Pub Date : 2026-01-18DOI: 10.31635/ccschem.025.202506818
Xin-Ya Cai, Xin Meng, Zhi-Gang Gu, Jian Zhang
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 {[Zr6Cu4(μ3-O)8L4(R/S-DPEN)4(DMF)4]} (R/S-ZrCuIIOC, L= Pamoic acid, DPEN= 1,2-diphenyl-1,2-ethanediamine) from achiral Zr based cages by introducing chiral Cu(II) complex (CuII(DPEN). Upon treatment with D-(+)-glucose catalysis, the nonluminescence R/S-ZrCuIIOC undergoes Cu(II)Cu(I) reduction, which proceeds without compromising the cluster‘s structural integrity or chiral configuration, yielding highly luminescent R/S-ZrCuIOC with prominent circularly polarized luminescence (CPL) activity. Concomitantly, this redox transformation simultaneously drives enantioselective oxidation of glucose to gluconic acid, thus enabling CPL-visualized enantioselective catalysis for the first time. In contrast, the chiral CuII(DPEN) complexes, lacking the stabilizing coordination environment and electronic modulation afforded by the Zr-based cluster, are directly reduced to Cu0 rather than forming luminescent Cu+ species, resulting in sustained non-luminescent. Furthermore, we introduce photo-curing 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 MOC and 3D-printable chiral monolithic materials, but also establishes a general chiral luminescence-based platform for visualizing asymmetric catalysis.
{"title":"3D-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.025.202506818","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506818","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/S</i>-DPEN)<sub>4</sub>(DMF)<sub>4</sub>]} (<i>R/S</i>-ZrCu<sup>II</sup>OC, L= Pamoic acid, DPEN= 1,2-diphenyl-1,2-ethanediamine) from achiral Zr based cages by introducing chiral Cu(II) complex (Cu<sup>II</sup>(DPEN). Upon treatment with D-(+)-glucose catalysis, the nonluminescence <i>R/S</i>-ZrCu<sup>II</sup>OC undergoes Cu(II)Cu(I) reduction, which proceeds without compromising the cluster‘s structural integrity or chiral configuration, yielding highly luminescent <i>R/S</i>-ZrCu<sup>I</sup>OC with prominent circularly polarized luminescence (CPL) activity. Concomitantly, this redox transformation simultaneously drives 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, lacking the stabilizing coordination environment and electronic modulation afforded by the Zr-based cluster, are directly reduced to Cu<sup>0</sup> rather than forming luminescent Cu<sup>+</sup> species, resulting in sustained non-luminescent. Furthermore, we introduce photo-curing 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 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":"30 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993302","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}
The saturation of planar pyridines through concurrent introduction of multiple substituents to access complex piperidines represents a highly attractive strategy in modern drug discovery. Capitalizing on the exceptional selectivity and unique capability of synthetic electrochemistry in generating diverse reactive intermediates, we herein develop an electrocatalytic saturation strategy for pyridines. It enables the chemo-, regio-, and stereoselective dearomative multi-functionalization of pyridines, yielding structurally complex piperidines decorated with four synthetically versatile functional groups. Preliminary mechanistic studies suggest that electrochemically generated cyanogen bromide promotes dearomatization of pyridines to form dihydropyridines, which subsequently undergo stereoselective electrochemical vicinal difunctionalization to afford the target multi-functionalized piperidines.
