Science China Chemistry最新文献

{"title":"Visible light-mediated 1,3-acylative chlorination of cyclopropanes employing benzoyl chloride as bifunctional reagents in NHC catalysis","authors":"Mingrui Li,&nbsp;Xiao Song,&nbsp;Xueyun Lu,&nbsp;Jiuli Xia,&nbsp;Guangfan Zheng,&nbsp;Qian Zhang","doi":"10.1007/s11426-024-2525-0","DOIUrl":"10.1007/s11426-024-2525-0","url":null,"abstract":"<div><p>Chlorine-substituted ketones are crucial intermediates in organic synthesis, and acyl chlorination of chemical feedstocks employing commercially available benzoyl chloride provides an atom-and-step economic route for their synthesis. While atom-transfer radical addition (ATRA) has proven effective for 1,2-acyl chlorination, the efficient realization of 1,3-acyl chlorination has remained a considerable challenge. In this study, an NHC/photocatalyst dual-catalyzed system was developed to facilitate the 1,3-acyl chlorination of cyclopropanes using benzoyl chloride as a bifunctional reagent. This strategy also enables the synthesis of acyl-cyclopropanes with quaternary carbon centers through a nucleophilic annulation process. The practical utility of this approach was demonstrated through large-scale synthesis, product derivatization, and the preparation of analogs of anti-psychotics, including haloperidol, melperone and fluanisone.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 8","pages":"3628 - 3635"},"PeriodicalIF":9.7,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145164186","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":"Pressure-induced cation and vacancy disorder-order transition and near-zero τf in deficient hexagonal perovskite Ba8ZnTa6O24 dielectrics","authors":"Bin Zheng,&nbsp;Ruiwen Ji,&nbsp;Cécile Genevois,&nbsp;Wenda Zhang,&nbsp;Xing Ming,&nbsp;Qiang Zhang,&nbsp;Mathieu Allix,&nbsp;Congling Yin,&nbsp;Xiaojun Kuang,&nbsp;Xianran Xing","doi":"10.1007/s11426-024-2566-3","DOIUrl":"10.1007/s11426-024-2566-3","url":null,"abstract":"<div><p>Pressure applications can enable the tuning of atomic/defect ordering and provide access to new functional materials. Here, we report that pressure-induced structural transformation featuring disorder-order transition of both cations and vacancies in the 8-layer deficient hexagonal perovskite tantalate dielectrics Ba₈ZnTa₆O₂₄, which transformed the structure from twin to shift and remarkably lowered the temperature coefficient of resonant frequency <i>τ</i>_f down to near zero (∼0.56 ppm/°C) from 38 ppm/°C for the twinned precursor. The atomic scale STEM-HAADF and EDS results confirm the ordering of Zn in the Ta host at the nanometer scale in the shifted material featuring well-ordered Ba₈ZnTa₆O₂₄ slabs intergrown with Ba₃ZnTa₂O₉ and Ba₅Ta₄O₁₅ monolayers and anti-phase grain boundaries as planar defects. The pressure-induced twin-shift structural transformation of Ba₈ZnTa₆O₂₄ features the rare constant concentration of the hexagonal stacked layers, which is allowed by the vacancy ordering at the central layers of face-shared octahedral (FSO) trimers avoiding the FSO <i>B-B</i> repulsion, and remarkably the faster cationic ordering kinetics compared with the 2:1 ordered complex perovskites. Although the inclusion of numerous planar defects and the oxidizable atomic defects led to significant <i>p</i>-type conduction and inhomogeneous electrical microstructures, resulting in an extraordinarily high extrinsic dielectric loss for the high-pressure shifted Ba₈ZnTa₆O₂₄ pellet, the intrinsically near-zero <i>τ</i>_f could make the shifted Ba₈ZnTa₆O₂₄ perovskite an ideal microwave dielectric resonator candidate if the defects could be eliminated.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 8","pages":"3510 - 3517"},"PeriodicalIF":9.7,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145163927","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":"Aegis of oxide passivation stabilizes catalytic methanol steam reforming","authors":"Han Yan,&nbsp;Jie Zeng","doi":"10.1007/s11426-025-2610-5","DOIUrl":"10.1007/s11426-025-2610-5","url":null,"abstract":"","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 6","pages":"2215 - 2216"},"PeriodicalIF":9.7,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145163296","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":"Stabilizing molecular contacts via amorphous structures","authors":"Yongzhen Wu","doi":"10.1007/s11426-025-2594-8","DOIUrl":"10.1007/s11426-025-2594-8","url":null,"abstract":"","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 5","pages":"1637 - 1638"},"PeriodicalIF":10.