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Cobalt(III) hydride HAT mediated enantioselective intramolecular hydroamination access to chiral pyrrolidines

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Science China Chemistry 2024年

作者： Qi meng Tao qin Huanran Miao Ge Zhang Qian Zhang State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis Department of Chemistry Northeast Normal University

Enantioenriched pyrrolidines and derivatives are ubiquitous substructures in compounds of importance to medicinal and biological chemistry. Herein, we report an efficient cobalt-catalyzed intramolecular asymmetric hydroamination reaction that produces chiral pyrrolidines with good to excellent yield and enantiocontrol. Compared with previously reported radicalinvolved methodologies for enantioenriched pyrrolidines, these conditions feature two elegant versatilities, enabling(1) the use of cobalt-catalyzed hydrogen atom transfer(HAT) to generate organocobalt intermediates that bring radical reaction to organometallic chemistry, and(2) enantioselective intramolecular C–N bond forging through an SN2-like displacement involving dynamic kinetic resolution(DKR). This approach provides a new alternative and efficient methodology for enantioselective radical-involved C-N bond construction that can be used in the synthesis of both chiral pyrrolidines and homologous nitrogen heterocycles.

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Metamorphic P-T conditions and ages of garnet-biotite schists in the Dahongshan Group from the southwestern Yangtze Block

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Acta Geochimica 2024年第4期43卷 707-718页

作者： Jun-xiao Ma Guang-shu Yang Yong-feng Yan xiao-Fei Xu Yun-hua Ren Hui Zhao xiao-jun Zheng Yuan qin Faculty of Land Resources Engineering Kunming University of Science and TechnologyKunming 650093China Geological Team 306 of Yunnan Non-Ferrous Metals Geological Bureau Kunming 650217China Yunnan Provincial Bureau of Non-Ferrous Geology Kunming 650051China

The Dahongshan Group,situated at the southwestern margin of the Yangtze Block,represents a geological unit characterized by relatively high-grade metamorphism in the *** paper investigates the garnet-biotite schist from the Laochanghe Formation of the Dahongshan Group,employing an integrated approach that includes petrological analysis,phase equilibrium modeling,and zircon U-Pb *** schist is mainly composed of garnet,biotite,plagioclase,quartz,rutile,and *** equilibrium modeling revealed the peak metamorphic conditions of 8-9 kbar and 635-675°*** further integrating the prograde metamorphic profile of garnet and geothermobarometric results,a clockwise P-T metamorphic evolution path is constructed,which includes an increase in temperature and pressure during the prograde ***-ICP-MS zircon U-Pb dating and zircon Ti thermometry constrains the post-peak metamorphic age of 831.2±7.2 *** with previously reported results,it is revealed that the southwestern margin of the Yangtze Block experienced a large-scale regional metamorphism during the Neoproterozoic(890-750 Ma),which is related to the collisional orogenic *** may be associated with the late-stage assembly of the Rodinia supercontinent or with local compression and subduction processes during the breakup of the Rodinia supercontinent.

关键词： Southwestern Yangtze Block Dahongshan Group Phase equilibrium modeling Zircon U-Pb dating Neoproterozoic metamorphism

Transdermal treatment for malignant melanoma by aptamer-modified tetrahedral framework nucleic acid delivery of vemurafenib

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Chinese Chemical Letters 2024年第4期35卷 260-267页

作者： Dexuan xiao Tianyu Chen Tianxu Zhang Sirong Shi Mei Zhang Xin qin Yunkun Liu Longjiang Li Yunfeng Lin State Key Laboratory of Oral Diseases National Clinical Research Center for Oral DiseasesWest China Hospital of StomatologySichuan UniversityChengdu 610041China Sichuan Provincial Engineering Research Center of Oral Biomaterials Chengdu 610041China Department of Head and Neck Oncology National Clinical Research Center for Oral DiseasesWest China Hospital of StomatologySichuan UniversityChengdu 610041China

