Chinese Journal of Chemistry最新文献

{"title":"Diastereoselective Formal [3+3] Cascade Cyclization towards Fused 4-Fluoroalkylated 3,4-Dihydro-2H-pyrans via Copper Catalysis","authors":"Weigao Hu,&nbsp;Jiawen Yin,&nbsp;Zhiyong Li,&nbsp;Yin Gao,&nbsp;Xuran Liu,&nbsp;Shenting Zhang,&nbsp;Wenzhu Yu,&nbsp;Lanmei Chen,&nbsp;Jia Zheng","doi":"10.1002/cjoc.70050","DOIUrl":"https://doi.org/10.1002/cjoc.70050","url":null,"abstract":"<div>\u0000 \u0000 <p>The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2<i>H</i>-pyran architectures. Nevertheless, the transformation for preparing fused-polycyclic ones still remains challenging yet highly desirable until now. Herein, we report a novel formal [3+3] cascade cyclization reaction to provide lactam-fused 4-fluoroalkylated 3,4-dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis. Of note, these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp²)-Cl and C(sp³)-H functionalization, which exhibited highly site-selectivity and stereoselectivity. Additionally, evaluations on biological activities of the obtained products revealed that several products display inhibitory activity against Siha and H1975 cancer cell lines.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 15","pages":"1806-1812"},"PeriodicalIF":5.5,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520179","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":"Precise Recognition and Quantification of Locus-Specific DNA Methylation Using Engineered ROS1†","authors":"Li Zeng,&nbsp;Fang-Yin Gang,&nbsp;Tong-Tong Ji,&nbsp;Shan Zhang,&nbsp;Xia Guo,&nbsp;Ying Hao,&nbsp;Jun Xiong,&nbsp;Zhen-Wei Wei,&nbsp;Neng-Bin Xie,&nbsp;Bi-Feng Yuan","doi":"10.1002/cjoc.70044","DOIUrl":"https://doi.org/10.1002/cjoc.70044","url":null,"abstract":"<div>\u0000 \u0000 <p>5-Methylcytosine (5mC) plays pivotal roles in numerous biological processes. To gain a deeper understanding of the biological functions of 5mC, it is essential to develop methods for its quantitative analysis. Herein, we engineered the repressor of silencing 1 (ROS1) protein to enhance its glycosylase/lyase activity towards 5mC, resulting in an engineered ROS1 (eROS1) protein that can effectively excise 5mC from DNA. Using eROS1, we developed a method termed engineered ROS1-mediated quantitative (eRMQ) analysis, for the locus-specific quantification of 5mC in genomic DNA. This method capitalizes on the ability of eROS1 to selectively cleave 5mC, which creates a one-nucleotide gap. The presence of this gap hinders the extension of DNA polymerase, leading to a reduction in extension products that can be evaluated using real-time quantitative PCR (qPCR). The limit of detection for the eRMQ method was as low as 1 fM. Using the eRMQ method, we achieved the quantitative analysis of 5mC at individual sites within genomic DNA and demonstrated a significant reduction in 5mC levels in lung cancer tissues compared to adjacent normal tissues. Taken together, this study introduces eRMQ method for the quantitative analysis of 5mC in DNA, offering a valuable tool for exploring epigenetic regulation in human diseases.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 15","pages":"1797-1805"},"PeriodicalIF":5.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520285","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":"Sulfonated Phosphine-Palladium/Bisguanidinium Ion Pair Catalyzed Enantioselective Allylic Amination","authors":"Longyi Xi,&nbsp;Rajakili Selvam,&nbsp;Xu Chen,&nbsp;Juan Du,&nbsp;Govindasamy Sekar,&nbsp;Jun Song,&nbsp;Junmin Zhang,&nbsp;Choon-Hong Tan","doi":"10.1002/cjoc.70047","DOIUrl":"https://doi.org/10.1002/cjoc.70047","url":null,"abstract":"<div>\u0000 \u0000 <p>In this study, we successfully developed ion pair catalysts consisting of chiral bisguanidinium (BG) cations and non-chiral sulphonated phosphine-palladium complexes as counterions. These ion pairs catalyzed allylic alkylation reactions with excellent enantioselectivities. Furthermore, these reactions can be easily performed on a gram-scale, demonstrating their potential for industrial applications. We were able to obtain ¹H NMR of the ion pair catalyst and identified the ³¹P NMR of the sulphonated phosphine-palladium complex.