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Acta Chimica sinica(English Edition) 1985年第4期3卷 362-368页

作者： chen qing-yun yang zhen-yu shanghai institute of organic chemistry,academia sinica,shanghai shanghai institute of organic chemistry Academia Sinica Shanghai

Perfluoroalkyl iodide RfI[Rf=（CF2）nO（CF2）2SO2F,n=2,（a）;n=4,（b）;（CF2）4Cl,（c）]reacted with substituted benzene C6H5Y（Y=alkyl,OCH3,CF3,F,Cl,Br,I）in the presence of copperin acetic anhydride to give the corresponding mixture of isomeric disubstituted benzene（RfC6H4Y）.The conversion and yield depend on both the amount of copper used and nature of *** explanation is that the reaction may involve a free radical *** perfluoroalkyl radicalcan be trapped by cyclohexene,isopropylbenzene and *** DMSO in place of acetic an-hydride as a solvent the reaction takes a different course,it is believed that the reaction in DMSOproceeds through a perfluoroalkylcopper intermediate.

关键词： Studies on fluoroalkylation and fluoroalkoxylation 2.Perfluoroalkylation of aromatics with perfluoroalkyl iodides in the presence of copper

氟烷基化和氟烷氧基化的研究 6.铜引发氟烷基碘对含硅炔烃的加成及其产物的化学转化

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化学学报 1986年第8期44卷 806-811页

作者：陈庆云杨震宇中国科学院上海有机化学研究所中国科学院上海有机化学研究所上海

在催化量的铜存在下,RfI（1）在很温和的条件下于乙腈中与乙炔基三甲基硅烷（CH≡CSiMe3）（2）反应,生成较高产率的（E）和（Z）-氟烷基化产物混合物（3）.在相同条件下,I（CF2）6I（4）也能与2反应,主要生成单烷基化产物[I（CF2）6CH=... 详细信息

在催化量的铜存在下,RfI（1）在很温和的条件下于乙腈中与乙炔基三甲基硅烷（CH≡CSiMe3）（2）反应,生成较高产率的（E）和（Z）-氟烷基化产物混合物（3）.在相同条件下,I（CF2）6I（4）也能与2反应,主要生成单烷基化产物[I（CF2）6CH=CISiMe3]（5）和少量的双烷基化产物[Me3SiCI=CH（CF2）6CH=CISiMe3]（6）.当1与双（三甲基硅基）乙炔（Me3SiC≡CSiMe3）反应得1∶1的加成产物[Ri（Me2SiCH2I）C=CHSiMe3]（7）和（RfMe3SiC=CISiMe3）（8）.3与氢氧化钾在乙醇中反应得到（E）-RfCH=CHI（9）;与氟化钾反应则生成9的Z和E的异构体混合物;在二氯甲烷中用叔丁醇钾处理则生成相应的炔烃（10）.3在室温下对酸稳定,用溴光照后则主要生成（E）-RfCH=CBrSiMe3（11）.

关键词：炔烃烷基化脂肪族不饱和烃取代反应加成 ppm 异构体产物乙炔基三甲基硅烷氟烷基化学转化

氟烷基化和氟烷氧基化的研究 2.在铜存在下氟烷基碘与芳烃的反应

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化学学报 1985年第11期43卷 1073-1078页

作者：陈庆云杨震宇中国科学院上海有机化学研究所中国科学院上海有机化学研究所上海

氟烷基碘（R,I）在铜存在下与芳烃,C6H5Y（Y=烷基,OCH3,CF3,F,Cl,Br,I）在乙酐中反应得到相应的氟烷基化芳烃（RfC6H4Y）混合物。转化率和产率与所用铜粉量和芳烃上的电子密度有关。带有供电子基的芳烃转化率和产率都较高;反之则低。反... 详细信息

氟烷基碘（R,I）在铜存在下与芳烃,C6H5Y（Y=烷基,OCH3,CF3,F,Cl,Br,I）在乙酐中反应得到相应的氟烷基化芳烃（RfC6H4Y）混合物。转化率和产率与所用铜粉量和芳烃上的电子密度有关。带有供电子基的芳烃转化率和产率都较高;反之则低。反应可能是自由基机理。氟烷基自由基能被环己烯和异丙苯所捕获。引发苯乙烯聚合生成含氟聚合物。芳环上的定位效应似乎也支持这一机理。若用DMSO为溶剂则可能是通过氟烷基铜中间体。

关键词：自由基机理异丙苯枯烯反应时间邻位异构体转化率氟烷基碘代苯碘苯四氢化苯环烯烃环己烯吸电子基芳烃产率

氟烷基化和氟烷氧基化的研究钯(O)催化氟烷基碘对烯烃的加成反应

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化学学报 1985年第11期43卷 1118-1120页