Melanoma is one of the most malignant skin tumors, whose high invasion is generally associated with BRAF gene mutation. Although new chemotherapeutic drugs, such as vemurafenib, have been developed to inhibit the growth of melanoma, these drugs are usually administered intravenously or orally, resulting in toxic side effects on major tissues and organs. Tetrahedral framework nucleic acids(tFNAs) are a novel type of DNA nanostructures with excellent biocompatibility and versatility which have been proven to penetrate through skin barrier with ease. In this study, we prepared t FNAs with vemurafenib and connected DNA aptamer AS1411 at the apex of t FNAs(AS1411-tFNAs/vemurafenib). On one hand, AS1411-tFNAs/vemurafenib could kill melanoma cells by blocking the mutated BRAF gene in vitro. Compared with free vemurafenib, AS1411-tFNAs/vemurafenib had no obvious toxicity to normal cells. On the other hand,AS1411-tFNAs could transfer vemurafenib to cross through the skin barrier and permeate into tumor tissues. In vivo, transdermal delivery of AS1411-t FNAs/vemurafenib could inhibit the growth of human A375melanoma, whose inhibiting effect was stronger than intravenous administration of vemurafenib. These results demonstrated the application prospects of tFNAs combined with chemotherapeutic drugs in skin tumors.

关键词： Melanoma Vemurafenib DNA nanostructure Transdermal treatment Side effect

Effect of Acupuncture on Endometrial Blood Flow in Women Undergoing in vitro Fertilization Embryo Transfer: A Single Blind, Randomized Controlled Trial

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Chinese Journal of Integrative Medicine 2024年第1期30卷 10-17页

作者： DONG Hao-xu Wu xiao ZHOU qin HUANG Dong-mei ZHANG Ming-min HUANG Guang-ying YANG Wei Department of Integrated Traditional Chinese and Western Medicine Tongji HospitalHuazhong University of Science and TechnologyWuhan(430030)China Department of Obstetrics and Gynecoiogy Tongji HospitalHuazhong University of Science and TechnologyWuhan(430030)China Institute of Integrated Traditional Chinese and Western Medicine Tongji HospitalHuazhong University of Science and TechnologyWuhan(430030)China Department of Reproductive Medicine Tongji HospitalHuazhong University of Science and TechnologyWuhan(430030)China

Objective: To evaluate the effect of manual acupuncture on endometrial blood flow parameters by three-dimensional(3D) power Doppler ultrasound in women undergoing in vitro fertilization embryo transfer(IVF-ET). Methods: Seventy patients undergoing IVF-ET were equally randomized into traditional or sham acupuncture treatment group for totally 4 days(from the day of oocyte aspiration to the day of embryo transfer) of treatment by random envelope method at the Reproductive Medicine Center and Outpatient Department of Integrated Traditional Chinese and Western Medicine, Tongji Hospital, Tongji Medicine College, Huazhong University of Science and Technology from January 2013 to December 2015. Patients in the traditional acupuncture group accepted traditional acupuncture methods with manual acupuncture, and Zhongji(CV3), Qihai(CV 6), Sanyinjiao(SP6), Taichong(LR 3), Tianshu(ST 25), Guilai(ST 29) and Zusanli(ST 36) were chosen. Patients at the sham acupuncture group accepted shallow acupuncture methods at 4 non-meridian points at each shoulder and upper arm. Outcome measures included endometrial ultrasonic indices such as vascularization index(VI), flow index(FI) and vascularization flow index(VFI), endometrial thickness and volume, subendometrial VI(sVI), subendometrial FI(sFI), subendometrial VFI(sVFI), implantation rate, clinical pregnancy rate, abortion rate, live birth rate and number of live births. Results: Finally, 34 patients in the traditional acupuncture group and 35 in the sham acupuncture group completed this trial. VI, FI and VFI of the traditional acupuncture group were significantly higher than those in the sham acupuncture group(P0.05). Conclusions: Manual acupuncture performed after oocyte aspiration and before transplantation improved the endometr

关键词： acupuncture endometrial blood flow endometrial receptivity in vitro fertilization randomized controlled trial