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 15","pages":"1813-1818"},"PeriodicalIF":5.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520284","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":"Copper-Catalyzed Cyclopropenation of Alkynes with Difluoromethyl Carbene†","authors":"Yong Yang,&nbsp;Paramasivam Sivaguru,&nbsp;Qingmin Song,&nbsp;Zhaohong Liu,&nbsp;Yong Ji,&nbsp;Wei Song,&nbsp;Karunanidhi Murali,&nbsp;Jacek Mlynarski,&nbsp;Xihe Bi","doi":"10.1002/cjoc.70040","DOIUrl":"https://doi.org/10.1002/cjoc.70040","url":null,"abstract":"<div>\u0000 \u0000 <p>The [2+1] cycloaddition of alkynes with fluoroalkyl carbenes represents the most straightforward approach for constructing fluoroalkylated cyclopropenes. However, until now, this strategy has not been applicable to difluoromethyl carbene, as its precursor, difluoromethyl diazomethane, tends to undergo [3+2] cycloaddition with alkynes to form pyrazoles. This study presents the first example of copper-catalyzed cyclopropenation of alkynes with difluoromethyl carbene, employing difluoroacetaldehyde triftosylhydrazone as the carbene precursor. A wide range of internal and terminal alkynes, featuring diverse functional groups, were efficiently converted into the corresponding difluoromethyl cyclopropenes in good to high yields. Mechanistic investigations, supported by DFT calculations, revealed that the bulky Tp^Br3Cu(NCMe) catalyst plays a pivotal role in facilitating the cyclopropenation of alkynes with difluoromethyl carbenes via a concerted pathway.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 15","pages":"1833-1840"},"PeriodicalIF":5.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520286","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":"Silylative Kinetic Resolution of Acyclic Secondary Benzylic Alcohols Catalyzed by Chiral Guanidine Having Axial Chirality Containing a Methoxy Group","authors":"Yuki Homma,&nbsp;Takahisa Ikeue,&nbsp;Kenya Nakata","doi":"10.1002/cjoc.70025","DOIUrl":"https://doi.org/10.1002/cjoc.70025","url":null,"abstract":"<p>New chiral guanidine catalysts having axial chirality containing a methoxy group were synthesized. Subsequently, their catalytic ability was examined by applying the silylative kinetic resolution of racemic alcohols using chlorosilanes. Based on an X-ray crystallographic analysis of the catalysts, the functional role of the methoxy group was predicted, and the plausible reaction pathways and a transition state were described. It was also revealed that the existence of hydrogen bonding between the methoxy group on the catalyst and hydrogen atom at C-1 position of the substrates was of great importance for attaining high selectivity and reactivity. The proposed method is applicable to various acyclic aryl, heteroaryl, and normal-alkyl alcohols exhibiting medium to high <i>s</i>-values (<i>s</i> = 15–96, 15 examples).</p><p>\u0000 </p>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 13","pages":"1553-1559"},"PeriodicalIF":5.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cjoc.70025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144191141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tactics to Improve the Photodynamic Therapeutic Efficacy Based on Nanomaterials","authors":"Yinghao Cao,&nbsp;Xiaoping Qian,&nbsp;Mengqi Shi,&nbsp;Xiang Sun,&nbsp;Jianhua Zou,&nbsp;Xiaoyuan Chen","doi":"10.1002/cjoc.202401177","DOIUrl":"https://doi.org/10.1002/cjoc.202401177","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <p>The development of photodynamic therapy (PDT), from its initial discovery of photodynamic effects to its current use in various medical conditions, is a testament to its therapeutic potential. Recent breakthroughs in nanotechnology have significantly enhanced the effectiveness of PDT. Typical nanomaterials (NMs), including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and nanozymes have been introduced to enhance the photodynamic efficacy because they can enhance the delivery of PSs, and effectively overcome insufficient targeting specificity, limited tissue penetration depth, and hypoxic microenvironments, thereby amplifying its therapeutic efficacy. However, the clinical application of these NMs in PDT faces several challenges, including