial applications, this review provides a comprehensive overview of how tailored zeolite architectures can optimize catalytic performance, paving the way for more efficient and sustainable processes.

沸石具有良好的微孔结构和特殊的形状选择特性,是广泛工业应用中不可缺少的催化剂。然而,它们的实际应用往往受到扩散限制的限制,这可能会阻碍反应物的可及性,影响产物的选择性,并加速催化剂的失活。这篇综述批判性地探讨了缓解这些扩散限制的策略,重点是分层结构,纳米沸石合成和先进的成型技术。我们讨论了基本的扩散理论,实验表征方法和新兴的方法,以提高沸石的质量输运。通过将基本原理与工业应用相结合,本综述全面概述了量身定制的沸石结构如何优化催化性能,为更高效和可持续的工艺铺平道路。
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引用次数: 0
Cuproptosis: mechanisms and nanotherapeutic strategies in cancer and beyond 铜增生:癌症及其他疾病的机制和纳米治疗策略
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-05-28 DOI: 10.1039/D5CS00083A
Lijie Mao, Ji Lu, Xinyu Wen, Zhiyi Song, Cai Sun, Yuanru Zhao, Fang Huang, Si Chen, Dongyang Jiang, Wenliang Che, Cheng Zhong, Chen Yu, Ke Li, Xiangyu Lu and Jianlin Shi

Cuproptosis, a novel form of copper (Cu)-dependent programmed cell death, is induced by directly binding Cu species to lipoylated components of the tricarboxylic acid (TCA) cycle. Since its discovery in 2022, cuproptosis has been closely linked to the field of materials science, offering a biological basis and bright prospects for the use of Cu-based nanomaterials in various disease treatments. Owing to the unique physicochemical properties of nanomaterials, Cu delivery nanosystems can specifically increase Cu levels at disease sites, inducing cuproptosis to achieve disease treatment while minimizing the undesirable release of Cu in normal tissues. This innovative nanomaterial-mediated cuproptosis, termed as “nanocuproptosis”, positions at the intersection of chemistry, materials science, pharmaceutical science, and clinical medicine. This review aims to comprehensively summarize and discuss recent advancements in cuproptosis across various diseases, with a particular focus on cancer. It delves into the biochemical basis of nanomaterial-mediated cuproptosis, the rational design for cuproptosis inducers, strategies for enhancing therapeutic specificity, and cuproptosis-centric synergistic cancer therapeutics. Beyond oncology, this review also explores the expanded applications of cuproptosis, such as antibacterial, wound healing, and bone tissue engineering, highlighting its great potential to open innovative therapeutic strategies. Furthermore, the clinical potential of cuproptosis is assessed from basic, preclinical to clinical research. Finally, this review addresses current challenges, proposes potential solutions, and discusses the future prospects of this burgeoning field, highlighting cuproptosis nanomedicine as a highly promising alternative to current clinical therapeutics.

cuprotosis是一种新型的铜(Cu)依赖性程序性细胞死亡,它是通过直接将Cu物种与三羧酸(TCA)循环的脂化组分结合而诱导的。自2022年发现铜钛以来,铜钛一直与材料科学领域紧密联系在一起,为铜基纳米材料在各种疾病治疗中的应用提供了生物学基础和光明前景。由于纳米材料独特的物理化学性质,铜递送纳米系统可以特异性地增加疾病部位的铜水平,诱导铜还原以实现疾病治疗,同时最大限度地减少正常组织中铜的不良释放。这种创新的纳米材料介导的铜移植,被称为“纳米铜移植”,处于化学、材料科学、制药科学和临床医学的交叉点。这篇综述旨在全面总结和讨论最近在各种疾病中的进展,特别关注癌症。它深入研究了纳米材料介导的铜增生的生化基础,铜增生诱导剂的合理设计,提高治疗特异性的策略,以及以铜增生为中心的协同癌症治疗方法。除肿瘤学外,本文还探讨了铜异体的广泛应用,如抗菌、伤口愈合和骨组织工程,强调其在开辟创新治疗策略方面的巨大潜力。此外,从基础研究、临床前研究到临床研究,对铜骨畸形的临床潜力进行了评估。最后,本文回顾了当前的挑战,提出了潜在的解决方案,并讨论了这一新兴领域的未来前景,强调了铜突起纳米医学作为当前临床治疗的一个非常有前途的替代方案。
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引用次数: 0
Desymmetrization strategy in natural product total synthesis 天然产物全合成中的不对称策略
IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-05-27 DOI: 10.1039/D5CS00092K
Haichao Liu, Kai Tang, Hao Zeng, Lijun Chen, Hong Liang and Yanxing Jia

Desymmetrization strategies have emerged as practical methods for the efficient construction of desired molecules from readily accessible symmetrical precursors. This approach has found widespread application in natural product total synthesis as it simplifies the materials preparation, enables the precise control of chirality formation, and inspires innovative retrosynthetic analysis. Here, we summarize recent advances (2014–2024) of the applications of desymmetrization strategies in natural product total synthesis, and showcase their advantages in designing new reactions and synthetic strategies, with the aim to foster their wider application in total synthesis.

去对称策略已经成为从容易获得的对称前体高效构建所需分子的实用方法。这种方法在天然产物全合成中得到了广泛的应用,因为它简化了材料的制备,能够精确控制手性的形成,并激发了创新的反合成分析。本文综述了非对称化策略在天然产物全合成中的应用进展(2014-2024),并展示了其在设计新反应和合成策略方面的优势,旨在促进其在全合成中的更广泛应用。
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引用次数: 0
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