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De novo synthesis of atropisomeric benzofurans via Cu/SPDO complex catalyzed asymmetric formal [3 + 2] annulation

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Science China Chemistry 2025年第1期68卷 174-180页

作者： Fan-Xiao Meng Xing-yu Wang Ka Lu Ju-Song Yang Fu-Min Zhang Ai-Jun ma Bao Du Yong-Qiang Tu State Key Laboratory of Applied Organic Chemistry College of Chemistry and Chemical Engineering Lanzhou University School of Chemistry and Chemical Engineering Shanghai Jiao Tong University School of Biotechnology and Health Sciences Wuyi University

Herein, the de novo synthesis of atropisomeric benzofurans through the Cu/spirocyclic-pyrrolidine-oxazoline(SPDO) complex catalyze asymmetric formal [3 + 2] cycloaddition between quinones and ynamides is explored, producing a range of structurally diverse axially chiral benzofurans in satisfactory yields with good to excellent enantioselectivities. Furthermore, density functional theory calculations were applied to explain the possible reaction mechanism.

关键词： benzofuran atropisomers novel de novo synthetic strategy asymmetric formal [3 + 2] cycladdition Cu/SPDO complex DFT calculations

全珊瑚海水混凝土单轴受压应力-应变全曲线试验研究

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建筑结构学报 2017年第1期38卷 144-151页

作者：达波余红发麻海燕张亚栋袁银峰余强谭永山糜人杰南京航空航天大学土木工程系江苏南京210016 青海大学土木工程学院青海西宁810016 中国人民解放军理工大学爆炸冲击防灾减灾国家重点实验室江苏南京210073 海军工程设计研究院北京100070

采用等应力循环加卸载法和等应变单调加载法,对棱柱体试件进行单轴受压试验获得全珊瑚海水混凝土的应力-应变全曲线,并对两种加载方法进行对比分析。试验结果表明:全珊瑚海水混凝土裂纹贯穿珊瑚骨料继续发展,单轴受压试件的破坏为脆性破... 详细信息

采用等应力循环加卸载法和等应变单调加载法,对棱柱体试件进行单轴受压试验获得全珊瑚海水混凝土的应力-应变全曲线,并对两种加载方法进行对比分析。试验结果表明:全珊瑚海水混凝土裂纹贯穿珊瑚骨料继续发展,单轴受压试件的破坏为脆性破坏,典型破坏状态主要为劈裂破坏,其主斜裂缝的倾角θ在65°~70°之间;残余应力与峰值应力的比值在0.292~0.525之间,说明全珊瑚海水混凝土破坏后仍具有较高的残余强度,破坏后强度逐步降低,具有一定的延性;不同强度等级全珊瑚海水混凝土的应力-应变全曲线的上升段趋势基本相似,但是随着强度等级提高,下降段的下降趋势越陡,破坏程度越剧烈;在相同强度等级下,全珊瑚海水混凝土比普通混凝土和轻集料混凝土的脆性更强。

关键词：全珊瑚海水混凝土等应力循环加卸载试验等应变单调加载试验单轴受压应力-应变全曲线

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Contribution of fungal biomass to persistent soil carbon across natural ecosystems

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Science China Earth Sciences 2025年

作者： Xiang WANG Guang-Hui yu Yakov KUZYAKOV bo-Hao YIN Andreas KAPPLER Cong-Qiang LIU bohai Coastal Critical Zone National Observation and Research Station Institute of Surface-Earth System Science School of Earth System Science Tianjin Key Laboratory of Earth Critical Zone Science and Sustainable Development in Bohai Rim Tianjin University Department of Soil Science of Temperate Ecosystems Department of Agricultural Soil Science University of G?ttingen Agro-Technological Institute Peoples Friendship University of Russia (RUDN University) Geomicrobiology Center for Applied Geosciences University of Tübingen Cluster of Excellence EXC 2124 Controlling Microbes to Fight Infection University of Tübingen

Fungi are known to be crucial in the formation and stabilization of soil organic matter through their exudates and dead residues (necromass). Yet, it remains unclear how fungi contribute to the persistence of carbon in soils over millennial scales across biomes. Here, this study fills the knowledge gap by linking fungal carbon stocks with minerals-associated carbon stocks across major biomes. A strong correlation between fungal biomass and reactive mineral-associated carbon stocks in soils across six biomes supports the substantial role of fungi in soil carbon persistence at the global level. High spatial resolution nanoscale secondary ion mass spectrometry revealed that fungi may stabilize carbon by forming organo-mineral associations through their close physical connection to reactive minerals and weathered nanoparticles. We propose a conceptual model that emphasizes the dualistic role of hypha-mineral interactions:(i) fungi accelerate organic matter decomposition by producing reactive oxygen species on the hypha-mineral interfaces, and (ii) fungi stabilize their residues on mineral surfaces, leading to millennial scale persistence of soil C. Concluding, fungi play a fundamental role in ecosystems that extends beyond the decomposition of persistent carbon. They are crucial in stabilizing carbon on mineral surfaces, thereby facilitating the long-term removal of carbon from rapid biotic cycling.

