CCS ChemistryPub Date : 2026-04-01DOI: 10.31635/ccschem.025.202505863
Peng Zhang, Liren Xu, Ke Wei, Bin Qin, Jinhai Wang, Xiaolong Sun
{"title":"Covalent and Dynamic Covalent Modification of Cysteine Residues on Peptides via Indanonalkene Conjugate Acceptors","authors":"Peng Zhang, Liren Xu, Ke Wei, Bin Qin, Jinhai Wang, Xiaolong Sun","doi":"10.31635/ccschem.025.202505863","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505863","url":null,"abstract":"Peptide/protein bioconjugation tools are crucial for advancing biological research and therapeutic drug development. Conventional methods primarily rely on the reactivity of cysteine thiol side chains, which often lack selectivity for cysteine residues in different chemical environments. With this research, we developed a new protocol that enabled the selective modification of <i>N</i>-terminal cysteine residues under mild conditions, forming a stable 1,4-thiazolidinene linkage through covalent conjugation with indanonalkene conjugate acceptors (IDAs). Additionally, dynamic covalent modifications occurred between intrachain vicinal dithiols, which could be reversed by GSH to release the native peptide. These two modification modes were orthogonally controlled by modulating the reaction pH, allowing for selective bifunctionalization of cysteine residues at different positions within a single peptide. We then applied this strategy to modify the <i>N</i>-terminal cysteine of the bioactive peptide Laminin (925–933), and the resulting conjugate was successfully used for targeted imaging of the 67 kDa laminin receptor (67LR) on the surface of HT-29 colon cancer cells. The chemoselective cysteine modification through IDA reagents establishes a valuable strategy for developing functional bioconjugates.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"28 1","pages":"1-11"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
CCS ChemistryPub Date : 2026-04-01DOI: 10.31635/ccschem.026.202506818
Xin-Ya Cai, Xin Meng, Zhi-Gang Gu, Jian Zhang
{"title":"Three-Dimensional-Printed Chiral Heterometallic Cluster Monoliths for Integrated Circularly Polarized Luminescent Sensing and Visualized Enantioselective Catalysis","authors":"Xin-Ya Cai, Xin Meng, Zhi-Gang Gu, Jian Zhang","doi":"10.31635/ccschem.026.202506818","DOIUrl":"https://doi.org/10.31635/ccschem.026.202506818","url":null,"abstract":"Atomically precise metal clusters have emerged as a new frontier in diverse catalytic applications, yet their development in direct, visualized enantioselective catalysis remains largely unexplored. Herein, we report a stepwise synthesis of structurally precise chiral heterometal Zr/Cu-organic clusters {[Zr<sub>6</sub>Cu<sub>4</sub>(μ<sub>3</sub>-O)<sub>8</sub>L<sub>4</sub>(<i>R</i>/<i>S</i>-DPEN)<sub>4</sub>(DMF)<sub>4</sub>]} (<i>R</i>/<i>S</i>-ZrCu<sup>II</sup>OC, L = Pamoic acid, DPEN = 1,2-diphenyl-1,2-ethanediamine) from achiral Zr-based cages by introducing a chiral Cu(II) complex (Cu<sup>II</sup>(DPEN). Upon <span>d</span>-(+)-glucose catalysis, the nonluminescent <i>R</i>/<i>S</i>-ZrCu<sup>II</sup>OC underwent Cu(II)→Cu(I) reduction, which proceeded without compromising the cluster’s structural integrity or chiral configuration, yielding highly luminescent <i>R</i>/<i>S</i>-ZrCu<sup>I</sup>OC with prominent circularly polarized luminescence (CPL) activity. Concomitantly, this redox transformation drove enantioselective oxidation of glucose to gluconic acid, thus enabling CPL-visualized enantioselective catalysis for the first time. In contrast, the chiral Cu<sup>II</sup>(DPEN) complexes, which lacked the stabilizing coordination environment and electronic modulation afforded by the Zr-based cluster, were directly reduced to Cu<sup>0</sup> rather than forming luminescent Cu<sup>+</sup> species, resulting in sustained nonluminescence. Furthermore, we introduced a photocuring three-dimensional (3D) printing strategy to fabricate chiral metal cluster composite monoliths, opening a route to macroscopic, designer chiral catalysts. This work not only advances the rational design of heterometallic chiral metal–organic cluster (MOC) and 3D-printable chiral monolithic materials but also establishes a general chiral luminescence-based platform for visualizing asymmetric catalysis.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"121 1","pages":"1818-1830"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599379","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
