Pub Date : 2026-01-01DOI: 10.31635/ccschem.025.202506282
Chuan Zhu, Jinyan Wan, Jiacheng Chen, Shiguan Wang, Yu Yang, Kai Chen, Patrick J. Walsh, Kai Guo, Chao Feng
An unmet challenge in radical relay difunctionalization of alkenes is the incorporation of two discrete transient radicals in a regiocontrolled manner under transition-metal-free conditions. Current protocols typically rely on persistent radicals or organometallic surrogates to trap radical adducts, thereby suppressing the undesired reactions but limiting the diversity. The direct use of two transient radicals remains synthetically elusive. We present a visible-light photoredox catalyzed alkene dialkylation strategy via a kinetically guided conjugative radical–radical coupling. This transition-metal-free approach enables two direct C(sp3)–C(sp3) bond formations across the C=C double bond using alkyl and allyl or benzyl radicals. Mechanistic investigations reveal the radical nature of the process. The success of this approach hinges on kinetically controlled radical addition to alkene substrates and the steric protection of the resulting radical adducts. This mild and functional-group-tolerant reaction exhibits broad substrate scope and tolerates structurally complex substrates, highlighting its potential for late-stage functionalization.
{"title":"Conjugative Radical–Radical Coupling: Transition-Metal-Free Dialkylation of Alkenes","authors":"Chuan Zhu, Jinyan Wan, Jiacheng Chen, Shiguan Wang, Yu Yang, Kai Chen, Patrick J. Walsh, Kai Guo, Chao Feng","doi":"10.31635/ccschem.025.202506282","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506282","url":null,"abstract":"An unmet challenge in radical relay difunctionalization of alkenes is the incorporation of two discrete transient radicals in a regiocontrolled manner under transition-metal-free conditions. Current protocols typically rely on persistent radicals or organometallic surrogates to trap radical adducts, thereby suppressing the undesired reactions but limiting the diversity. The direct use of two transient radicals remains synthetically elusive. We present a visible-light photoredox catalyzed alkene dialkylation strategy via a kinetically guided conjugative radical–radical coupling. This transition-metal-free approach enables two direct C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond formations across the C=C double bond using alkyl and allyl or benzyl radicals. Mechanistic investigations reveal the radical nature of the process. The success of this approach hinges on kinetically controlled radical addition to alkene substrates and the steric protection of the resulting radical adducts. This mild and functional-group-tolerant reaction exhibits broad substrate scope and tolerates structurally complex substrates, highlighting its potential for late-stage functionalization.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"69 1","pages":"453-464"},"PeriodicalIF":11.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895614","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}
Chiral molecules bearing multiple stereocenters are prevalent in natural products and pharmaceuticals, with their absolute and relative configurations critically influencing biological activity. Consequently, the stereodivergent synthesis of all possible stereoisomers is of great importance, especially for comprehensive structure-activity relationship studies. However, conventional asymmetric catalytic methods typically favor the formation of a single major diastereomer, rendering access to the complete set of stereoisomers highly challenging. In recent years, synergistic dual catalysis has emerged as an effective strategy to this challenge. This approach employs a combination of two distinct chiral catalysts, such as metal/organo, metal/metal, or organo/organo catalytic systems, to enable precise control over enantio- and diastereoselectivity at two stereocenters. This minireview summarizes recent advances in synergistic dual catalytic strategies for the stereodivergent synthesis of multistereocentric compounds. Key aspects include catalyst types, reaction classes, mechanistic insights, and current limitations. In addition, perspectives on future opportunities and challenges in this rapidly evolving field are also discussed.