作者：陈庆云杨震宇中国科学院上海有机化学研究所中国科学院上海有机化学研究所上海上海

氟烷基碘通过光、热、自由基引发剂引发对烯烃加成。1984年Ojima等报道过渡金属羰基络合物也能催化氟烷基碘对重键的加成。我们前已报道铜在乙酐、二缩二乙二醇二甲醚(DG)或乙腈中通过单电子转移引发氟烷基碘与烯烃、炔烃反应,反应条... 详细信息

氟烷基碘通过光、热、自由基引发剂引发对烯烃加成。1984年Ojima等报道过渡金属羰基络合物也能催化氟烷基碘对重键的加成。我们前已报道铜在乙酐、二缩二乙二醇二甲醚(DG)或乙腈中通过单电子转移引发氟烷基碘与烯烃、炔烃反应,反应条件温和产率较高。但钯是否也能催化氟烷基碘与烯烃反应仍属未知。本文首次报道四(三苯基膦)合钯(O)催化氟烷基碘对烯烃的加成反应。

关键词：羰基络合物单电子转移氟烷基过渡金属自由基引发剂烷氧基化二乙二醇二甲醚乙酐三苯基庚烯

氟烷基化和氟烷氧基化的研究 8.钯(O)催化氟烷基碘对炔烃的加成反应

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化学学报 1986年第10期44卷 1025-1029页

作者：陈庆云杨震宇中国科学院上海有机化学研究所中国科学院上海有机化学研究所上海

四（三苯基膦）钯（O）在温和的条件下能催化氟烷基碘RFI[RF=（CF2）nCl,n=2;n=4;n=6;RF=（CF3）nCF3,n=3;n=1;RF=H（CF2）4]对炔烃（CH≡CC4H9,CH≡CSiMe3,CH≡CPh）加成生成较高产率的加成产物.二（三苯基膦）二氯化钯（II）和二（三... 详细信息

四（三苯基膦）钯（O）在温和的条件下能催化氟烷基碘RFI[RF=（CF2）nCl,n=2;n=4;n=6;RF=（CF3）nCF3,n=3;n=1;RF=H（CF2）4]对炔烃（CH≡CC4H9,CH≡CSiMe3,CH≡CPh）加成生成较高产率的加成产物.二（三苯基膦）二氯化钯（II）和二（三苯基膦）氟烷基碘化钯（II）在同样的条件下无催化作用.2,2-硝基,亚硝基丙烷能部分阻止反应,这表明反应的可能中间体是自由基.而不是二（三苯基膦）氟烷基碘化钯（II）.

关键词：加成反应加成产物高产率炔烃脂肪族不饱和烃硝基丙烷氟烷基

氟烷基化和氟烷氧基化的研究 4.铜引发氟烷基碘对乙烯基三甲基硅烷的加成及其立体专一性合成相应的烯烃

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化学学报 1986年第3期44卷 265-269页

作者：陈庆云杨震宇中国科学院上海有机化学研究所中国科学院上海有机化学研究所上海

在催化量的铜存在下,氟烷基碘RFI（1）与乙烯基三甲基硅烷（2）在乙腈中反应生成高产率的氟烷基化产物8,二碘化物I（CF2）nI（4）也能与2反应生成单烷基化产物5和双烷基化产物6,5和6量的相对比例取决于所用2的量.这类反应能被对苯二酚阻... 详细信息

在催化量的铜存在下,氟烷基碘RFI（1）与乙烯基三甲基硅烷（2）在乙腈中反应生成高产率的氟烷基化产物8,二碘化物I（CF2）nI（4）也能与2反应生成单烷基化产物5和双烷基化产物6,5和6量的相对比例取决于所用2的量.这类反应能被对苯二酚阻止:被对二硝基苯部分阻止,碘苯未能捕获到氟烷基铜中间体.表明反应可能是单电子转移引发的自由基链式机理.3与二乙胺反应得高产率的反式氟烷基三甲基硅乙烯7.3与氢氧化钾在乙醇中反应得到的是7及其顺式异构体的混合物,将混合物用少量的溴处理可得纯的反式烯烃.