concerns regarding biocompatibility, long-term biosafety, and economic feasibility. To further advance PDT, researchers should focus on designing NMs to improve therapeutic outcomes, exploring combination therapies with PDT, and conducting translational clinical trials to validate the safety and therapeutic efficacy of these novel PDT approaches. This review summarizes the recent progress in PDT based on NMs, especially MOFs, COFs and nanozymes and their application in disease treatment. We aim to provide guidance for future research and clinical practice in advancing NMs-enhanced PDT, paving the way for more effective therapeutic strategies.</p>\u0000 \u0000 <p></p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Key Scientists</h3>\u0000 \u0000 <p></p>\u0000 </section>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 14","pages":"1731-1755"},"PeriodicalIF":5.5,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292785","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":"Shape Selective Anion Recognition of Calix[4]resorcinarene-Based Receptors through C—H Hydrogen Bonding","authors":"Kejia Yan,&nbsp;Yi Shi,&nbsp;Zhiyao Wang,&nbsp;Jianmin Jiao,&nbsp;Kaiya Wang,&nbsp;Xiao-Yu Hu","doi":"10.1002/cjoc.70028","DOIUrl":"https://doi.org/10.1002/cjoc.70028","url":null,"abstract":"<div>\u0000 \u0000 <p>This study explores the synthesis of calix[4]resorcinarene-based anion receptors and their shape selective recognition properties. Electron withdrawing groups are modified at the bridging site of the resorcinarene scaffold, leading to a reduction in the electron density of the receptors. The number of fluorine atoms in the receptors is adjusted to regulate their ability to bind anions. Our results demonstrate that these receptors bind with anions in two manners: electropositive \"H\" atoms in the concave cavity bind with non-spherical anion [MeSO₃]⁻ and the lower \"crown\" binds with spherical anion [Cl]⁻. The two binding modes are both driven by C—H∙∙∙anion hydrogen bonding. Besides, mass spectrometric experiments and density functional theory (DFT) calculations also verified the binding mechanism.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 14","pages":"1651-1656"},"PeriodicalIF":5.5,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292786","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":"Wood-Based and Wood-Inspired Thermal Management Materials†","authors":"Yuying Wu,&nbsp;Junqing Chen,&nbsp;Chao Xu,&nbsp;Chaoji Chen","doi":"10.1002/cjoc.202401322","DOIUrl":"https://doi.org/10.1002/cjoc.202401322","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <p>Given the global resource constraints and substantial energy consumption, the innovative development of efficient and precise thermal management materials represents a significant step forward in improving energy efficiency and promoting ecological and environmental sustainability. The unique structure of natural wood with its porous anisotropy provides new insights and strategies for the design of advanced thermal management materials. However, present reviews often fail to provide a comprehensive and systematic analysis of the inherent structural advantages, as well as the strategies pertinent to the construction and utilization of wood-based and biomimetic materials. This review explores the evolution of wood and its biomimetic structures in the field of thermal management materials, detailing the basic structures and compositions of wood and timber, as well as explaining how these materials can be processed and constructed with physical/chemical strategies. In addition, we highlight recent advances in such materials in the fields of thermal insulation, radiative cooling, heat transfer, and thermal energy storage. Finally, we offer some unique insights on the challenges and future developments for the scale-up of the use of such materials, providing our perspectives on their potential for broader implementation.