{"title":"Stereodivergent Synthesis of Multistereocentric Compounds by Synergistic Dual Catalysis","authors":"Panpan Li, Shaozi Sun, Liang Wei, Weiwei Zi, Chun-Jiang Wang, Wanbin Zhang","doi":"10.31635/ccschem.025.202506468","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506468","url":null,"abstract":"Chiral molecules bearing multiple stereocenters are prevalent in natural products and pharmaceuticals, with their absolute and relative configurations critically influencing biological activity. Consequently, the stereodivergent synthesis of all possible stereoisomers is of great importance, especially for comprehensive structure-activity relationship studies. However, conventional asymmetric catalytic methods typically favor the formation of a single major diastereomer, rendering access to the complete set of stereoisomers highly challenging. In recent years, synergistic dual catalysis has emerged as an effective strategy to this challenge. This approach employs a combination of two distinct chiral catalysts, such as metal/organo, metal/metal, or organo/organo catalytic systems, to enable precise control over enantio- and diastereoselectivity at two stereocenters. This minireview summarizes recent advances in synergistic dual catalytic strategies for the stereodivergent synthesis of multistereocentric compounds. Key aspects include catalyst types, reaction classes, mechanistic insights, and current limitations. In addition, perspectives on future opportunities and challenges in this rapidly evolving field are also discussed.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"12 1","pages":"81-114"},"PeriodicalIF":11.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895511","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 : 2026-01-01DOI: 10.31635/ccschem.025.202506153
Xiaozhi Zhang, Dongyue An, Rong Zhang, Yunqi Liu, Xuefeng Lu
Helicenes are a quintessential class of aromatic molecules characterized by their inherent chirality. In recent years, helicene-derived macrocycles have attracted significant attention and witnessed rapid advancements due to their unique conjugated geometries and topological structures, which endow them with intriguing properties such as chirality, self-assembly, and supramolecular organization. However, these macrocycles still face several challenges, including synthetic difficulties stemming from high strain energy, a limited understanding of structure-property relationships, and restricted practical applications. This review is the first to highlight recent progress in helicene-derived macrocycles, categorizing them based on their geometric configurations. It provides an in-depth analysis of their synthetic strategies and explores the correlation between their structures and properties. Furthermore, the potential future directions and applications are discussed.
{"title":"Helicene-Derived Macrocycles: Geometry, Synthesis, and Properties","authors":"Xiaozhi Zhang, Dongyue An, Rong Zhang, Yunqi Liu, Xuefeng Lu","doi":"10.31635/ccschem.025.202506153","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506153","url":null,"abstract":"Helicenes are a quintessential class of aromatic molecules characterized by their inherent chirality. In recent years, helicene-derived macrocycles have attracted significant attention and witnessed rapid advancements due to their unique conjugated geometries and topological structures, which endow them with intriguing properties such as chirality, self-assembly, and supramolecular organization. However, these macrocycles still face several challenges, including synthetic difficulties stemming from high strain energy, a limited understanding of structure-property relationships, and restricted practical applications. This review is the first to highlight recent progress in helicene-derived macrocycles, categorizing them based on their geometric configurations. It provides an in-depth analysis of their synthetic strategies and explores the correlation between their structures and properties. Furthermore, the potential future directions and applications are discussed.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"22 1","pages":"60-80"},"PeriodicalIF":11.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903254","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 : 2026-01-01DOI: 10.31635/ccschem.025.202405289
Yiqian Wu, Fan Jiang, Haoyu Peng, Xueyan Que, Jing Peng, Jiuqiang Li, Yue Wang, Liyong Yuan, Weiqun Shi, Maolin Zhai
The efficient recovery of rhenium (Re), a scarce metal closely associated with the energy and aerospace industries, is essential for alleviating global Re resource tension. For the first time, we propose a radiosensitization reduction method to selectively reclaim ReO4− as ReO2 from its aqueous solutions, utilizing a stable Hf-based metal–organic framework, Hf-BPY, as an effective radiation sensitizer. While interacting with γ-rays or electron beams (EBs), Hf-BPY provides Hf6-cluster arrays with high atomic number, exhibiting radiation attenuation ability that enhances the radiolysis of water, which further increases the yield of reductive hydrated electrons (eaq−) from 2.80 × 10−7 to 4.05 × 10−7 mol/J. As a clean reduction method, the reaction is propelled directly by the enriched eaq−, without the need for any sacrificial agents. Pure ReO2 is obtained with resistance to reoxidation and redissolution. This laboratory-proven approach is further scaled up to liter scale, achieving the recovery of 0.568 and 0.468 g/L of ReO2 using γ-ray and EB irradiation, respectively. Along with its cyclic ability to maintain a stable reduction ratio over seven radiation cycles, this approach holds great potential for industrial Re recovery. The feasibility of radiosensitization reduction for the decontamination of heavy metal pollution is further confirmed, adding to the evidence of its prospects for broad application.