{"title":"Chemo-, Regio-, and Stereoselective Electrochemical Dearomative Multi-functionalization of Pyridines","authors":"Zhihua Wang, Wang-Fu Liang, Chen-Xu Gong, Xinglei He, Jing-Heng Li, Yuqi Lin, Ke-Yin Ye","doi":"10.31635/ccschem.025.202507069","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507069","url":null,"abstract":"The saturation of planar pyridines through concurrent introduction of multiple substituents to access complex piperidines represents a highly attractive strategy in modern drug discovery. Capitalizing on the exceptional selectivity and unique capability of synthetic electrochemistry in generating diverse reactive intermediates, we herein develop an electrocatalytic saturation strategy for pyridines. It enables the chemo-, regio-, and stereoselective dearomative multi-functionalization of pyridines, yielding structurally complex piperidines decorated with four synthetically versatile functional groups. Preliminary mechanistic studies suggest that electrochemically generated cyanogen bromide promotes dearomatization of pyridines to form dihydropyridines, which subsequently undergo stereoselective electrochemical vicinal difunctionalization to afford the target multi-functionalized piperidines.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"30 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972527","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}
Pub Date : 2026-01-12DOI: 10.31635/ccschem.025.202507044
Baojie Yu, Fangrun Ge, Yao Wang
Nature possesses an extraordinary capacity to produce complex frameworks from simple starting materials, and in particular, it sometimes allows a maximum bond formation of reactant by consecutive cascade reactions. However, mimicking such capacity in laboratory remains a long-standing challenge. Herein, we report that, enabled by a rationally designed chalcogen-bonding catalyst, reactions between eight-membered cycloalkenes or exocyclic alkenes and aldehydes proceeded to afford cyclization products. We demonstrate an extreme case in which, using aryl-substituted cyclooctenes, as many as six ring carbons-four sp3 and two sp2-of an eight-membered carbocycle participated in the bond-forming events, approaching the maximum bond formation achievable with a cyclooctene system. In this process, up to seven reactant molecules are incorporated into a single product, yielding tetracyclic frameworks that contain both bridged and spiro rings. To our knowledge, this catalytic system sets a record for the number of bonds formed in non-polymeric products via noncovalent catalysis.
{"title":"Towards Maximum Bond Formation of Cyclooctenes Enabled by Chalcogen Bonding Catalysis","authors":"Baojie Yu, Fangrun Ge, Yao Wang","doi":"10.31635/ccschem.025.202507044","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507044","url":null,"abstract":"Nature possesses an extraordinary capacity to produce complex frameworks from simple starting materials, and in particular, it sometimes allows a maximum bond formation of reactant by consecutive cascade reactions. However, mimicking such capacity in laboratory remains a long-standing challenge. Herein, we report that, enabled by a rationally designed chalcogen-bonding catalyst, reactions between eight-membered cycloalkenes or exocyclic alkenes and aldehydes proceeded to afford cyclization products. We demonstrate an extreme case in which, using aryl-substituted cyclooctenes, as many as six ring carbons-four sp<sup>3</sup> and two sp<sup>2</sup>-of an eight-membered carbocycle participated in the bond-forming events, approaching the maximum bond formation achievable with a cyclooctene system. In this process, up to seven reactant molecules are incorporated into a single product, yielding tetracyclic frameworks that contain both bridged and spiro rings. To our knowledge, this catalytic system sets a record for the number of bonds formed in non-polymeric products via noncovalent catalysis.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"39 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955829","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}
Pub Date : 2026-01-12DOI: 10.31635/ccschem.025.202506952
Zhi-Hao Chen, Lu Liu, Yun-Bo Wang, Fu-Hao Zhang, Qian-Qian Peng, Xiao-Chen Wang
Lewis acid-catalyzed enantioselective [3+2] dipolar cycloaddition reactions between 1,3-dipoles and C=C or C≡C bonds conjugated with carbonyl groups have been extensively explored, affording highly diastereo- and enantioselective transformations with diverse metal-based Lewis acids. However, these methods generally rely on structurally engineered, auxiliary-containing dipolarophiles to achieve bidentate coordination with the catalyst. In contrast, unmodified monodentate dipolarophiles remain challenging because the competitive coordination of the dipole suppresses reactivity, and the structural flexibility of the Lewis acid-dipolarophile complex undermines enantiocontrol. Here we report the first enantioselective [3+2] cycloaddition of nitrones with monodentate alkynones, enabled by a spiro-bicyclic bisborane catalyst. Mechanistic studies and DFT calculations reveal that alkynone activation occurs through a dynamic equilibrium involving the catalyst, nitrone, and alkynone, while multiple noncovalent interactions between the catalyst and both reaction partners stabilize the transition-state structures for cycloaddition, which is essential for enantiocontrol. Moreover, this catalytic system is also amenable to the diastereo- and enantioselective cycloaddition of nitrones with monodentate enones.