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Double [5]carbohelicene: facile synthesis, chiroptical properties,isomerization study, and lasing application

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Science China Chemistry 2025年第1期68卷 233-240页

作者： Peipei Liu Yantong Li Meng-Xiang Wu Hao Kang Xiao-Li Zhao Lin Xu Linlin Liu Xiaodong Li Junfeng Fang Zhiwei Fang Ya Cheng Hai-bo Yang Huakang yu Xueliang Shi State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical ProcessesSchool of Chemistry and Molecular Engineering East China Normal University School of Physics and Optoelectronics South China University of Technology Institute of Polymer Optoelectronic materials & Devices State Key Laboratory of Luminescent Materials & Devices South China University of Technology School of Physics and Electronic Science Engineering Research Center of Nanophotonics & Advanced Instrument Ministry of EducationEast China Normal University State Key Laboratory of Precision Spectroscopy School of Physics and Electronic Science East China Normal University

Double carbohelicenes have attracted considerable attention due to their aesthetic structures, distinct π-conjugation extension, inherent chirality, and intriguing optical and electronic properties. Herein, the concise de novo synthesis of a new double[5]carbohelicene 1 together with its chiroptical properties, isomerization process and lasing application is presented. 1 was synthesized by a simple protocol involving the formation of a 6,6′-bipentacene as the key intermediate. It is worth noting that1 existed as two diastereomers 1-PP/MM and 1-PM, which were successfully isolated and unambiguously confirmed by Xray crystallography. The optical resolution of the racemic 1-PP/MM was successfully achieved by chiral-phase highperformance liquid chromatography（HPLC）, and 1-PP and 1-MM were characterized by circular dichroism. Interestingly, it was found that 1-PP/MM could be completely isomerized to 1-PM upon heating, and the detailed thermodynamics and kinetics of the isomerization process were systematically investigated. 1-PM exhibited deep-red luminescence with emission maximum at 723 nm and fluorescence quantum yield as high as 32.95%. Consequently, we can showcase the lasing application of 1-PM by doping with epoxy resin to assemble a bottle microlaser spontaneously, which the lasing wavelength is 796.6 nm at a threshold of 0.8 m J cm-2. We believe that our studies, including the facile synthesis methodology, detailed isomerization studies, and lasing application, will shed some light on the design and synthesis of novel carbohelical systems with more functions.

关键词： double carbohelicene optical resolution organic laser isomerization X-ray diffraction

Homologous CoS2 interface with directed electron transfer and strong chloridion repulsion for efficient seawater oxidation

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Science China Chemistry 2025年

作者： yuan Tian Jiang-bo Chen Jie Ying Ge Tian yu-Xuan Xiao Yi Lu Si-Ming Wu Wei Geng Ling Shen Xiao-yu Yang State Key Laboratory of Advanced Technology for materials Synthesis and Processing and School of Materials Science and Engineering and Shenzhen Research Institute & Laoshan Laboratory Wuhan University of Technology School of Chemical Engineering and Technology Sun Yat-Sen University National Energy Key Laboratory for New Hydrogen-Ammonia Energy Technologies Foshan Xianhu Laboratory

Seawater electrolysis is a highly promising method to produce high energy density hydrogen,especially in dry areas that have scarce freshwater ***,application of seawater electrolysis is confronted by two major problems associated with catalysts employed for the anodic oxygen evolution reaction （OER） including the competitive hypochlorite evolution reaction（HCER） and strong chloridion （Cl–） triggered *** studies aimed at overcoming these problems,a facile method has been developed to synthesize a homologous CoS2heterojunction as an OER *** to a difference in work functions at the interface and increased electron density,this material has directed electron transfer and strong chloridion repulsion properties,*** have shown that CoS2achieves low overpotentials of 289 and 322 mV at 10 ma cm-2current density in respective alkaline （1 M KOH） and alkaline simulated seawater ***,the outstanding stability of CoS2is reflected in a negligible decline in activity during promotion of the OER for 100 *** of density functional theory calculations reveal that the homologous CoS2heterojunction promotes directed electron transport for optimizing adsorption/desorption of reactive species and heightens the Cl-adsorption energy for strongly repulsing Cl-,phenomena that enhance OER performance in alkaline simulated seawater.

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Molecular mechanism and research progress of traditional Chinese medicine in the treatment of prostate cancer

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Traditional Medicine Research 2025年第1期10卷 62-72页

作者： Hai-Luo Wang Ruo-Ran Zhang Hao Wang Peng Xu Jing-Kai Wang bo Chen Hao Xu Deng Pan yu-Yang ma Kun Pang Department of Urology Xuzhou Central HospitalXuzhou Clinical School of Xuzhou Medical CollegeXuzhou 221009China Graduate School Jiangsu UniversityZhenjiang 212013China Graduate School Bengbu Medical UniversityBengbu 233040China Department of Urology The Peixian People’s HospitalXuzhou 221699China.