CCS ChemistryPub Date : 2026-04-01DOI: 10.31635/ccschem.026.202607362
Hai Xu, Lu Lu, Chunling Huang, Lei Liu, Hui Bian, Hua Zhang, Juyoung Yoon
{"title":"Self-Assembling Nonhomodimeric Cyanine Photosensitizers for Efficient Tumor Targeting and Type I Photodynamic Therapy","authors":"Hai Xu, Lu Lu, Chunling Huang, Lei Liu, Hui Bian, Hua Zhang, Juyoung Yoon","doi":"10.31635/ccschem.026.202607362","DOIUrl":"https://doi.org/10.31635/ccschem.026.202607362","url":null,"abstract":"In recent years, homodimeric photosensitizers have achieved remarkable progress in cancer therapy, yet research on their nonhomodimeric counterparts remains limited. Herein, we present a rational “strengths-for-strengths” design strategy that integrates a near-infrared–absorbing cyanine dye with a triphenylamine-based pyridinium salt photosensitizer known for its high reactive oxygen species (ROS) generation efficiency. Photophysical studies and theoretical calculations reveal that the introduction of the pyridinium unit precisely tunes the excited-state energy levels, markedly reduces the S<sub>1</sub>–T<sub>3</sub> energy gap, and facilitates efficient type I ROS generation. The resulting nonhomodimeric molecule self-assembles into uniform nanoparticles in aqueous media, enabling improved in vivo delivery and tumor accumulation via the enhanced permeability and retention effect. The molecule also exhibits strong mitochondrial targeting and outstanding type I photodynamic activity, thereby achieving potent tumor growth inhibition. This work highlights the untapped potential of nonhomodimeric photosensitizers in cancer photodynamic therapy and offers a versatile molecular design paradigm for developing next-generation high-performance photosensitizers.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"22 1","pages":"1924-1936"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147617680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
CCS ChemistryPub Date : 2026-04-01DOI: 10.31635/ccschem.025.202506929
Yanjun Li, Simon L. Homölle, Lutz Ackermann
{"title":"Photoinduced Copper-Catalyzed C–H Activation Enables Access to Bicyclo[1.1.1]pentane Azole Isosteres","authors":"Yanjun Li, Simon L. Homölle, Lutz Ackermann","doi":"10.31635/ccschem.025.202506929","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506929","url":null,"abstract":"Bicyclo[1.1.1]pentane (BCP)-substituted azoles represent exciting scaffolds in pharmaceutical research; however, their development has been significantly hindered by the complexity of their multistep de novo syntheses. In contrast, we herein report on a photoinduced copper-catalyzed C–H activation strategy that enables the direct access to BCP-azole isosteres. This strategy features ample substrate scope, tolerating a wide range of azoles and sensitive functional groups, even those bearing multiple nitrogen atoms. Mechanistic studies suggested a copper-azole species as the key intermediate in the catalysis. This approach was further applied to the rapid preparation of challenging Fsp<sup>3</sup>-rich natural product derivatives.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"144 1","pages":"1791-1800"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
CCS ChemistryPub Date : 2026-04-01DOI: 10.31635/ccschem.026.202507217
Mingyuan Shao, Nelcari-Trinidad Ramírez-Márquez, Zhendong Liu, Javier García-Martínez
{"title":"Harnessing Kinetic Control in Zeolite Synthesis and Interconversion to Enhance Catalytic Performance","authors":"Mingyuan Shao, Nelcari-Trinidad Ramírez-Márquez, Zhendong Liu, Javier García-Martínez","doi":"10.31635/ccschem.026.202507217","DOIUrl":"https://doi.org/10.31635/ccschem.026.202507217","url":null,"abstract":"Recent advances in zeolite synthesis increasingly emphasize accelerated routes for framework discovery and modification aimed at catalytic applications. Two complementary strategies, ultrafast synthesis and partial interzeolite transformation, have emerged as powerful tools to reshape how zeolite structures are accessed, modified, and optimized. Ultrafast synthesis compresses crystallization times from days to minutes or even seconds by