Chinese Medicine Prolongs Overall Survival of Chinese Patients with Advanced Gastric Cancer: Treatment Pattern and Survival Analysis of a 20-Year Real-World Study

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Chinese Journal of Integrative Medicine 2024年第6期30卷 489-498页

作者： CAO Ni-da ZHU xiao-hong MA Fang-qi XU Yan DONG Jia-huan qin meng-meng LIU Tian-shu ZHU Chun-chao GUO Wei-jian DING Hong-hua GUO Yuan-biao LIU Li-kun SONG Jin-jie WU Ji-ping CHENG Yue-lei ZENG Lin ZHAO Ai-guang Oncology Department I Longhua Hospital Shanghai University of Traditional Chinese MedicineShanghai200032China Oncology Department Zhongshan HospitalFudan UniversityShanghai200032China Gastrointestinal Surgery Department Renji HospitalShanghai Jiaotong University School of MedicineShanghai200127China Oncology Department Fudan University Shanghai Cancer CenterShanghai200032China Oncology Department Shanghai General HospitalShanghai Jiaotong University School of MedicineShanghai200080China Traditional Chinese Medicine Department Ruijin HospitalShanghai Jiaotong University School of MedicineShanghai200025China Oncology Department Shanxi Traditional Chinese Medicine HospitalTaiyuan030012China Oncology Department Xiyuan HospitalChina Academy of Chinese Medical ScienceBeijing102445China Oncology Department Yunnan Province Hospital of Traditional Chinese MedicineKunming650021China Oncology Department Shuguang HospitalShanghai University of Traditional Chinese MedicineShanghai201203China Shanghai NewCore Biotechnology Co. Ltd.Shanghai200240China

Objective To describe the treatment patterns and survival status of advanced gastric cancer(AGC)in China in the past two decades,and objectively evaluate the impact of standardized Chinese medicine(CM)treatment on the survival of AGC *** This multicenter registry designed and propensity score analysis study described the diagnosis characteristics,treatment-pattern development and survival status of AGC from 10 hospitals in China between January 1,2000 and July 31,*** survival(OS)was evaluated between non-CM cohort(standard medical treatment)and CM cohort(integrated standard CM treatment≥3 months).Propensity score matching(PSM)and inverse probability of treatment weighting(IPTW)were performed to adjust any difference in average outcomes for *** A total of 2,001 patients histologically confirmed locally advanced and/or metastasis stomach and gastroesophageal junction adenocarcinoma were *** them,1,607 received systemic chemotherapy,215(10.74%)accepted molecular targeted therapy,44(2.2%)received checkpoint inhibitor therapy,and 769(38.43%)received ***-drug regimen was the main choice for first-line treatment,with fluoropyrimidine plus platinum as the most common regimen(530 cases,60.09%).While 45.71%(16 cases)of patients with HER2 amplification received trastuzumab in *** application of apatinib increased(33.33%)in *** application of checkpoint inhibitors has increased since *** analysis showed that Lauren mixed type(P=0.017),cycles of first-line treatment>6(P=0.000),CM(P=0.000),palliative gastrectomy(P=0.000),trastuzumab(P=0.011),and apatinib(P=0.008)were independent prognostic factors for the OS of *** PSM and IPTW,the median OS of CM cohort and non-CM cohort was 18.17 and 12.45 months,respectively(P<0.001).Conclusions In real-world practice for AGC in China,therapy choices consisted with ***-drug regimen was the main first-line *** CM treatment was an independent

关键词： advancedgastriccancer real-world study treatment pattern survival analysis Chinese medicine

Constraints on the primordial curvature power spectrum by pulsar timing array data:a polynomial parameterization approach

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Communications in Theoretical Physics 2024年第1期76卷 96-104页

作者： qin Fei School of Mathematics and Physics Hubei Polytechnic UniversityHuangshi 435003China

The recent stochastic signal observed jointly by NANOGrav,parkes pulsar timing array,European pulsar timing array,and Chinese pulsar timing array can be accounted for by scalarinduced gravitational waves(SIGWs).The source of the SIGWs is from the primordial curvature perturbations,and the main contribution to the SIGWs is from the peak of the primordial curvature power *** effectively model this peak,we apply the Taylor expansion to parameterize *** the Taylor expansion parameterization,we apply Bayesian methods to constrain the primordial curvature power spectrum based on the NANOGrav 15 year data *** constraint on the primordial curvature power spectrum possesses a degree of generality,as the Taylor expansion can effectively approximate a wide range of function profiles.