关键词：三甲基硅 ppm 甲基硅烷反应顺式异构体乙烯基链烯烃基有机层反式单电子碘化氢氢化合物二乙胺氟烷基烯烃脂肪族不饱和烃加成

Studies on fluoroalkylation and fluoroalkoxylation——8. Palladium(0)-catalyzed addition reaction of fluoroalkyl iodides with alkynes

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Chinese Journal of chemistry 1986年第4期4卷 370-375页

作者： chen qing-yun yang zhen-yu shanghai institute of organic chemistry, academia sinica, shanghai shanghai institute of organic chemistry Academia Sinica Shanghai

Fluoroalkyl iodide RFI [RF=（CF2）_nCl, n=2, 4, 6; CF3（CF2）_n, n=1, 3; H（CF2）4lreacted with alkyne （CH≡CC4H9; CH≡CSiMe3; CH≡CC6H5） in the presence of catalytic amountsof tetrakis （triphenylphosphine） palladium （0） to give a mixture of E and Z-fluoroalkylated *** reaction could not be catalyzed by dichloro--bis （triphenylphosphine）palladium （Ⅱ） and fluoro-alkyl complex of palladium （Ⅱ）. 2-Nitro-2--nitrosopropane partly suppressed the reaction. Itis believed that the reaction proceeds through a free radical intermediate rather than fluoroalkyl complexof palladium （Ⅱ）.

关键词： Palladium catalyzed addition reaction of fluoroalkyl iodides with alkynes Studies on fluoroalkylation and fluoroalkoxylation

Association of Human Whole-blood NAD+Levels with Nabothian Cyst

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Biomedical and Environmental Sciences 2024年第5期37卷 471-478页

作者： XU Ling WANG yue Xuan WANG Wei FAN Xue chen Xue yu ZHOU Tian yun LIU yu He yu Ye yang Fan JU zhen yu ZHOU Yong WANG Deng Liang Clinical Research institute Shanghai General HospitalShanghai Jiao Tong University School of MedicineShanghai 200080China NHC Key Lab of Reproduction Regulation Shanghai Engineering Research Center of Reproductive Health Drugs and DevicesShanghai Institute for Biomedical and Pharmaceutical TechnologiesShanghai 200237China Department of Applied Statistics Johannes Kepler University LinzLinz 4040Austria Hematology Center Beijing Key Laboratory of Pediatric Hematology OncologyNational Key Discipline of Pediatrics(Capital Medical University)Key Laboratory of Major Diseases in ChildrenMinistry of EducationBeijing Children's HospitalCapital Medical UniversityNational Center for Children's HealthBeijing 100045China Department of Biostatistics School of Public HealthCheeloo College of MedicineShandong UniversityJinan 250012ShandongChina Clinical Medicine School of Basic MedicineShanghai Medical College Fudan UniversityShanghai 200032China Department of Biochemistry and Molecular Biology Hengyang Medical SchoolUniversity of South ChinaHengyang 421001HunanChina Administrative Office Total Quality Management OfficeTotal Quality Management InstituteShanghai General HospitalShanghai Jiao Tong University School of MedicineShanghai 200080China The First Affiliated Hospital of Jinan University Institute of Aging and Regenerative MedicineJinan UniversityJinan 510632GuangzhouChina Department of Scientific Research The First Affiliated Hospital of Huzhou UniversityHuzhou 313000ZhejiangChina Department of Neurosurgery Neurosurgery Research InstituteThe First Affiliated HospitalFujian Medical UniversityFuzhou 350005FujianChina Department of Neurosurgery Binhai Branch of National Regional Medical CenterThe First Affiliated HospitalFujian Medical UniversityFuzhou 350209FujianChina Fujian Provincial institutes of Brain Disorders and Brain Sciences The First Affiliated HospitalFujian Medical UniversityFuzhou 350005FujianChina Fujian Provincial Clinical Research Center for Neurological

Objective Little is known about the association between whole-blood nicotinamide adenine dinucleotide(NAD^(+))levels and nabothian *** study aimed to assess the association between NAD^(+)levels and nabothian cysts in healthy Chinese *** Multivariate logistic regression analysis was performed to analyze the association between NAD^(+)levels and nabothian *** The mean age was 43.0±11.5 years,and the mean level of NAD^(+)was 31.3±5.3μmol/*** cysts occurred in 184(27.7%)participants,with single and multiple cysts in 100(15.0%)and84(12.6%)participants,*** total nabothian cyst prevalence gradually decreased from37.4%to 21.6%from Q1 to Q4 of NAD^(+)and the prevalence of single and multiple nabothian cysts also decreased across the NAD^(+)*** compared with the highest NAD^(+)quartile(≥34.4μmol/L),the adjusted odds ratios with 95%confidence interval of the NAD^(+)Q1 was 1.89(1.14–3.14)for total nabothian *** risk of total and single nabothian cysts linearly decreased with increasing NAD^(+)levels,while the risk of multiple nabothian cysts decreased more rapidly at NAD^(+)levels of 28.0 to35.0μmol/***:Low NAD^(+)levels were associated with an increased risk of total and multiple nabothian cysts.