{"title":"Asymmetric [3+2] Dipolar Cycloaddition of Nitrones with Alkynones or Enones Catalyzed by Spiro-Bicyclic Bisborane Catalysts","authors":"Zhi-Hao Chen, Lu Liu, Yun-Bo Wang, Fu-Hao Zhang, Qian-Qian Peng, Xiao-Chen Wang","doi":"10.31635/ccschem.025.202506952","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506952","url":null,"abstract":"Lewis acid-catalyzed enantioselective [3+2] dipolar cycloaddition reactions between 1,3-dipoles and C=C or C≡C bonds conjugated with carbonyl groups have been extensively explored, affording highly diastereo- and enantioselective transformations with diverse metal-based Lewis acids. However, these methods generally rely on structurally engineered, auxiliary-containing dipolarophiles to achieve bidentate coordination with the catalyst. In contrast, unmodified monodentate dipolarophiles remain challenging because the competitive coordination of the dipole suppresses reactivity, and the structural flexibility of the Lewis acid-dipolarophile complex undermines enantiocontrol. Here we report the first enantioselective [3+2] cycloaddition of nitrones with monodentate alkynones, enabled by a spiro-bicyclic bisborane catalyst. Mechanistic studies and DFT calculations reveal that alkynone activation occurs through a dynamic equilibrium involving the catalyst, nitrone, and alkynone, while multiple noncovalent interactions between the catalyst and both reaction partners stabilize the transition-state structures for cycloaddition, which is essential for enantiocontrol. Moreover, this catalytic system is also amenable to the diastereo- and enantioselective cycloaddition of nitrones with monodentate enones.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"29 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955828","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}
Despite the recent impressive progress in synthesizing α-substituted aliphatic amines, the photoredox catalytic generation of C,N,N-trialkyl α-amino radicals from aliphatic amides for cross-coupling with other catalytically generated radicals remains unresolved. In this report, we present the design and successful implementation of an iridium-photoredox tandem catalysis-based reductive cross-coupling of aliphatic tertiary amides with 4-cyanopyridines, resulting in the formation of α-pyridin-4-yl alkylamines. This process is facilitated both by the TfOH-promoted iminium ion intermediates formation and by the subsequent photocatalytic single electron transfer to generate C,N,N-trialkyl α-amino radicals. This method is also enabled by proton-coupled electron transfer to generate polarity-matched persistent 4-cyano-1,4-dihydropyridine radical partners, thus allowing radical–radical cross-coupling reactions. The value of this method was demonstrated by the one-pot transformation of products into α-piperidein-4-yl, α-piperidin-4-yl, and 1,2-dihydropyridin-4-yl alkylamines, as well as by diversification of several bioactive molecules and medicinal agents.
{"title":"Unlocking Aliphatic Tertiary Amides as Versatile Substrates for Photocatalytic Reductive Cross-Coupling Reactions","authors":"Zheng-Yun Weng, Yu-Qing Li, Wen-Xin He, Zi-Yi Chen, Pei-Qiang Huang","doi":"10.31635/ccschem.025.202506810","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506810","url":null,"abstract":"Despite the recent impressive progress in synthesizing α-substituted aliphatic amines, the photoredox catalytic generation of <i>C,N,N</i>-trialkyl α-amino radicals from aliphatic amides for cross-coupling with other catalytically generated radicals remains unresolved. In this report, we present the design and successful implementation of an iridium-photoredox tandem catalysis-based reductive cross-coupling of aliphatic tertiary amides with 4-cyanopyridines, resulting in the formation of α-pyridin-4-yl alkylamines. This process is facilitated both by the TfOH-promoted iminium ion intermediates formation and by the subsequent photocatalytic single electron transfer to generate <i>C,N,N</i>-trialkyl α-amino radicals. This method is also enabled by proton-coupled electron transfer to generate polarity-matched persistent 4-cyano-1,4-dihydropyridine radical partners, thus allowing radical–radical cross-coupling reactions. The value of this method was demonstrated by the one-pot transformation of products into α-piperidein-4-yl, α-piperidin-4-yl, and 1,2-dihydropyridin-4-yl alkylamines, as well as by diversification of several bioactive molecules and medicinal agents.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"40 1","pages":"1-14"},"PeriodicalIF":11.2,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949972","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}