{"title":"Radiosensitization Reduction by a Hf-Based Metal–Organic Framework for Gram-Scale Recovery of Rhenium","authors":"Yiqian Wu, Fan Jiang, Haoyu Peng, Xueyan Que, Jing Peng, Jiuqiang Li, Yue Wang, Liyong Yuan, Weiqun Shi, Maolin Zhai","doi":"10.31635/ccschem.025.202405289","DOIUrl":"https://doi.org/10.31635/ccschem.025.202405289","url":null,"abstract":"The efficient recovery of rhenium (Re), a scarce metal closely associated with the energy and aerospace industries, is essential for alleviating global Re resource tension. For the first time, we propose a radiosensitization reduction method to selectively reclaim ReO<sub>4</sub><sup>−</sup> as ReO<sub>2</sub> from its aqueous solutions, utilizing a stable Hf-based metal–organic framework, Hf-BPY, as an effective radiation sensitizer. While interacting with γ-rays or electron beams (EBs), Hf-BPY provides Hf<sub>6</sub>-cluster arrays with high atomic number, exhibiting radiation attenuation ability that enhances the radiolysis of water, which further increases the yield of reductive hydrated electrons (e<sub>aq</sub><sup>−</sup>) from 2.80 × 10<sup>−7</sup> to 4.05 × 10<sup>−7</sup> mol/J. As a clean reduction method, the reaction is propelled directly by the enriched e<sub>aq</sub><sup>−</sup>, without the need for any sacrificial agents. Pure ReO<sub>2</sub> is obtained with resistance to reoxidation and redissolution. This laboratory-proven approach is further scaled up to liter scale, achieving the recovery of 0.568 and 0.468 g/L of ReO<sub>2</sub> using γ-ray and EB irradiation, respectively. Along with its cyclic ability to maintain a stable reduction ratio over seven radiation cycles, this approach holds great potential for industrial Re recovery. The feasibility of radiosensitization reduction for the decontamination of heavy metal pollution is further confirmed, adding to the evidence of its prospects for broad application.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"19 1","pages":"1-13"},"PeriodicalIF":11.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895512","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}
Bacterial biological warfare agents (BBWAs) pose a severe global threat due to their high pathogenicity, rapid transmission, and potential for mass casualties. Conventional detection methods, such as culture-based identification and polymerase chain reaction (PCR), are hindered by limitations in time consumption, operational complexity, and adaptability to complex environments. Surface-enhanced Raman spectroscopy (SERS) has emerged as a transformative analytical tool, offering the simplicity of optical detection, molecular fingerprint specificity, and single-molecule sensitivity. This mini-review systematically reports recent advancements (2019–2024) in SERS-based technologies for BBWA detection, including label-free direct detection leveraging nanostructured substrates, antibody-reporter molecule labeling for enhanced specificity, immunomagnetic separation to address low-concentration samples, and microfluidic-SERS integration enabling portable on-site analysis. These innovations highlight SERS’s potential in biodefense, environmental monitoring, clinical diagnostics, and food safety. Recent breakthroughs in machine learning, particularly deep-learning-assisted spectral analysis, enhance multiplexed, real-time pathogen detection. Despite such progress, challenges persist in substrate consistency, signal stability, and field deployment. Emerging solutions, including atomic-scale substrate engineering, artificial intelligence (AI)-driven data interpretation, and hybrid enrichment-detection platforms, promise to bridge the gap between laboratory precision and adaptability to practical testing environments. By synthesizing advancements across interdisciplinary fields, this review underscores SERS’s evolving role as a rapid, ultrasensitive, and field-deployable tool for combating biosecurity threats, ultimately contributing to global health security frameworks.
