A phosphrous-containing poly(aryl ether ketone) was synthesized derived from bisphenol-A and bis[4-(4- fluorobenzoyl)phenyl] phenyl phosphine oxide (FPPPO) by nucleophilic substitution reaction. The structure of...A phosphrous-containing poly(aryl ether ketone) was synthesized derived from bisphenol-A and bis[4-(4- fluorobenzoyl)phenyl] phenyl phosphine oxide (FPPPO) by nucleophilic substitution reaction. The structure of the polymer was characterized by FT-IR, ^1H-NMR and ^31p-NMR. The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature (Tg) of the polymer was 205℃, and the 5% weight loss temperature under nitrogen was 475℃. Good solubility of the polymer in organic solvents, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and chloroalkanes was observed, flexible film was obtained from the polymer's CH2Cl2 solution. The limiting oxygen index (LOI) of the PAEK was 40, which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.展开更多
A stereoselective synthetic route to △~5-dehydrosugiyl methyl ether was developed from (S)-(-)-α-cyclocitral, DDQ as a better oxidant for enone was used.
Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound w...Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.展开更多
Two polymeric adsorbents, poly(methyl p-vinylbenzyl ether) and poly(phenyl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene. Their adsorption property for phenol in hexane solution was investig...Two polymeric adsorbents, poly(methyl p-vinylbenzyl ether) and poly(phenyl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene. Their adsorption property for phenol in hexane solution was investigated. The results showed that the two adsorbents adsorb phenol from hexane solution through hydrogen-bonding and π-π stacking interaction.展开更多
The facile enantioselective synthesis of the di-O-methyl ethers of (-)-agatharesinol (1b), (-)-sugiresionl (2b), (+)-nyasol (3b) and (+)-tetrahydronyasol (4) were achieved in high yield. The absolute...The facile enantioselective synthesis of the di-O-methyl ethers of (-)-agatharesinol (1b), (-)-sugiresionl (2b), (+)-nyasol (3b) and (+)-tetrahydronyasol (4) were achieved in high yield. The absolute configuration of (+)-3a was confirmed via first total synthesis of (+)-3b and (+)-4.展开更多
A series of(R)-2-phenyl-4,5-dihydrothiazole-4-carboxamide derivatives containing a sulfur ether moiety were synthesized and characterized on the basis of NMR and elemental analysis(EA). The crystal structure of(R)-N-(...A series of(R)-2-phenyl-4,5-dihydrothiazole-4-carboxamide derivatives containing a sulfur ether moiety were synthesized and characterized on the basis of NMR and elemental analysis(EA). The crystal structure of(R)-N-(2-methyl-1-(methylthio)propan-2-yl)-2-(4-nitrophenyl)-4,5-dihydrothiazole-4-carboxamide(13 d) was determined to show R configuration. The bioasssy results indicated that most title compounds displayed good and broad spectrum antifungal activities against several phytopathogenic fungi. The structure activity relationships were discussed. Based on the antifungal activity of title compounds against Phytophthora capsici, a CoMSIA calculation was performed to establish a 3 D-QSAR model, which revealed that electrostatic and hydrophobic fields were the two most significant factors for antifungal activity. According to the established 3D-QSAR model, structure optimization was carried out to find(R)-N-((R)-1-(methylthio)propan-2-yl)-2-(p-tolyl)-4,5-dihydrothiazole-4-carboxamide(15 h)with excellent activity against Phytophthora capsici, thus emerging as a new lead compound for novel antiphytopathogenic fungus agent development.展开更多
The biosafety of methyl tertiary-butyl ether(MTBE),mainly used as a gasoline additive,has long been a contentious topic.In addition to its routine toxicities,MTBE has been demonstrated to disrupt glucose and lipid met...The biosafety of methyl tertiary-butyl ether(MTBE),mainly used as a gasoline additive,has long been a contentious topic.In addition to its routine toxicities,MTBE has been demonstrated to disrupt glucose and lipid metabolism and contribute to the development of type2 diabetes as well as obesity.As one of the morbidities related to dyslipidemia,atherosclerosis is worthy of being investigated under MTBE exposure.Since foam cells derived from macrophages play pivotal roles during atherosclerosis development,we studied the effects of MTBE on macrophages in vitro and assessed the effect of MTBE on atherosclerosis plaque formation with the ApoE^(-/-)mouse model in uiuo for the first time.Our results demonstrated that exposure to MTBE at environmentally relevant concentrations decreased the expression of ABCA1 and ABCG1,which are responsible for macrophage cholesterol efflux,at both mRNA and protein levels in THP-1 macrophages.Consequently,treatment with MTBE inhibited the transport of cholesterol from macrophages to High-density lipoprotein.ApoE^(-/-)mice exposed to MTBE at environmentally relevant concentrations(100,1000μg/kg)displayed significant increases in lesion area in the aorta and aortic root compared to vehicletreated ones.Further analysis indicated that MTBE exposure enhanced the macrophagespecific marker Mac-2 contents within plaques in the aortic root,implying that MTBE could promote macrophage-derived foam cell formation and thus accelerate atherosclerosis plaque formation.We for the first time demonstrated the pro-atherogenic effect of MTBE via eliciting disruption of macrophage cholesterol efflux and accelerating foam cell formation and atherosclerosis plaque development.展开更多