Pub Date : 2026-01-09DOI: 10.31635/ccschem.025.202507034
Jing Wang, Ke Zhang, Yu-Zhe Chen, Chen-Ho Tung, Li-Zhu Wu
Phosphorescence brightness (Bp = nεΦp), a crucial optical performance parameter for nanoparticle, remains undefined and unoptimized due to the inherent trade-off between phosphor density (n) and quantum yield (Φp) under nanoconfinement. Here, we employ the robust models of silica nanoparticles for Bp quantification and propose a supramolecular co-assembly approach that decouples n and Φp by incorporating sterically bulky spacers. These spacers spatially isolate phosphors within SiO2 nanoparticle matrices, thereby suppressing aggregation-caused quenching-as validated by comprehensive photophysical studies-and enabling efficient triplet emission. This approach results in an 85-fold enhancement in Bp, allowing its systematic quantification for the first time. This strategy demonstrates broad applicability across diverse phosphors and retains exceptional brightness upon integration into polymer films. Furthermore, the spacer facilitates enhanced phosphorescence energy transfer (up to 94.9%) to photochromic dithienylethene derivatives in SiO2 microspheres, enabling dynamic modulation of emission. This work not only establishes a quantitative foundation for phosphorescence brightness of nanoparticles for the first time, but also provides a versatile supramolecular platform for the rational design of high-performance room-temperature phosphorescent nanomaterials.
{"title":"Overcoming the n-Φp Trade-off: Co-Assembly Enhanced Organic Phosphorescence Brightness in Water-Dispersible Nanoparticles","authors":"Jing Wang, Ke Zhang, Yu-Zhe Chen, Chen-Ho Tung, Li-Zhu Wu","doi":"10.31635/ccschem.025.202507034","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507034","url":null,"abstract":"Phosphorescence brightness (B<sub>p</sub> = nεΦ<sub>p</sub>), a crucial optical performance parameter for nanoparticle, remains undefined and unoptimized due to the inherent trade-off between phosphor density (n) and quantum yield (Φ<sub>p</sub>) under nanoconfinement. Here, we employ the robust models of silica nanoparticles for B<sub>p</sub> quantification and propose a supramolecular co-assembly approach that decouples n and Φ<sub>p</sub> by incorporating sterically bulky spacers. These spacers spatially isolate phosphors within SiO<sub>2</sub> nanoparticle matrices, thereby suppressing aggregation-caused quenching-as validated by comprehensive photophysical studies-and enabling efficient triplet emission. This approach results in an 85-fold enhancement in B<sub>p</sub>, allowing its systematic quantification for the first time. This strategy demonstrates broad applicability across diverse phosphors and retains exceptional brightness upon integration into polymer films. Furthermore, the spacer facilitates enhanced phosphorescence energy transfer (up to 94.9%) to photochromic dithienylethene derivatives in SiO<sub>2</sub> microspheres, enabling dynamic modulation of emission. This work not only establishes a quantitative foundation for phosphorescence brightness of nanoparticles for the first time, but also provides a versatile supramolecular platform for the rational design of high-performance room-temperature phosphorescent nanomaterials.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"8 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145937968","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}
Pub Date : 2026-01-08DOI: 10.31635/ccschem.025.202507105
Xin Li, Ying-Wei Yang
Nanoimpellers, an essential class of molecular machines enabling photocontrolled cargo delivery, have succeeded in amorphous matrices but face spatial confinement challenges in crystalline frameworks. Here, we construct azobenzene-pendant metal-organic framework (MOF)-based nanoimpeller platforms through dimensional control, achieving efficient on-demand delivery. By synthesizing two-dimensional (2D) layered Zn-Azo-MOF-1 and three-dimensional (3D) network Zn-Azo-MOF-2 with identical components, we achieve an order-of-magnitude enhancement in photoisomerization efficiency for the 2D framework (cis%: 33% vs. 3%). Mechanical grinding triggers interlayer sliding within the 2D structure, thereby breaking spatial confinement and activating high-efficiency photoisomerization. Analyses of rotational barriers and framework-pendant interactions reveal how dimensionality and mechanical activation synergistically tune the spatial confinement that governs photoswitching kinetics. This work establishes nanoimpeller design concepts in crystalline frameworks and provides dimensional engineering principles for stimuli-responsive materials with programmable switching behavior.