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143918984","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":"Energy-generating lithium recovery integrated with gas capture","authors":"Zhuozhao Wu,&nbsp;Guangmin Zhou","doi":"10.1007/s11426-025-2596-7","DOIUrl":"10.1007/s11426-025-2596-7","url":null,"abstract":"","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 6","pages":"2212 - 2214"},"PeriodicalIF":9.7,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145163297","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":"Nickel-single-atom enriched conjugated coordination polymers for efficient urea oxidation electrocatalysis","authors":"Longsheng Zhang,&nbsp;Yidan Ding,&nbsp;Hui Zheng,&nbsp;Ziwei Ma,&nbsp;Jinyu Ye,&nbsp;Yunxia Liu,&nbsp;Yizhe Zhang,&nbsp;Shouhan Zhang,&nbsp;Haiping Lin,&nbsp;Tianxi Liu","doi":"10.1007/s11426-024-2552-2","DOIUrl":"10.1007/s11426-024-2552-2","url":null,"abstract":"<div><p>Urea oxidation reaction (UOR) electrocatalysis, a promising anodic reaction with lower overpotentials than the oxygen evolution reaction, can work in tandem with many cathodic reactions to improve energy-conversion efficiencies. Among other catalysts, single-atom catalysts (SACs) possess immense potential as high-performance and low-cost catalysts towards UOR, owing to their numerous advantages such as metal-utilization efficiency and low-coordination metal sites. Nevertheless, systematic studies remain unexplored for the local coordination structures of SACs regulating their UOR pathways, which severely impedes further performance advancement. Here, we aim to construct the mechanistic picture of UOR pathways on SACs, using two nickel-single-atom enriched conjugated coordination polymers (named Ni–N–CP and Ni–O–CP) with well-defined NiN₄ and NiO₄ coordination structures for the proof-of-concept studies. The Ni–O–CP exhibits exceptional UOR performance with a turnover frequency of 0.51 s⁻¹, significantly outperforming the Ni–N–CP (0.38 s⁻¹) and other state-of-the-art SACs towards UOR. Our theoretical calculations combined with <i>in-situ</i> Fourier transform infrared and ultraviolet-visible spectroscopy measurements elucidate that two UOR pathways towards NO₂⁻ and N₂ products were identified, which critically depends on the participation of the as-generated ammonia species in the UOR process. This work provides insights for regulating the activity and selectivity of UOR electrocatalysis.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 9","pages":"4381 - 4388"},"PeriodicalIF":9.7,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011680","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":"Recent progress in electrocatalytic C-N coupling of CO2 and inorganic N-containing small molecules","authors":"Huijuan Jing,&nbsp;Jun Long,&nbsp;Dunfeng Gao,&nbsp;Guoxiong Wang,&nbsp;Jianping Xiao","doi":"10.1007/s11426-024-2539-x","DOIUrl":"10.1007/s11426-024-2539-x","url":null,"abstract":"<div><p>The conversion and utilization of carbon dioxide (CO₂) is one of the central topics in the energy and environmental research community. The development of electrocatalytic CO₂ reduction technology is expected to bring more economic and environmental benefits to the carbon-neutral policy. Although researchers have conducted extensive and in-depth studies on the electrocatalytic CO₂ reduction to derive diverse carbonaceous products such as C₁ and C₂₊, the introduction of inorganic nitrogenous molecules in the electrocatalytic CO₂ reduction can further expand the production of more valuable C-N bond-containing chemicals, such as amides, amines, and urea. This review focuses on the research progress in the electrochemical C-N coupling of CO₂ with diverse nitrogenous small molecules (NH₃, N₂, NO, NO₂⁻, and NO₃⁻) in aqueous solution. The C-N coupling mechanisms and electrocatalytic performance of catalysts towards different products have been discussed in depth from both computational and experimental aspects. On this basis, the research directions and prospects in this field are proposed, aiming to provide valuable insights into future research on electrocatalytic C-N coupling.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 9","pages":"4047 - 4067"},"PeriodicalIF":9.7,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011601","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":"Design of fluorine-rich poly(arylene amine) membranes for liquid aliphatic hydrocarbon separation","authors":"Chao Zhang,&nbsp;Zhi-Kang Xu","doi":"10.1007/s11426-025-2557-y","DOIUrl":"10.1007/s11426-025-2557-y","url":null,"abstract":"","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 5","pages":"1635 - 1636"},"PeriodicalIF":10.