</p>\u0000 \u0000 <p>\u0000 </p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Key Scientists</h3>\u0000 \u0000 <p>Wood-based and wood-inspired materials have achieved significant advancements in thermal management, owing to the sustained efforts of numerous scientists. In 1941, J. D. MacLean carried out the first systematic study on the thermodynamic properties of wood. In 2006, the freeze-drying method developed by Sylvain Deville paved the way for the emergence of biomimetic wood porous materials. In 2015, Lennart Bergstrom prepared biomimetic wood insulation materials via freeze-drying. In 2016, Liangbing Hu initiated a series of physical and chemical approaches, which propelled the development of wood-based thermal management materials. In 2017, Jian Li prepared a Magneto-thermal conversion wood-based material for thermal insulation. In 2022, Shuhong Yu developed an aerogel with a wood-inspired oriented channel structure for thermal insulation. In 2023, Yiqiang Wu developed a bionic skeleton wood-based thermal phase change material. In the same year, Chaoji Chen exploited 3D printing technology to develop biomimetic wood thermal management materials applicable to seawater evaporation.</p>\u0000 \u0000 <p>\u0000 </p>\u0000 </section>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 14","pages":"1691-1706"},"PeriodicalIF":5.5,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292787","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":"Biomimetic and Biological Applications of DNA Coacervates","authors":"Yuqi Zeng,&nbsp;Long Zhao,&nbsp;Yihao Liu,&nbsp;Tianhuan Peng,&nbsp;Yifan Lyu,&nbsp;Quan Yuan","doi":"10.1002/cjoc.202401276","DOIUrl":"https://doi.org/10.1002/cjoc.202401276","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Comprehensive Summary</h3>\u0000 \u0000 <p>Recent progress in nanotechnology and synthetic biology has demonstrated the potential of DNA coacervates for biomimetic and biological applications. DNA coacervates are micron-scale, membrane-free, spherical structures formed by liquid-liquid phase separation of DNA materials. They uniquely combine the programmability of DNA with the fluidic properties of coacervates, allowing for controlled modulation of their structures, biomimetic and biological functions, and dynamic behaviors through rational sequence design. This review summarizes methods for the formation of different DNA coacervates and explores their extensive applications in biomimicry, biosensing and therapeutics. Limitations and prospects of DNA coacervates are also discussed.</p>\u0000 \u0000 <p>\u0000 </p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Key Scientists</h3>\u0000 \u0000 <p></p>\u0000 </section>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 12","pages":"1442-1462"},"PeriodicalIF":5.5,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074706","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":"Photocatalytic Germylation via Direct Hydrogen Atom Transfer","authors":"Wenshan Wang,&nbsp;Yan Liu,&nbsp;Gonghong Qiu,&nbsp;Igor B. Krylov,&nbsp;Alexander O. Terent’ev,&nbsp;Shuxia Cao,&nbsp;Kai Sun,&nbsp;Xiaolan Chen,&nbsp;Lingbo Qu,&nbsp;Bing Yu","doi":"10.1002/cjoc.70038","DOIUrl":"https://doi.org/10.1002/cjoc.70038","url":null,"abstract":"<div>\u0000 \u0000 <p>An innovative visible-light-driven direct hydrogen atom transfer (<i>d</i>-HAT) of Ge–H bond has been developed, wherein the photoexcited 9,10-phenanthraquinone (<b>PC</b>_<b>HAT</b><b>9</b>) serves as an efficient photocatalyst for the generation of germanium-centered radicals from germanium hydrides including Ph₃GeH, ^<i>n</i>Bu₃GeH, and Ph₂GeH₂. By employing hypervalent iodine reagents as SOMOphiles, this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed by β-cleavage of a carboxyl radical to yield a diverse array of ethynyl-, vinyl-, nitrile-, and phenyl-functionalized germanes. The methodological leap signifies a noteworthy departure from the previous photocatalytic indirect hydrogen atom transfer (<i>i</i>-HAT) relying on combined usage of PC_SET with abstractors, which not only advances the methodology for creating germanium radicals in a photocatalytic fashion but also provides access to structurally novel and pharmaceutically promising organogermanium compounds that are difficult to synthesize by routine methods.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 14","pages":"1664-1672"},"PeriodicalIF":5.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292811","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}