{"title":"Surface-Enhanced Raman Spectroscopy for Detection of Bacterial Biological Warfare Agents: A Review","authors":"Pengwei Duan, Xiao Xia Han, Bing Zhao, Hidetoshi Sato, Yukihiro Ozaki, Weidong Ruan","doi":"10.31635/ccschem.025.202506651","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506651","url":null,"abstract":"Bacterial biological warfare agents (BBWAs) pose a severe global threat due to their high pathogenicity, rapid transmission, and potential for mass casualties. Conventional detection methods, such as culture-based identification and polymerase chain reaction (PCR), are hindered by limitations in time consumption, operational complexity, and adaptability to complex environments. Surface-enhanced Raman spectroscopy (SERS) has emerged as a transformative analytical tool, offering the simplicity of optical detection, molecular fingerprint specificity, and single-molecule sensitivity. This mini-review systematically reports recent advancements (2019–2024) in SERS-based technologies for BBWA detection, including label-free direct detection leveraging nanostructured substrates, antibody-reporter molecule labeling for enhanced specificity, immunomagnetic separation to address low-concentration samples, and microfluidic-SERS integration enabling portable on-site analysis. These innovations highlight SERS’s potential in biodefense, environmental monitoring, clinical diagnostics, and food safety. Recent breakthroughs in machine learning, particularly deep-learning-assisted spectral analysis, enhance multiplexed, real-time pathogen detection. Despite such progress, challenges persist in substrate consistency, signal stability, and field deployment. Emerging solutions, including atomic-scale substrate engineering, artificial intelligence (AI)-driven data interpretation, and hybrid enrichment-detection platforms, promise to bridge the gap between laboratory precision and adaptability to practical testing environments. By synthesizing advancements across interdisciplinary fields, this review underscores SERS’s evolving role as a rapid, ultrasensitive, and field-deployable tool for combating biosecurity threats, ultimately contributing to global health security frameworks.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"3 1","pages":"1-25"},"PeriodicalIF":11.2,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796177","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 : 2025-12-20DOI: 10.31635/ccschem.025.202506666
Chengxu Li, Yuanxin Gu, Tianjun Zhang, Manyi Yang, Qiming Sun
The methylcyclohexane–toluene (MCH–TOL) redox pair is a promising liquid organic hydrogen carrier (LOHC) system for safe and efficient hydrogen storage; however, its application is hindered by the lack of efficient and stable catalysts for reversible hydrogen release and uptake under mild conditions. Here, we report a robust strategy for constructing ultrasmall and well-dispersed Pt–FeOx nanoparticles anchored on self-pillared silicalite-1 (SP-S-1) zeolite nanosheets using a facile incipient wetness co-impregnation method. The resulting PtFe1.0/SP-S-1 catalyst exhibited remarkable catalytic performance for both MCH dehydrogenation and TOL hydrogenation, enabled by its high surface accessibility, enhanced mass transfer, and strong Pt–FeOx synergistic interactions. Strikingly, it achieved a record-high hydrogen generation rate of 3965 mmolH2 gPt−1 min−1 at 350 °C, representing the top level among the state-of-the-art heterogeneous catalysts under comparable conditions. Density functional theory (DFT) calculations revealed that FeOx incorporation lowered the energy barrier for C–H bond activation in MCH, enriched the electronic density around Pt to facilitate TOL desorption, and enhanced Pt dispersion by suppressing nanoparticle aggregation. This study highlights the exceptional promise of nanosheet-based zeolite-supported metallic catalysts for reversible LOHC reactions, while offering fundamental mechanistic insights that could drive the rational design of advanced catalytic systems for future hydrogen energy technologies.
{"title":"Zeolite Nanosheet-Confined Pt–FeOx Catalysts for Reversible Hydrogen Cycling via the Methylcyclohexane–Toluene System","authors":"Chengxu Li, Yuanxin Gu, Tianjun Zhang, Manyi Yang, Qiming Sun","doi":"10.31635/ccschem.025.202506666","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506666","url":null,"abstract":"The methylcyclohexane–toluene (MCH–TOL) redox pair is a promising liquid organic hydrogen carrier (LOHC) system for safe and efficient hydrogen storage; however, its application is hindered by the lack of efficient and stable catalysts for reversible hydrogen release and uptake under mild conditions. Here, we report a robust strategy for constructing ultrasmall and well-dispersed Pt–FeO<sub><i>x</i></sub> nanoparticles anchored on self-pillared silicalite-1 (SP-S-1) zeolite nanosheets using a facile incipient wetness co-impregnation method. The resulting PtFe<sub>1.0</sub>/SP-S-1 catalyst exhibited remarkable catalytic performance for both MCH dehydrogenation and TOL hydrogenation, enabled by its high surface accessibility, enhanced mass transfer, and strong Pt–FeO<sub><i>x</i></sub> synergistic interactions. Strikingly, it achieved a record-high hydrogen generation rate of 3965 mmol<sub>H2</sub> g<sub>Pt</sub><sup>−1</sup> min<sup>−1</sup> at 350 °C, representing the top level among the state-of-the-art heterogeneous catalysts under comparable conditions. Density functional theory (DFT) calculations revealed that FeO<sub><i>x</i></sub> incorporation lowered the energy barrier for C–H bond activation in MCH, enriched the electronic density around Pt to facilitate TOL desorption, and enhanced Pt dispersion by suppressing nanoparticle aggregation. This study highlights the exceptional promise of nanosheet-based zeolite-supported metallic catalysts for reversible LOHC reactions, while offering fundamental mechanistic insights that could drive the rational design of advanced catalytic systems for future hydrogen energy technologies.