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143919027","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":"Unlocking the potential of iridium-osmium carbolong conjugates: a high-performance photocatalyst for melanoma therapy","authors":"Haobing Wang,&nbsp;Hui Wang,&nbsp;Shiyan Chen,&nbsp;Fengshu Cao,&nbsp;Xiuyang Wang,&nbsp;Pingyu Zhang,&nbsp;Huaiyi Huang,&nbsp;Haiping Xia","doi":"10.1007/s11426-024-2533-4","DOIUrl":"10.1007/s11426-024-2533-4","url":null,"abstract":"<div><p>Structural modification and optimization of photosensitizers can improve their photophysical properties, thereby enhancing the therapeutic efficacy of photodynamic therapy (PDT). Here we designed and synthesized a novel bimetallic iridium-osmium complex <b>Ir-Os1</b> as a photosensitizer for PDT of melanoma under 550 nm ight-emitting diode (LED) light irradiation. Compared with the mononuclear metal complexes, <b>Ir-Os1</b> exhibited a significantly higher molar absorption coefficient, resulting in outstanding reactive oxygen species (ROSs) generation and improved photocatalytic oxidation of NADH during the irradiation process. Both <i>in vivo</i> and <i>in vitro</i> studies demonstrated effective inhibition of melanoma cell growth and excellent photocytotoxicity under light irradiation. More interestingly, <b>Ir-Os1</b> was able to hinder the production of bioenergetic substances in cancer cells via the glycolytic pathway, leading to adenosine triphosphate (ATP) starvation-induced cell death and ultimately disrupting cellular energy metabolism. This study suggests that a bimetallic strategy can enhance the photocatalytic efficiency.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 8","pages":"3689 - 3698"},"PeriodicalIF":9.7,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145168508","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":"Modulating alkyl groups in hybrid quaternary ammonium salts to design polar glass-ceramic with strong nonlinear optical response","authors":"Ding-Chong Han,&nbsp;Shuai Chen,&nbsp;Ya-Nan Fan,&nbsp;Zi-Luo Fang,&nbsp;Yong-Peng Liang,&nbsp;Wei-Xiong Zhang","doi":"10.1007/s11426-024-2542-3","DOIUrl":"10.1007/s11426-024-2542-3","url":null,"abstract":"<div><p>Organic-inorganic hybrid glass-ceramics have received ever-growing attention as nascent research hotspots due to their extraordinary optical properties, e.g., nonlinear optical response, whereas the documented hybrid glass-ceramics are associated with underlying steric effects of quaternary phosphonium cations with a large triphenylphosphanyl group (–PPh₃). In contrast, numerous hybrid salts based on more easily accessible quaternary ammonium cations have been reported, but they have rarely been fabricated as glass-ceramics or even glasses. Herein, we present four hybrid quaternary ammonium salts, (R₃NBn)[FeCl₄] (Bn = benzyl; R = Me for <b>1</b>, Et for <b>2</b>, Pr for <b>3</b>, and Bu for <b>4</b>, respectively), which belong to space groups <i>P</i>-1, <i>Pbca, Pna</i>2₁, and <i>P</i>3₁, respectively, and undergo intriguing solid-liquid phase transitions at melting temperatures of 355, 356, 368, and 330 K, respectively. Unlike <b>1–3</b> revealing fast recrystallization during the subsequent cooling processes, <b>4</b> with the longer and more flexible butyl groups shows a much slower recrystallization rate due to the reduced attractive interactions between organic cations and inorganic anions and the increased repulsion from the adjacent cations. As a result, <b>4</b> exhibits thermally-induced reversible crystal-liquid-glass-crystal transformations with vitrified temperature of 248 K and recrystallized on-set temperature of 286 K. Strikingly, a glass-ceramic thin film of <b>4</b> with inner polar micro-crystals embedded in glass was manufactured under ambient conditions. This thin film unfolds great enhancement of second-harmonic generation response, being approximately 12 times larger than its poly-crystalline form, without any poling treatments. The investigation provides the first access to polar glass-ceramic in hybrid quaternary ammonium salts and offers promising insights for designing glass-ceramics in diverse hybrid salts.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 9","pages":"4141 - 4149"},"PeriodicalIF":9.7,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011625","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}