关键词： Nicotinamide adenine dinucleotide Nabothian cyst Female Risk factor

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Mixing states and secondary formation processes of organic nitrogen-containing single particles in Guangzhou,China

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Journal of Environmental Sciences 2024年第4期138卷 62-73页

作者： Lijun yun Chunlei cheng Suxia yang Zaihua Wang Mei Li Qi En Zhong LiyuanMao Sulin Liu Xiaoya cheng Duanying chen Fan yang zhen Zhou institute of Mass Spectrometry and Atmospheric Environment Guangdong Provincial Engineering Research Center for on-line source apportionment system of air pollutionJinan UniversityGuangzhou 510632China Guangdong-Hongkong-Macao Joint Laboratory of Collaborative Innovation for Environmental Quality Guangzhou 510632China State Key Laboratory of Loess and Quaternary Geology Institute of Earth EnvironmentChinese Academy ScienceXi’an 710061China institute for Environment and Climate Research Jinan UniversityGuangzhou 510632China Guangdong Academy of Sciences Institute of Resources Utilization and Rare Earth DevelopmentGuangzhou 510650China Environmental Monitoring Station of Pudong New District Shanghai 201200China

organic nitrogen(ON)compounds play a significant role in the light absorption of brown carbon and the formation of organic aerosols,however,the mixing state,secondary formation processes,and influencing factors of ON compounds are still *** paper reports on the mixing state of ON-containing particles based on measurements obtained using a highperformance single particle aerosol mass spectrometer in January 2020 in *** ON-containing particles accounted for 21% of the total detected single particles,and the particle count and number fraction of the ON-containing particles were two times higher at night than during the *** prominent increase in the content of ON-containing particles with the enhancement of NO_xmainly occurred at night,and accompanied by high relative humidity and nitrate,which were associated with heterogeneous reactions between organics and gaseous NO_(x)and/or NO_(3)*** synchronous decreases in ON-containing particles and the mass absorption coefficient of water-soluble extracts at 365 nm in the afternoon may be associated with photo-bleaching of the ON species in the *** addition,the positive matrix factorization analysis found five factors dominated the formation processes of ON particles,and the nitrate factor(33%)mainly contributed to the production of ON particles at *** results of this study provide unique insights into the mixing states and secondary formation processes of the ON-containing particles.

关键词： organic nitrogen compounds Single particles Mixing state Secondary formation Nighttime chemistry

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Atmospheric chemistry of 2-nitrobenzaldehyde:Initiated by photo-excitation,OH-oxidation,and small TiO_(2) clusters adsorption catalysis

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Journal of Environmental Sciences 2024年第5期139卷 123-137页

作者： Feng-yang Bai Xiang-Huan Liu Ting-Ting Meng Zhou yu Yi-chen Wang Shuang Ni zhen Zhao institute of Catalysis for Energy and Environment College of Chemistry and Chemical EngineeringShenyang Normal UniversityShenyang 110034China

The fate of 2-nitrobenzaldehyde(2-NBA)is of interest in atmospheric chemistry as it is a semi-volatile organic compound with high *** study presents a quantum chemical study of the gas-phase reactions of 2-NBA photo-excitation and OH-oxidation in the absence and presence of small TiO_(2) *** further understand the unknown photolysis mechanism,the photo-reaction pathways of ground singlet state and the lying excited triplet state of 2-NBA were investigated including the initial and subsequent reactions of proton transfer,direct CO,NO_(2),and HCO elimination routes in the presence of O_(2) and ***,the OH-mediated degradation of 2-NBA proceeded via five H-extraction and six OH-addition channels by indirect mechanism,which follows a succession of reaction steps initiated by the formation of weakly stable intermediate *** H-extraction from the-CHO group was the dominant pathway with a negative activation energy of-1.22 kcal/*** calculated rate coefficients at 200–600 K were close to the experimental data in literature within 308-352 K,and the kinetic negative temperature independence was found in both experimental literature and computational ***,2-NBA was favored to be captured onto small TiO_(2) clusters via six adsorption configurations formed via various combination of three types of bonds of Ti…O,Ti…C,and O…H between the molecularly adsorbed 2-NBA and TiO_(2) *** indicted that the chemisorptions of aldehyde oxygen have largest *** results suggested adsorption conformations have a respectable impact on the catalysis *** study is significant for understanding the atmospheric chemistry of 2-nitrobenzaldehyde.

关键词： 2-nitrobenzaldehyde OH radical oxidation Rate coefficient Photolysis mechanism Adsorption catalysis

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