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"20 1","pages":"1-14"},"PeriodicalIF":11.2,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145801489","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 : 2025-12-20DOI: 10.31635/ccschem.025.202506694
Zhuoyuan Yang, Shuniao Feng, Pan Xu
Achieving contra-thermodynamic positional isomerization of alkenes presents a fundamental challenge in synthetic chemistry. The strategic conversion of synthetically commodious isomers to elusive analogs offers distinct advantages for chemical space exploration. Here, we report a photocatalytic hydrogen atom transfer strategy that enables direct deconjugation of readily accessible α,β-dehydro amino acids to conventionally challenging β,γ-dehydro amino acids. Leveraging decatungstate (TBADT) as a catalyst under 390 nm light irradiation, the protocol selectively abstracts γ-C–H bonds to generate delocalized allylic radicals. Selective hydrogen-atom donation at the oxygen site forms a dienol intermediate whose tautomerization drives endergonic isomerization. This mechanistic paradigm overcomes microscopic reversibility constraints and operates under mild conditions, accommodating geometrically locked trans substrates, complex pharmaceuticals, and bioactive natural products inaccessible to classical photoisomerization. Mechanistic studies indicate that C–H cleavage is the rate-determining step and supports the proposed radical-dienol pathway.
{"title":"Harnessing Photocatalytic Hydrogen Atom Transfer for Deconjugative Isomerization of α,β-Dehydro Amino Acids","authors":"Zhuoyuan Yang, Shuniao Feng, Pan Xu","doi":"10.31635/ccschem.025.202506694","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506694","url":null,"abstract":"Achieving contra-thermodynamic positional isomerization of alkenes presents a fundamental challenge in synthetic chemistry. The strategic conversion of synthetically commodious isomers to elusive analogs offers distinct advantages for chemical space exploration. Here, we report a photocatalytic hydrogen atom transfer strategy that enables direct deconjugation of readily accessible α,β-dehydro amino acids to conventionally challenging β,γ-dehydro amino acids. Leveraging decatungstate (TBADT) as a catalyst under 390 nm light irradiation, the protocol selectively abstracts γ-C–H bonds to generate delocalized allylic radicals. Selective hydrogen-atom donation at the oxygen site forms a dienol intermediate whose tautomerization drives endergonic isomerization. This mechanistic paradigm overcomes microscopic reversibility constraints and operates under mild conditions, accommodating geometrically locked trans substrates, complex pharmaceuticals, and bioactive natural products inaccessible to classical photoisomerization. Mechanistic studies indicate that C–H cleavage is the rate-determining step and supports the proposed radical-dienol pathway.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"22 1","pages":"1-11"},"PeriodicalIF":11.2,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813287","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}
Near-infrared (NIR) detection is pivotal to the advancement of noninvasive biomedical monitoring. However, simultaneously achieving contact and contactless health detection remains a critical challenge. Although the NIR organic photodetector (OPD) offers intrinsic flexibility for such applications, its low sensitivity, slow response, and poor wavelength selectivity significantly hinders its application in dual-mode detection. Here, we develop a high-performance NIR OPD through a synergistic molecular design and ternary compensation strategy. By introducing a quinoidal π-bridge into a CH-series acceptor, we synthesize a narrow-bandgap acceptor, ZCH-1, realizing a broad spectral absorption ranging from 300 to 1100 nm. Moreover, integrating the donor D18 into the binary OPD effectively passivates trap states and suppresses electron injection, leading to a reduced dark current (8.4 × 10−9 A cm−2), improved responsivity (0.41 A W−1), enhanced specificity detectivity (4.1 × 1012 Jones) at 950 nm, and a rapid response time of 2.4 μs. These metrics represent state-of-the-art balanced NIR OPD for detection beyond 950 nm. Moreover, this device enables real-time physiological measurement in both contact and contactless modes at distances up to 70 mm. Given this performance, coupled with its cost-effective and large-area processing, the high-performance NIR OPD presents a promising platform for next-generation wearable health monitoring and remote healthcare systems.