纳米叶轮是一种重要的分子机器，可以实现光控制货物的输送，它在非晶基质中取得了成功，但在晶体框架中面临空间限制的挑战。本文通过尺寸控制构建了偶氮苯悬垂金属有机框架（MOF）纳米叶轮平台，实现了高效的按需交付。通过合成具有相同组分的二维（2D）层状Zn-Azo-MOF-1和三维（3D）网状Zn-Azo-MOF-2，我们实现了二维框架光异构化效率的数量级提高（cis%: 33% vs. 3%）。机械研磨触发二维结构层间滑动，从而打破空间限制，激活高效光异构化。旋转屏障和框架-垂坠相互作用的分析揭示了维度和机械激活如何协同调节控制光开关动力学的空间限制。这项工作在晶体框架中建立了纳米叶轮设计概念，并为具有可编程开关行为的刺激响应材料提供了尺寸工程原理。
{"title":"Breaking Spatial Confinement to Unlock MOF-Based Nanoimpellers for Photocontrolled Cargo Delivery through Dimensional Engineering","authors":"Xin Li, Ying-Wei Yang","doi":"10.31635/ccschem.025.202507105","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507105","url":null,"abstract":"Nanoimpellers, an essential class of molecular machines enabling photocontrolled cargo delivery, have succeeded in amorphous matrices but face spatial confinement challenges in crystalline frameworks. Here, we construct azobenzene-pendant metal-organic framework (MOF)-based nanoimpeller platforms through dimensional control, achieving efficient on-demand delivery. By synthesizing two-dimensional (2D) layered Zn-Azo-MOF-1 and three-dimensional (3D) network Zn-Azo-MOF-2 with identical components, we achieve an order-of-magnitude enhancement in photoisomerization efficiency for the 2D framework (<i>cis</i>%: 33% vs. 3%). Mechanical grinding triggers interlayer sliding within the 2D structure, thereby breaking spatial confinement and activating high-efficiency photoisomerization. Analyses of rotational barriers and framework-pendant interactions reveal how dimensionality and mechanical activation synergistically tune the spatial confinement that governs photoswitching kinetics. This work establishes nanoimpeller design concepts in crystalline frameworks and provides dimensional engineering principles for stimuli-responsive materials with programmable switching behavior.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"511 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938011","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}
Pub Date : 2026-01-08DOI: 10.31635/ccschem.025.202506655
Zhaozhong Wang, Lan Hui, Xueting Zhang, Chenxuan Liu, Yuliang Li
Defect engineering is a promising strategy to improve the catalytic performance of electrocatalysts, attracting significant attention from the scientific community. We successfully controlled the defect structure of the electrocatalysts, leading to changes to the surface structure, including step-like, twin boundaries (TB), angularlike, and grain boundaries (GB). We found that this nanoparticle with a multi-defect structure demonstrated an excellent mass activity (23.5 A mgPt−1) that was 26.1 and 19.6 times higher than that of commercial Pt/C and conventional Pt nanoparticles towards the methanol oxidation reaction (MOR). This catalyst shows extremely outstanding durability with no activity decay after 10000 cycles. Operando studies and computational investigation (DFT) suggested that the TBs were readily reactive with CO, significantly promoting the electrooxidation of carbon monoxide. Meanwhile, the GBs significantly reduced the adsorption of CO on the platinum surface. These defect structures generate strong tensile and compressive strains at the interface, greatly promoting the interactions between the catalyst and intermediate and changing the catalytic process/activity of the traditional catalytic system in the catalytic effect. Such a catalytic system demonstrated transformative performance in methanol oxidation.