Two novel silver(I) complexes [Ag(DPEphos)(dppe)]Cl O4(1) and [Ag(DPEphos)-(dppe)]SCN(2)(DPEphos = bis[2-(diphenylphosphino)phenyl]ether, dppe = bis(diphenylphosphino)ethane) are synthesized and ch...Two novel silver(I) complexes [Ag(DPEphos)(dppe)]Cl O4(1) and [Ag(DPEphos)-(dppe)]SCN(2)(DPEphos = bis[2-(diphenylphosphino)phenyl]ether, dppe = bis(diphenylphosphino)ethane) are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821(12), b = 12.6620(11), c = 36.025(3) ?, β = 112.633(2)°, V = 6265.7(9) ?3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F(000) = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections(I 〉 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021(13), b = 12.6100(11), c = 35.920(3) A, β = 112.852(2)°, V = 6220.2(9) A3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F(000) = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections(I 〉 2σ(I)). In mono-nuclear complexes 1 and 2, the Ag(I) atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals(doublets or triplets) which can be attributed to the coupling of the 107,109Ag–31P(from DPEphos or dppe ligand). All the emission peaks of these complexes are attributed to ligand-centered(π-π*) transitions.展开更多
Synthesis and electrochemical polymerization of 9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene (EO-F) into poly[9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene] (EO-PF) films are reported....Synthesis and electrochemical polymerization of 9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene (EO-F) into poly[9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene] (EO-PF) films are reported. The boron trifluoride diethyl etherate electrolyte enables facile preparation of EO-PF films at lower potential compared to LiCIOa/MeCN and the electrochemical polymerizations are discussed. The EO-PF shows good electrochemical behavior and can be dissolved in solvents such as DMSO and THF. The solubility of EO-PF in THF is 2 mg.mL-1 and the number average molecular weight is 35300 with a polydispersity index of 1.65. The side chains on C9 position of the monomer maintain unchanged aRer electrooxidation into corresponding polymer. The EO-PF dissolved in THF under 365 nm ultraviolet light is sky blue light emitting with the Commission Internationale de L'Eclairage-CIE coordinates of (0.19, 0.15). The electropolymerized EO-PF is used for the first time in chemosensing metal ions, demonstrating fluorescence quenching for Mn2+ and Fe3+ while fluorescence enhancement for Cr6+ ions.展开更多
The photoinduced electron-transfer reaction of N,N,N′,N′-tetra-(p-methylphenyl)-4,4′-diamino-1,1′-diphenyl ether (TPDAE) and fullerenes (C 60/C 70) by nanosecond laser flash photolysis occurred in benzonitri...The photoinduced electron-transfer reaction of N,N,N′,N′-tetra-(p-methylphenyl)-4,4′-diamino-1,1′-diphenyl ether (TPDAE) and fullerenes (C 60/C 70) by nanosecond laser flash photolysis occurred in benzonitrile. Transient absorption spectral measurements were carried out during 532 nm laser flash photolysis of a mixture of the fullerenes (C 60/C 70) and TPDAE. The electron transfer from the TPDAE to excited triplet state of the fullerenes (C 60/C 70) quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C 60/C 70) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes (C 60/C 70) and radical cations of TPDAE are expected to appear.展开更多
In order to find novel herbicidal active compounds, a series of N-(2,2-dimethyl-7-alkoxy-2,3-dihydro- benzofuran-5-yl)-2-(4-arylxoyphenoxy)propionamides was designed, prepared and evaluated for their herbicidal ac...In order to find novel herbicidal active compounds, a series of N-(2,2-dimethyl-7-alkoxy-2,3-dihydro- benzofuran-5-yl)-2-(4-arylxoyphenoxy)propionamides was designed, prepared and evaluated for their herbicidal activity. Bioassay results showed that most of the title compounds had excellent and selective herbicidal activity against the monocotyledonous grasses. In particular, compounds lg and lm showed 100% inhibition against the growth of three monocotyledonous grasses under both postemergence and preemergence treatments at the dose of 2250 g/hm2 (1 hm2= 104 m2), and could be used as lead compounds for further development of novel potential herbicidal agents.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.50203008).
文摘A phosphrous-containing poly(aryl ether ketone) was synthesized derived from bisphenol-A and bis[4-(4- fluorobenzoyl)phenyl] phenyl phosphine oxide (FPPPO) by nucleophilic substitution reaction. The structure of the polymer was characterized by FT-IR, ^1H-NMR and ^31p-NMR. The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature (Tg) of the polymer was 205℃, and the 5% weight loss temperature under nitrogen was 475℃. Good solubility of the polymer in organic solvents, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and chloroalkanes was observed, flexible film was obtained from the polymer's CH2Cl2 solution. The limiting oxygen index (LOI) of the PAEK was 40, which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.