近红外（NIR）检测是推进无创生物医学监测的关键。然而，同时实现接触式和非接触式健康检测仍然是一个重大挑战。虽然近红外有机光电探测器（OPD）为此类应用提供了固有的灵活性，但其低灵敏度、慢响应和较差的波长选择性严重阻碍了其在双模检测中的应用。在这里，我们通过协同分子设计和三元补偿策略开发了高性能的近红外OPD。通过在ch系列受体中引入抛物线π桥，合成了窄带隙受体ZCH-1，实现了在300 ~ 1100 nm范围内的广谱吸收。此外，将给体D18整合到二元OPD中，有效地钝化了陷阱态并抑制了电子注入，从而降低了暗电流（8.4 × 10−9 a cm−2），提高了响应率（0.41 a W−1），增强了950 nm的特异性检测率（4.1 × 1012 Jones），并提高了响应时间（2.4 μs）。这些指标代表了最先进的平衡NIR OPD，用于950 nm以上的检测。此外，该设备可以在距离达70毫米的距离内以接触和非接触模式进行实时生理测量。鉴于这种性能，加上其成本效益和大面积处理，高性能NIR OPD为下一代可穿戴健康监测和远程医疗系统提供了一个有前途的平台。
{"title":"Enhanced Sensitivity of Near-Infrared Organic Photodetectors via Ternary Compensation for Contact/Contactless Vitality Surveillance","authors":"Jing Zhang, Tingting Guo, Ruiman Han, Hanzhe Shi, Jing Feng, Chen Geng, Mengfan Li, Yu Zhu, Guangkun Song, Yanqing Yang, Xiangjun Lin, Wanyue Zhang, Zhaoyang Yao, Xiangjian Wan, Wangqiao Chen, Guanghui Li, Yongsheng Chen","doi":"10.31635/ccschem.025.202506094","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506094","url":null,"abstract":"Near-infrared (NIR) detection is pivotal to the advancement of noninvasive biomedical monitoring. However, simultaneously achieving contact and contactless health detection remains a critical challenge. Although the NIR organic photodetector (OPD) offers intrinsic flexibility for such applications, its low sensitivity, slow response, and poor wavelength selectivity significantly hinders its application in dual-mode detection. Here, we develop a high-performance NIR OPD through a synergistic molecular design and ternary compensation strategy. By introducing a quinoidal π-bridge into a CH-series acceptor, we synthesize a narrow-bandgap acceptor, ZCH-1, realizing a broad spectral absorption ranging from 300 to 1100 nm. Moreover, integrating the donor D18 into the binary OPD effectively passivates trap states and suppresses electron injection, leading to a reduced dark current (8.4 × 10<sup>−9</sup> A cm<sup>−2</sup>), improved responsivity (0.41 A W<sup>−1</sup>), enhanced specificity detectivity (4.1 × 10<sup>12</sup> Jones) at 950 nm, and a rapid response time of 2.4 μs. These metrics represent state-of-the-art balanced NIR OPD for detection beyond 950 nm. Moreover, this device enables real-time physiological measurement in both contact and contactless modes at distances up to 70 mm. Given this performance, coupled with its cost-effective and large-area processing, the high-performance NIR OPD presents a promising platform for next-generation wearable health monitoring and remote healthcare systems.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"1 1","pages":"1-13"},"PeriodicalIF":11.2,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807643","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 incorporation of trifluoromethyl groups into organic molecules represents a powerful strategy for modulating their physical, chemical, and biological properties. Although the 2H-pyran scaffold is a privileged structure in bioactive compounds, practical methods for constructing trifluoromethylated 2H-pyrans remain limited. Herein, we report a palladium-catalyzed cascade reaction between trifluoroacetylsilanes and 1,3-enynes that efficiently produces diverse 6-CF3-2H-pyrans in good yields. This transformation demonstrates broad substrate scope, excellent functional group tolerance, and high regio- and chemoselectivity. Computational studies reveal a reaction mechanism involving palladium-catalyzed C–Si insertion into the alkyne moiety, followed by oxa-6π-electrocyclization of the in situ generated trifluoromethylated oxatrienes. The synthetic utility of this methodology is further demonstrated through gram-scale synthesis and versatile downstream transformations.
