The sperm DNA fragmentation index(DFI)is a metric used to assess DNA fragmentation within sperm.During in vitro fertilizationembryo transfer(IVF-ET),high sperm DFI can lead to a low fertilization rate,poor embryo deve...The sperm DNA fragmentation index(DFI)is a metric used to assess DNA fragmentation within sperm.During in vitro fertilizationembryo transfer(IVF-ET),high sperm DFI can lead to a low fertilization rate,poor embryo development,early miscarriage,etc.A kinase anchoring protein(AKAP)is a scaffold protein that can bind protein kinase A(PKA)to subcellular sites of specific substrates and protects the biophosphorylation reaction.Sperm protein antigen 17(SPA17)can also bind to AKAP.This study intends to explore the reason for the decreased fertilization rate observed in high sperm DFI(H-DFI)patients during IVF-ET.In addition,the study investigates the expression of AKAP,protein kinase A regulatory subunit(PKARIl),and SPA17 between H-DFI and low sperm DFI(L-DFI)patients.SPA17 at the transcriptional level is abnormal,the translational level increases in H-DFI patients,and the expression of AKAP4/PKARIl protein decreases.H,O,has been used to simulate oxidative stress damage to spermatozoa during the formation of sperm DFI.It indicates that H,O,increases the expression of sperm SPA17 protein and suppresses AKAP4/PKARIl protein expression.These processes inhibit sperm capacitation and reduce acrosomal reactions.Embryo culture data and IVF outcomes have been documented.The H-DFI group has a lower fertilization rate.Therefore,the results indicate that the possible causes for the decreased fertilization rate in the H-DFI patients have included loss of sperm AKAP4/PKARIl proteins,blocked sperm capacitation,and reduced occurrence of acrosome reaction.展开更多
This article described an unprecedented synthesis of trifluoromethylthiophosphonium salts from allyl trifluoromethyl sulfoxide and phosphines in the presence of trimethylsilyl trifluoromethanesulfonate(TMSOTf)through ...This article described an unprecedented synthesis of trifluoromethylthiophosphonium salts from allyl trifluoromethyl sulfoxide and phosphines in the presence of trimethylsilyl trifluoromethanesulfonate(TMSOTf)through Mislow-Evans-type rearrangement.The resulting trifluoromethylthiophosphonium salts were firstly isolated and fully characterized.These fluoroalkylphosphonium salts,as exemplified by trifluoromethylthio triphenylphosphonium salt(6a),exhibited unique and versatile reaction with nucleophiles and deoxygenative trifluoromethylthiolation reaction of carboxylic acids.Furthermore,the photoredox catalytic tunable radical hydrotrifluoromethylation and hydrotrifluoromethythiolation of unactivated alkenes with 6a was successfully.展开更多
A novel gem-difluoromethylenated castanospermine analogue B was designed and synthesized, starting from 3-bromo-3,3-difluoropropene and L-（-）-malic acid. The key steps involve substitution cyclization reaction and R...A novel gem-difluoromethylenated castanospermine analogue B was designed and synthesized, starting from 3-bromo-3,3-difluoropropene and L-（-）-malic acid. The key steps involve substitution cyclization reaction and RCM reaction to construct the aza fused bicyclic framework.展开更多
A silver-mediated oxidative trifluoromethylation of easily accessibleαα-trifluoromethyl alcohols with TMSCF3 was developed to access novel CF3(OCF3)CH-containing compounds.Deprotonation of CF3(OCF3)CH-substituted ar...A silver-mediated oxidative trifluoromethylation of easily accessibleαα-trifluoromethyl alcohols with TMSCF3 was developed to access novel CF3(OCF3)CH-containing compounds.Deprotonation of CF3(OCF3)CH-substituted arenes afforded synthetically useful CF3O-substituted gem-difluoroalkenes.Furthermore,evaluation of the lipophilicities(log P)indicated that CH(OCF3)CF3 is more lipophilic than the common fluorinated motifs such as CF3,OCF3,and SCF3,thus rendering the CH(OCF3)CF3 motif appealing in drug discovery.展开更多
3-CF3 S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles,respectively,promoted by persulfate.This protocol possesses good fu...3-CF3 S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles,respectively,promoted by persulfate.This protocol possesses good functional group tolerance and high yields.Mechanistic studies suggested that a classic two-step radical process was involved,which includes addition of CF3 S radical to triple bond and cyclization with SMe moiety.展开更多
N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed ...N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F_(2) was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F_(2) in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine-promoted desulfonylation for formation of N-fluoroarenesulfonamide (ArSO_(2)NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron-withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.展开更多
基金This study was supported by Hebei Natural Science Foundation(H2022206019)Science and Technology(S and T)Program of Hebei(21377721D)+1 种基金Hebei Province Medical Technology Tracking Project(GZ2021028)Medical Science Research Project of Hebei Province(20170084,and 20211494).