exploiting intensified thermal fields, preorganized precursors, and nonclassical nucleation pathways. Partial interzeolite transformation, in contrast, expands the accessible structural space through controlled topotactic transformations, enabling hybrid frameworks that are difficult or impossible to obtain via direct synthesis. Although distinct in practice, both approaches are governed by kinetic control rather than equilibrium-driven crystallization, shifting the conceptual framework of zeolite synthesis. From this perspective, zeolite formation can be viewed as a continuous and tunable transformation process rather than a sequence of discrete steps. This mini-review critically examines recent progress in ultrafast synthesis and partial interzeolite transformation, highlighting their mechanistic foundations, points of convergence, and mutual reinforcement. By integrating these strategies under a unified kinetic-control framework, the review outlines how accelerated synthesis and controlled transformation can enable rapid framework discovery, structural diversification, and property optimization for catalytic applications.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"34 1","pages":"1762-1779"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
CCS ChemistryPub Date : 2026-04-01DOI: 10.31635/ccschem.025.202505833
Chentao Fang, Keke Mao, Tianxin Liu, Wanbing Gong, Xiaomin Ji, Zheyue Li, Jiayi Li, Chuansheng Hu, Ran Long, Yujie Xiong
{"title":"New Dual-Ligand Metal–Organic Framework for Cocatalyst-Free and Solvent-Free Carbon Dioxide Cycloaddition to Carbonates","authors":"Chentao Fang, Keke Mao, Tianxin Liu, Wanbing Gong, Xiaomin Ji, Zheyue Li, Jiayi Li, Chuansheng Hu, Ran Long, Yujie Xiong","doi":"10.31635/ccschem.025.202505833","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505833","url":null,"abstract":"The rational design and synthesis of low-cost and high-efficiency heterogeneous catalysts with acid-base active sites for synergistically carbon dioxide (CO<sub>2</sub>) cycloaddition to value-added cyclic carbonates remains a big challenge. Here, a new dual-ligand metal–organic framework (MOF) catalyst, denoted as [Zn(Bdc-NH<sub>2</sub>)(Bpy)]<sub>n</sub>, is innovatively designed and synthesized via a simple hydrothermal strategy, which simultaneously possesses a novel ZnO<sub>2</sub>N<sub>2</sub> Lewis acid site and a N–H…O Lewis base site. As a result, this catalyst displays a highly efficient and selective CO<sub>2</sub> cycloaddition performance under solvent-free and cocatalyst-free conditions for the production of important cyclic carbonates due to the synergistic effect of rich acid and base sites. In addition, via in situ characterizations and density functional theory calculations, the reaction pathways and mechanisms are revealed. This dual-ligand MOF exhibits moderate reactant adsorption, reaction energy with CO<sub>2</sub>, and favorable product desorption, thus promoting excellent CO<sub>2</sub> cycloaddition performance under cocatalyst-free and solvent-free conditions. This work provides an advanced and promising dual-ligand MOF for constructing an acid-base synergistically catalytic system for crucial catalytic reactions.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"112 1","pages":"1-21"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147620414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Organocatalytic Enantio-, Atrop-, and Diastereoselective Macrocyclization of Quinone Methides","authors":"Ting Yao, Chang Yuan, Xiaoyu Wang, Hongxuan Zhai, Changgui Zhao","doi":"10.31635/ccschem.025.202506108","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506108","url":null,"abstract":"Although installation of a substituent on the ansa chain has been employed to modulate conformational stability and pharmacological properties in cyclophane systems, the detailed relationship between structure and occurrence of planar chirality remains underexplored. Herein, we report the first chiral phosphoric acid-catalyzed enantio-, atrop-, and diastereoselective macrocyclization of quinone methides with alcohols, achieving stereoselective control over the central and planar chiralities. A unique naphthol auxiliary group facilitated macrocyclization and control of the stereoselectivity. A variety of Type III planar-chiral [n]paracyclophanes containing a previously challenging accessible chiral ansa chain were synthesized. Thermal epimerization studies revealed that incorporation of a benzylic substituent on the ansa bridge significantly enhanced conformational stability in Type III [n]paracyclophane, thereby allowing two-atom elongation of the ansa chain while maintaining planar chirality within these constrained macrocyclic frameworks.