{"title":"Synthesis of Trifluoromethylated 2H-Pyrans Enabled by Pd-Catalyzed Cascade Cyclization of Trifluoroacetylsilanes and 1,3-Enynes","authors":"Peishen Jin, Xiaoqian He, Shanshan Liu, Xiaotian Qi, Xiao Shen","doi":"10.31635/ccschem.025.202506597","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506597","url":null,"abstract":"The incorporation of trifluoromethyl groups into organic molecules represents a powerful strategy for modulating their physical, chemical, and biological properties. Although the <i>2H</i>-pyran scaffold is a privileged structure in bioactive compounds, practical methods for constructing trifluoromethylated <i>2H</i>-pyrans remain limited. Herein, we report a palladium-catalyzed cascade reaction between trifluoroacetylsilanes and 1,3-enynes that efficiently produces diverse 6-CF<sub>3</sub>-<i>2H</i>-pyrans in good yields. This transformation demonstrates broad substrate scope, excellent functional group tolerance, and high regio- and chemoselectivity. Computational studies reveal a reaction mechanism involving palladium-catalyzed C–Si insertion into the alkyne moiety, followed by oxa-6π-electrocyclization of the in situ generated trifluoromethylated oxatrienes. The synthetic utility of this methodology is further demonstrated through gram-scale synthesis and versatile downstream transformations.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"6 1","pages":"1-9"},"PeriodicalIF":11.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807670","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 : 2025-12-18DOI: 10.31635/ccschem.025.202506819
Chengfeng Shen, Xiangyue Wei, Qiuyue Chen, Lei Yan, Xuan Zhao, Xuehui Liu, Shimei Xu, Yu-Zhong Wang
Polyolefins are widely used across industries due to their low cost and excellent stability. However, their inert C–C and C–H bonds pose a significant challenge for functional modification. Meanwhile, the environmental impact of polyolefin waste represents a significant and intensifying issue, rendering its disposal a major challenge. Herein, we developed renewable, recyclable, and durable resins while sustaining the capability to modularly construct various functionalities, called the “LEGO strategy,” via upcycling polyethylene (PE) into multifunctional materials through a two-step process: controlled degradation into macromolecular PE blocks containing active groups, followed by reconstruction with functional blocks via dynamic imine bonds. This approach enabled the incorporation of diverse functionalities, such as flame retardancy, ultraviolet shielding, antistatic performance, and cationic dyeability in an on-demand manner, while enhancing mechanical performance. Moreover, the dynamic nature of the imine bonds and the hydrophobic property of PE chains imparts both excellent water stability and recyclability. This approach offers a new pathway for upcycling polyolefins into diverse functional materials, addressing both environmental concerns and application demands.
{"title":"On-Demand Upcycling of Polyethylene Wastes to Recyclable Multifunctional Materials by LEGO Strategy","authors":"Chengfeng Shen, Xiangyue Wei, Qiuyue Chen, Lei Yan, Xuan Zhao, Xuehui Liu, Shimei Xu, Yu-Zhong Wang","doi":"10.31635/ccschem.025.202506819","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506819","url":null,"abstract":"Polyolefins are widely used across industries due to their low cost and excellent stability. However, their inert C–C and C–H bonds pose a significant challenge for functional modification. Meanwhile, the environmental impact of polyolefin waste represents a significant and intensifying issue, rendering its disposal a major challenge. Herein, we developed renewable, recyclable, and durable resins while sustaining the capability to modularly construct various functionalities, called the “LEGO strategy,” via upcycling polyethylene (PE) into multifunctional materials through a two-step process: controlled degradation into macromolecular PE blocks containing active groups, followed by reconstruction with functional blocks via dynamic imine bonds. This approach enabled the incorporation of diverse functionalities, such as flame retardancy, ultraviolet shielding, antistatic performance, and cationic dyeability in an on-demand manner, while enhancing mechanical performance. Moreover, the dynamic nature of the imine bonds and the hydrophobic property of PE chains imparts both excellent water stability and recyclability. This approach offers a new pathway for upcycling polyolefins into diverse functional materials, addressing both environmental concerns and application demands.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"23 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796176","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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