缺陷工程是改善电催化剂催化性能的一种很有前途的策略，受到了科学界的广泛关注。我们成功地控制了电催化剂的缺陷结构，导致表面结构的变化，包括阶梯状、孪晶界（TB）、角状和晶界（GB）。我们发现，这种具有多缺陷结构的纳米颗粒在甲醇氧化反应（MOR）中表现出优异的质量活性（23.5 a mgPt−1），分别是商业Pt/C和传统Pt纳米颗粒的26.1和19.6倍。该催化剂具有非常出色的耐久性，经过10000次循环后活性不衰减。Operando研究和计算研究（DFT）表明，TBs很容易与CO反应，显著促进一氧化碳的电氧化。同时，GBs显著降低了CO在铂表面的吸附。这些缺陷结构在界面处产生强烈的拉伸和压缩应变，极大地促进了催化剂与中间体之间的相互作用，在催化效果上改变了传统催化体系的催化过程/活性。这种催化体系在甲醇氧化中表现出转化性能。
{"title":"Controllable Manufacturing of Multiple Defects for Efficient Methanol Oxidation","authors":"Zhaozhong Wang, Lan Hui, Xueting Zhang, Chenxuan Liu, Yuliang Li","doi":"10.31635/ccschem.025.202506655","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506655","url":null,"abstract":"Defect engineering is a promising strategy to improve the catalytic performance of electrocatalysts, attracting significant attention from the scientific community. We successfully controlled the defect structure of the electrocatalysts, leading to changes to the surface structure, including step-like, twin boundaries (TB), angularlike, and grain boundaries (GB). We found that this nanoparticle with a multi-defect structure demonstrated an excellent mass activity (23.5 A mg<sub>Pt</sub><sup>−1</sup>) that was 26.1 and 19.6 times higher than that of commercial Pt/C and conventional Pt nanoparticles towards the methanol oxidation reaction (MOR). This catalyst shows extremely outstanding durability with no activity decay after 10000 cycles. Operando studies and computational investigation (DFT) suggested that the TBs were readily reactive with CO, significantly promoting the electrooxidation of carbon monoxide. Meanwhile, the GBs significantly reduced the adsorption of CO on the platinum surface. These defect structures generate strong tensile and compressive strains at the interface, greatly promoting the interactions between the catalyst and intermediate and changing the catalytic process/activity of the traditional catalytic system in the catalytic effect. Such a catalytic system demonstrated transformative performance in methanol oxidation.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"28 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955831","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}
Amphiphilic fullerene derivatives demonstrate promising antineoplastic activity through interactions with tumor-associated proteins and modulation of the tumor microenvironment. However, their target identification remains challenging owing to unique three-dimensional molecular structures and limitations of conventional screening approaches. In this study, we applied competitive activity-based protein profiling (ABPP) to map potential targets of four amphiphilic fullerene derivatives, using the competitive ratio (C-ratio) as a quantitative measure of binding affinity. Leveraging these data, we developed Uni-Full, a tailored AI model based on the Uni-Clip framework, which integrates contrastive learning and a list-wise ranking loss to enhance affinity prediction and generalization. Uni-Full showed a strong correlation with experimental data and accurately identified both established and novel TAEPC targets, including PES1 and PHF19, while effectively minimizing false positives and false negatives. Experimental validation confirmed that TAEPC directly binds PES1, disrupting its nucleolar localization and inhibiting cancer cell proliferation. Our study establishes Uni-Full as a robust, proteome-wide prediction framework that bridges chemoproteomics and AI, accelerating the development of fullerene-based anticancer therapeutics.