关键词： pulsar timing array scalar-induced gravitational waves inflation

Effect of Jianpi Shengxue Tablet on Iron Metabolism and Nutritional Status in Patients with Renal Anemia:A Prospective,Randomized,Open,Parallel Controlled and Multicenter Clinical Study

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Current Medical Science 2024年第3期44卷 603-610页

作者： Juan YANG meng-yuan LIANG Yu LI Hao ZHANG Wei LI Jing LV Li-ping DONG Jing-song JIN Cheng YANG qing-hong ZHANG Li LONG Rong ZOU Yi GAO Dan SONG Chun-qin PAN Ying YAO xiao-lin ZHAN xiao-hui WANG Department of Nephrology Tongji HospitalTongji Medical CollegeHuazhong University of Science and TechnologyWuhan430030China Department of Nephrology The First People’s Hospital of GuiyangGuiyang550000China Department of Nephrology The Third Xiangya HospitalCentral South UniversityChangsha410000China Department of Nephrology The First Affiliated Hospital of Xi’an Jiaotong UniversityXi’an710061China Department of Nephrology Wuhan No. 4 HospitalWuhan430033China Department of Nephrology Hubei Provincial Hospital of Traditional Chinese MedicineWuhan430060China Department of Nephrology Central Theater General Hospital of PLAWuhan430064China Department of Nephrology Taihe HospitalShiyan442000China Department of Nephrology Third People’s Hospital of Hubei ProvinceWuhan430033China Department of Nephrology Hubei Province Integrated Traditional Chinese and Western Medicine Hospital of Hubei provinceWuhan430024China Department of Nephrology Xi’an No.3 HospitalAffiliated Hospital of Northwest UniversityXi’an710000China Department of Nephrology Shenzhen Guangming District People’s HospitalShenzhen518000China Department of Nephrology Xiantao First People’s HospitalXiantao433000China Department of Nutrition Tongji HospitalTongji Medical CollegeHuazhong University of Science and TechnologyWuhan430030China Department of Nephrology Huangshi Central HospitalHuangshi435000China Department of Nephrology The Fifth Hospital of WuhanWuhan430050China

Objective This study aimed to analyze the clinical efficacy of the Jianpi Shengxue tablet for treating renal *** A total of 200 patients with renal anemia from December 2020 to December 2022 were enrolled and randomly divided into two *** in the control group were treated with polysaccharide-iron complex,and those in the experimental group were administered Jianpi Shengxue *** 8 weeks of continuous treatment,the therapeutic outcomes regarding anemia were compared between the two *** After treatment,the red blood cell(RBC)count,hematocrit(HCT),reticulocyte percentage(RET),ferritin(SF),serum iron(SI),transferrin saturation(TSAT),and serum albumin(ALB)all increased(P<0.01),and the clinical symptom score and total iron binding capacity decreased(P<0.01)in the experimental ***,the improvements in RBC,HCT,RET,SF,SI,TAST,ALB,and clinical symptoms(fatigue,anorexia,dull skin complexion,numbness of hands and feet)in the experimental group were significantly greater than those in the control group(P<0.05).The total effective rate for treating renal anemia was significantly higher in the experimental group than in the control group(P<0.01).Conclusion The Jianpi Shengxue tablet demonstrates efficacy in treating renal anemia,leading to significant improvements in the laboratory examination results and clinical symptoms of patients with renal anemia.