文摘The sperm DNA fragmentation index(DFI)is a metric used to assess DNA fragmentation within sperm.During in vitro fertilizationembryo transfer(IVF-ET),high sperm DFI can lead to a low fertilization rate,poor embryo development,early miscarriage,etc.A kinase anchoring protein(AKAP)is a scaffold protein that can bind protein kinase A(PKA)to subcellular sites of specific substrates and protects the biophosphorylation reaction.Sperm protein antigen 17(SPA17)can also bind to AKAP.This study intends to explore the reason for the decreased fertilization rate observed in high sperm DFI(H-DFI)patients during IVF-ET.In addition,the study investigates the expression of AKAP,protein kinase A regulatory subunit(PKARIl),and SPA17 between H-DFI and low sperm DFI(L-DFI)patients.SPA17 at the transcriptional level is abnormal,the translational level increases in H-DFI patients,and the expression of AKAP4/PKARIl protein decreases.H,O,has been used to simulate oxidative stress damage to spermatozoa during the formation of sperm DFI.It indicates that H,O,increases the expression of sperm SPA17 protein and suppresses AKAP4/PKARIl protein expression.These processes inhibit sperm capacitation and reduce acrosomal reactions.Embryo culture data and IVF outcomes have been documented.The H-DFI group has a lower fertilization rate.Therefore,the results indicate that the possible causes for the decreased fertilization rate in the H-DFI patients have included loss of sperm AKAP4/PKARIl proteins,blocked sperm capacitation,and reduced occurrence of acrosome reaction.
基金This work was supported by the National Natural Science Foundation of China(21991121,22271298)the National Key Research and Development Program of China(2021YFF0701700).
文摘This article described an unprecedented synthesis of trifluoromethylthiophosphonium salts from allyl trifluoromethyl sulfoxide and phosphines in the presence of trimethylsilyl trifluoromethanesulfonate(TMSOTf)through Mislow-Evans-type rearrangement.The resulting trifluoromethylthiophosphonium salts were firstly isolated and fully characterized.These fluoroalkylphosphonium salts,as exemplified by trifluoromethylthio triphenylphosphonium salt(6a),exhibited unique and versatile reaction with nucleophiles and deoxygenative trifluoromethylthiolation reaction of carboxylic acids.Furthermore,the photoredox catalytic tunable radical hydrotrifluoromethylation and hydrotrifluoromethythiolation of unactivated alkenes with 6a was successfully.
基金the National Natural Science Foundation of China (Nos. 21272036, 21332010)the National Basic Research Program of China (No. 2012CB21600)
文摘A novel gem-difluoromethylenated castanospermine analogue B was designed and synthesized, starting from 3-bromo-3,3-difluoropropene and L-（-）-malic acid. The key steps involve substitution cyclization reaction and RCM reaction to construct the aza fused bicyclic framework.
基金This work was supported by the National Natural Science Foundation of China(Nos.21421002,21991211)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)Youth Innovation Promotion Association CAS(No.2016234).
文摘A silver-mediated oxidative trifluoromethylation of easily accessibleαα-trifluoromethyl alcohols with TMSCF3 was developed to access novel CF3(OCF3)CH-containing compounds.Deprotonation of CF3(OCF3)CH-substituted arenes afforded synthetically useful CF3O-substituted gem-difluoroalkenes.Furthermore,evaluation of the lipophilicities(log P)indicated that CH(OCF3)CF3 is more lipophilic than the common fluorinated motifs such as CF3,OCF3,and SCF3,thus rendering the CH(OCF3)CF3 motif appealing in drug discovery.
基金the National Natural Science Foundation of China(Nos.21991123,21677094)for financial support。
文摘3-CF3 S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles,respectively,promoted by persulfate.This protocol possesses good functional group tolerance and high yields.Mechanistic studies suggested that a classic two-step radical process was involved,which includes addition of CF3 S radical to triple bond and cyclization with SMe moiety.
基金The National Natural Science Foundation of China （21332010, 21421002）, the Strategic Priority Research Program of the Chinese Academy of Sciences （XDB20000000）, and Youth Innovation Pro- motion Association CAS （No. 2016234） are greatly acknowledged for funding this work.
基金The National Natural Science Foundation of China(21991211)the National Key Research and Development Program of China(2021YFF0701700)are greatly acknowledged for funding this work.
文摘N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F_(2) was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F_(2) in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine-promoted desulfonylation for formation of N-fluoroarenesulfonamide (ArSO_(2)NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron-withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.