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"29 1","pages":"1-10"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147617679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Effects of Geometric Isomerism and Crystal Size on Ultra-Narrowband Near-Infrared Emission from Organic Crystals","authors":"Hao Zhang, Linfeng Lan, Baolei Tang, Liang Li, Panče Naumov, Hongyu Zhang","doi":"10.31635/ccschem.025.202505843","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505843","url":null,"abstract":"Narrowband near-infrared (NIR) emissive materials are indispensable for advancing optical communications, biological imaging, and precision sensing technologies. Despite their potential, achieving precise control over the emission profile while ensuring the long-term stability of the material remains a significant challenge. In this study, we utilized a diaminomaleonitrile derivative to demonstrate an approach that combines geometric (<i>cis-trans</i>) isomerism and crystal size to control the ultra-narrowband NIR emission of an organic crystalline material. By systematically optimizing key parameters, including light exposure, temperature, and solvent diffusion dynamics, we established a robust platform for controlled and preferential growth of its two isomers with specific optical properties. Remarkably, the crystals of the <i>cis</i>-isomer exhibited size-dependent narrowing of the NIR emission band, with an impressive narrow full-width-at-half-maximum of 40 nm (0.096 eV), while the <i>trans</i>-isomer exhibited ultra-narrowband NIR emission with outstanding photostability attributed to its rigid, planar molecular structure. Comprehensive theoretical and experimental analyses revealed the critical role of intermolecular interactions and vibrational relaxation in modulating their emission characteristics. This study establishes a robust methodology for the preparation of narrowband organic NIR-emissive materials.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"09 1","pages":"1-13"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Metalloligand Enabling Cobalt-Catalyzed anti-Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes","authors":"Dongyang Wang, Peihao Wang, Qi Zhang, Xuebing Leng, Hui Chen, Liang Deng","doi":"10.31635/ccschem.025.202505983","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505983","url":null,"abstract":"Metal-catalyzed hydrosilylation of alkynes with hydrosilanes is a useful method for the preparation of vinylsilanes that are useful reagents in organic synthesis and the silicone industry. 3d metal catalysts affecting the hydrosilylation reactions of tertiary silanes, however, are elusive. Herein, we present selective <i>anti</i>-Markovnikov hydrosilylation reactions of terminal alkynes with tertiary silanes using a dicobalt complex [(Xantphos)(CO)Co(μ-CO)<sub>2</sub>Co(CO)<sub>3</sub>] (Xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)) as the catalyst. This catalytic reaction furnishes β-(<i>E</i>)-vinylsilanes in good to high yields and shows good functional group compatibility. Reactivity studies on the dicobalt complex pointed out that the alkyne-bridged dicobalt species is a key intermediate. Theoretical calculations further suggested that the reaction of alkyne-bridged dicobalt intermediate with tertiary silane on a triplet energy surface is the rate- and regioselectivity determining step, and that during catalysis, the (Xantphos)(CO)Co site in the dicobalt catalyst functions as a bulky noninnocent metalloligand to assist the low-coordinate cobalt site Co(CO)<sub>2</sub> in mediating the activation and selective transformation of tertiary silanes.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"16 1","pages":"1-13"},"PeriodicalIF":11.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147599380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}