关键词： Jianpi Shengxue tablet renal anemia randomized open parallel control multicenter clinical study

Characteristics of the microbial communities regulate soil multi-functionality under different cover crop amendments in Ultisol

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Journal of Integrative Agriculture 2024年第6期23卷 2099-2111页

作者： Guilong Li xiaofen Chen Wenjing qin Jingrui Chen Ke Leng Luyuan Sun Ming Liu meng Wu Jianbo Fan Changxu Xu Jia Liu Soil and Fertilizer&Resources and Environment Institute Jiangxi Academy of Agricultural SciencesNanchang 330200China Key Laboratory of Acidified Soil Amelioration and Utilization Ministry of Agriculture and Rural AffairsNanchang 330200China Ecological Experimental Station of Red Soil Chinese Academy of SciencesYingtan 335211China

The use of cover crops is a promising strategy for influencing the soil microbial consortium,which is essential for the delivery of multiple soil functions(i.e.,soil multifunctionality).Nonetheless,relatively little is known about the role of the soil microbial consortium in mediating soil multifunctionality under different cover crop amendments in dryland ***,we assessed the multifunctionality of soils subjected to four cover crop amendments(control,non-amended treatment;RD,radish monoculture;HV,hairy vetch monoculture;and RDHV,radish-hairy vetch mixture),and we investigated the contributions of soil microbial richness,network complexity,and ecological clusters to soil *** results demonstrated that cover crops whose chemical composition differed from that of the main plant crop promoted higher multifunctionality,and the radish-hairy vetch mixture rendered the highest *** obtained evidence that changes in soil microbial richness and network complexity triggered by the cover crops were associated with higher soil ***,specialized microbes in a key ecological cluster(ecological cluster 2)of the soil microbial network were particularly important for maintaining soil *** results highlight the importance of cover crop-induced variations in functionally important taxa for promoting the soil multifunctionality of dryland Ultisols.

关键词： cover crops soil multifunctionality microbial richness network complexity ecological cluster

Gene cloning,protein expression,and enzymatic characterization of a double-stranded RNA degrading enzyme in Apolygus lucorum

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Insect Science 2024年第1期31卷 119-133页

作者： Jie-Yu Zhang Jing Zhao Keyan Zhu-Salzman qin-qin Ji Yi-Ping Jiang Liu-Bin xiao De-Jin Xu Guang-Chun Xu Lin-Quan Ge Yong-An Tan College of Plant Protection Yangzhou UniversityYangzhouJiangsu ProvinceChina Institute of Plant Protection Jiangsu Academy of Agricultural SciencesNanjingJiangsu ProvinceChina Department of Entomology Texas A&M UniversityCollege StationTXUSA Taizhou Customs of the People's Republic of China TaizhouJiangsu ProvinceChina

RNA interference(RNAi)is a powerful tool that post-transcriptionally silences target genes in eukaryotic ***,silencing efficacy varies greatly among different insect ***,we met with little success when attempting to knock down genes in the mirid bug Apolygus lucorum via dsRNA *** disappearance of double-stranded RNA(dsRNA)could be a potential factor that restricts RNAi ***,we found that dsRNA can be degraded in midgut fluids,and a dsRNase of ***(AldsRNase)was identified and *** alignment indicated that its 6 key amino acid residues and the Mg2+-binding site were similar to those of other insects’*** signal peptide and endonuclease non-specific domain shared high sequence identity with the brown-winged green stinkbug Plautia stali *** showed high salivary gland and midgut expression and was continuously expressed through the whole life cycle,with peaks at the 4th instar ecdysis in the whole *** purified AldsRNase protein obtained by heterologously expressed can rapidly degrade *** comparing the substrate specificity of AldsRNase,3 specific substrates(dsRNA,small interfering RNA,and dsDNA)were all degraded,and the most efficient degradation is ***,immunofluorescence revealed that AldsRNase was expressed in the cytoplasm of midgut *** cloning and functional study of AldsRNase,the enzyme activity and substrate specificity of the recombinant protein,as well as the subcellular localization of nuclease,the reason for the disappearance of dsRNA was explained,which was useful in improving RNAi efficiency in *** and related species.

关键词： Apolygus lucorum cloning dsRNase enzymatic activity protein expression