Prostate cancer(PCa)is one of the most common malignant tumors in the male genitourinary system,ranking second in incidence *** Chinese medicine(TCM),as an important component of complementary and alternative medicine,shows unique advantages in cancer *** herbal medicine is usually composed of multiple ingredients and involves multiple signaling pathways,which showed function of inducing apoptosis of cancer cells,arresting the cell cycle,inhibiting invasion and metastasis,reducing drug resistance,and regulating immune *** therapy is also an important treatment of ***,Physical therapy such as acupuncture or Tai Chi and Qigong are gaining increased recognition in the management of PCa,particularly in addressing issues like urinary incontinence and bone metastasis-related *** article reviews the TCM treatment and therapy of PCa,in order to provide new research avenues and treatment options for the treatment of PCa with TCM and improve the quality of life of patients.

关键词： traditional Chinese medicine prostate cancer Chinese herbal medicine physical therapy

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基于样本空间分布距离的支持向量机

智能计算机与应用 2016年第5期6卷 77-80,84页

作者：于波李海峰马琳哈尔滨工业大学计算机科学与技术学院哈尔滨150001 哈尔滨理工大学软件学院哈尔滨150040

由于支持向量机(Support Vector machine,SVM)在处理样本不平衡分布时会有偏向性,使少数类别的分类错误率的上界高于多数样本类别。分析总结了针对该问题当前的研究方法,并指出存在问题。研究分析针对不平衡样本SVM分类识别率的倾向性... 详细信息

由于支持向量机(Support Vector machine,SVM)在处理样本不平衡分布时会有偏向性,使少数类别的分类错误率的上界高于多数样本类别。分析总结了针对该问题当前的研究方法,并指出存在问题。研究分析针对不平衡样本SVM分类识别率的倾向性问题。考虑全局样本信息,提出了3种针对所有样本空间分布距离信息的方法。在UCI数据集上进行实验,结果证明MSEDR-SVM(Mean Sample Euclidean Distance Ratio-SVM)能够有效增加少数样本类别的F-值。从而改善标准的SVM只依靠支持向量样本构建分类超平面的局限性。

关键词： SVM 不平衡样本分布 MSEDR-SVM

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Design high-performance narrowband emitters for blue light-emitting diodes through manipulating resonance structure of aromatic heterocycles

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Science China Chemistry 2025年

作者： yue yu Lei Xu Wenle Tan yuyu Pan Jiyin Xiao bohan Wang Guangjun Tian yuguang ma Lei Ying Institute of Polymer Optoelectronic materials and Devices Guangdong Basic Research Center of Excellence for Energy and Information Polymer Materials State Key Laboratory of Luminescent Materials and Devices South China University of Technology School of Petrochemical Engineering Shenyang University of Technology Key Laboratory for Microstructural material Physics of Hebei Province School of Science Yanshan University

Narrowband light-emitting materials play critical roles in improving the color gamut and energy consumption of electroluminescence. Herein we demonstrated that by regulating the ground state resonance structure form of emitters with polycyclic aromatic heterocycles, the high-energy vibration of the C–C bond can be effectively suppressed, resulting in narrow emission like classical cyanine dyes. The designed compounds consist of twist and planar conformation, while having differences in the orientation of the positioning electron-donating(nitrogen) and electron-accepting(carbonyl) groups in the polycyclic aromatic hydrocarbon skeleton. The resulting compound Ac-Ph-Ac with a dominated zwitterionic resonance structure exhibits a relatively wide electroluminescent profile with the full width at half maximum(FWHM) of 42 nm and moderate device performance. In contrast, the “soliton transition” of 2AcPh based on the cyanine limit character effectively suppresses C–C stretching vibration in the polycyclic aromatic heterocycle skeleton, leading to a narrow electroluminescent profile with FWHM of 30 nm(0.16 eV)associated with an impressively high external quantum efficiency of 28.52%, which is among the highest efficiencies of so far reported non-sensitized organic light-emitting diodes.

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Catalytic atroposelective synthesis of indolyl quinazolinones bearing N-N/C-C diaxes

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Science China Chemistry 2025年

作者： Ning-Yi Wang Shuo Gao Zhu-Di Shu Bei-Bei Cheng Chun ma yu-Chen Zhang Feng Shi Research Center of Chiral Functional Heterocycles School of Chemistry and Materials Science Jiangsu Normal University School of Petrochemical Engineering Changzhou University School of Chemistry and Chemical Engineering Henan Normal University

The first catalytic atroposelective synthesis of indole derivatives bearing N-N/C-C diaxes has been established by the strategy of de novo ring formation. By this strategy, various indolyl quinazolinones bearing vicinal N-N/C-C diaxes were synthesized in high yields with overall good diastereoselectivities and excellent enantioselectivities via chiral phosphoric acid-catalyzed onepot asymmetric formal (5+1) cycloaddition/oxidation reaction. Moreover, such indolyl quinazolinones bearing vicinal N-N/CC diaxes have good configurational stability and could be converted into new chiral ligands with applications in asymmetric catalysis. Therefore, this work not only offered a new member for the family of diaxial atropisomers, but also provided a powerful strategy for catalytic asymmetric synthesis of atropisomers bearing N-N/C-C diaxes.

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