{"title":"Uni-Full: An AI Model for Accurate Prediction of Protein Targets of Amphiphilic Fullerene Derivatives","authors":"Libin Yang, Zehu Wang, Zhanfeng Wang, Wenkang Jiang, Yicheng Lu, Bowen Li, Ziyi Zhang, Jiao Li, Feng Yu, Qingqing Guo, Jie Li, Chunru Wang, Chunli Bai","doi":"10.31635/ccschem.025.202506796","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506796","url":null,"abstract":"Amphiphilic fullerene derivatives demonstrate promising antineoplastic activity through interactions with tumor-associated proteins and modulation of the tumor microenvironment. However, their target identification remains challenging owing to unique three-dimensional molecular structures and limitations of conventional screening approaches. In this study, we applied competitive activity-based protein profiling (ABPP) to map potential targets of four amphiphilic fullerene derivatives, using the competitive ratio (C-ratio) as a quantitative measure of binding affinity. Leveraging these data, we developed Uni-Full, a tailored AI model based on the Uni-Clip framework, which integrates contrastive learning and a list-wise ranking loss to enhance affinity prediction and generalization. Uni-Full showed a strong correlation with experimental data and accurately identified both established and novel TAEPC targets, including PES1 and PHF19, while effectively minimizing false positives and false negatives. Experimental validation confirmed that TAEPC directly binds PES1, disrupting its nucleolar localization and inhibiting cancer cell proliferation. Our study establishes Uni-Full as a robust, proteome-wide prediction framework that bridges chemoproteomics and AI, accelerating the development of fullerene-based anticancer therapeutics.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"125 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938010","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}
Fullerene-based materials, particularly [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), are extensively employed as electron transport materials (ETMs) in inverted perovskite solar cells (PSCs) due to their superior electron transport properties. However, their insufficient passivation capability and tendency to aggregates in films can lead to interfacial charge accumulation and charge carrier recombination losses, ultimately compromising both the efficiency and stability of PSCs. To address these challenges, we developed a novel fullerene derivative, PC61BP, by grafting a cyano-phosphate (CNPhP) functional group to fullerene. The phosphate moiety and -CN group in PC61BP can coordinate with under-coordinated Pb2+ ions on the perovskite surface, facilitating defect passivation and suppressing charge non-radiative recombination. Importantly, the incorporation of CNPhP group can modulate intermolecular interactions among PC61BP molecules, preventing aggregation and promoting the formation of a more uniform film. Consequently, the inverted devices using PC61BP as ETM achieve a champion power conversion efficiency (PCE) of 26.01%, markedly outperforming the PC61BM-based control device (PCE = 24.59%), along with improved stability. Moreover, the 1.01 cm2 devices using PC61BP as ETM achieve a high efficiency of 24.48%. This study offers a promising strategy for advancing the performance of inverted PSCs through the rational design of fullerene-based ETMs.
{"title":"Functional Fullerene Electron Transport Material Beyond PC61BM for Efficient Inverted Perovskite Solar Cells","authors":"Zhenyou Guo, Hang Liu, Yuhan Liu, Yihang Yao, Peiyu Hu, Yuping Gao, Xingbang Gao, Weikai Zhao, Yanna Hou, Wenjuan Feng, Yu Chen, Zhiyuan Xu, Ziyang Hu, Guankui Long, Yongsheng Liu","doi":"10.31635/ccschem.025.202507064","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507064","url":null,"abstract":"Fullerene-based materials, particularly [6,6]-phenyl-C<sub>61</sub>-butyric acid methyl ester (PC<sub>61</sub>BM), are extensively employed as electron transport materials (ETMs) in inverted perovskite solar cells (PSCs) due to their superior electron transport properties. However, their insufficient passivation capability and tendency to aggregates in films can lead to interfacial charge accumulation and charge carrier recombination losses, ultimately compromising both the efficiency and stability of PSCs. To address these challenges, we developed a novel fullerene derivative, PC<sub>61</sub>BP, by grafting a cyano-phosphate (CNPhP) functional group to fullerene. The phosphate moiety and -CN group in PC<sub>61</sub>BP can coordinate with under-coordinated Pb<sup>2+</sup> ions on the perovskite surface, facilitating defect passivation and suppressing charge non-radiative recombination. Importantly, the incorporation of CNPhP group can modulate intermolecular interactions among PC<sub>61</sub>BP molecules, preventing aggregation and promoting the formation of a more uniform film. Consequently, the inverted devices using PC<sub>61</sub>BP as ETM achieve a champion power conversion efficiency (PCE) of 26.01%, markedly outperforming the PC<sub>61</sub>BM-based control device (PCE = 24.59%), along with improved stability. Moreover, the 1.01 cm<sup>2</sup> devices using PC<sub>61</sub>BP as ETM achieve a high efficiency of 24.48%. This study offers a promising strategy for advancing the performance of inverted PSCs through the rational design of fullerene-based ETMs.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"35 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145937970","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}
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