基金the National Natural Science Foundation of China (No. 29372050) for financial support.
文摘A stereoselective synthetic route to △~5-dehydrosugiyl methyl ether was developed from (S)-(-)-α-cyclocitral, DDQ as a better oxidant for enone was used.
文摘Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.
基金the National Natural Science Foundation of China(No.29974015)the Visiting Scholar Foundation of Key Lab.In University for the financial support
文摘Two polymeric adsorbents, poly(methyl p-vinylbenzyl ether) and poly(phenyl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene. Their adsorption property for phenol in hexane solution was investigated. The results showed that the two adsorbents adsorb phenol from hexane solution through hydrogen-bonding and π-π stacking interaction.
基金Projet supported by-the-Speei-al Doctorial Program Funds of the Ministry of Education of China (No. 20040730008), Gansu Science Foundation (No. 3ZS051-A25-004).
文摘The facile enantioselective synthesis of the di-O-methyl ethers of (-)-agatharesinol (1b), (-)-sugiresionl (2b), (+)-nyasol (3b) and (+)-tetrahydronyasol (4) were achieved in high yield. The absolute configuration of (+)-3a was confirmed via first total synthesis of (+)-3b and (+)-4.
基金financially supported by the Scientific Project of Tianjin Municipal Education Commission(No. 2018KJ008)Tianjin Natural Science Foundation(No. 16JCYBJC29400)
文摘A series of(R)-2-phenyl-4,5-dihydrothiazole-4-carboxamide derivatives containing a sulfur ether moiety were synthesized and characterized on the basis of NMR and elemental analysis(EA). The crystal structure of(R)-N-(2-methyl-1-(methylthio)propan-2-yl)-2-(4-nitrophenyl)-4,5-dihydrothiazole-4-carboxamide(13 d) was determined to show R configuration. The bioasssy results indicated that most title compounds displayed good and broad spectrum antifungal activities against several phytopathogenic fungi. The structure activity relationships were discussed. Based on the antifungal activity of title compounds against Phytophthora capsici, a CoMSIA calculation was performed to establish a 3 D-QSAR model, which revealed that electrostatic and hydrophobic fields were the two most significant factors for antifungal activity. According to the established 3D-QSAR model, structure optimization was carried out to find(R)-N-((R)-1-(methylthio)propan-2-yl)-2-(p-tolyl)-4,5-dihydrothiazole-4-carboxamide(15 h)with excellent activity against Phytophthora capsici, thus emerging as a new lead compound for novel antiphytopathogenic fungus agent development.
基金supported by the National Key R&D Program of China(Nos.2019YFC1605800,2018YFC0406302)the National Natural Science Foundation of China(Nos.21806179,21672255)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB14040201)。
文摘The biosafety of methyl tertiary-butyl ether(MTBE),mainly used as a gasoline additive,has long been a contentious topic.In addition to its routine toxicities,MTBE has been demonstrated to disrupt glucose and lipid metabolism and contribute to the development of type2 diabetes as well as obesity.As one of the morbidities related to dyslipidemia,atherosclerosis is worthy of being investigated under MTBE exposure.Since foam cells derived from macrophages play pivotal roles during atherosclerosis development,we studied the effects of MTBE on macrophages in vitro and assessed the effect of MTBE on atherosclerosis plaque formation with the ApoE^(-/-)mouse model in uiuo for the first time.Our results demonstrated that exposure to MTBE at environmentally relevant concentrations decreased the expression of ABCA1 and ABCG1,which are responsible for macrophage cholesterol efflux,at both mRNA and protein levels in THP-1 macrophages.Consequently,treatment with MTBE inhibited the transport of cholesterol from macrophages to High-density lipoprotein.ApoE^(-/-)mice exposed to MTBE at environmentally relevant concentrations(100,1000μg/kg)displayed significant increases in lesion area in the aorta and aortic root compared to vehicletreated ones.Further analysis indicated that MTBE exposure enhanced the macrophagespecific marker Mac-2 contents within plaques in the aortic root,implying that MTBE could promote macrophage-derived foam cell formation and thus accelerate atherosclerosis plaque formation.We for the first time demonstrated the pro-atherogenic effect of MTBE via eliciting disruption of macrophage cholesterol efflux and accelerating foam cell formation and atherosclerosis plaque development.
基金supported by the National Natural Science Foundation of China(Nos.21171119 and 81573822)the National High Technology Research and Development Program 863 of China(No.2012AA063201)+1 种基金the Technology Foundation for Selected Overseas Chinese,the Beijing Municipal Education Commission(KM201510028006)the Scientific Research Base Development Program of the Beijing Municipal Commission of Education
文摘Two novel silver(I) complexes [Ag(DPEphos)(dppe)]Cl O4(1) and [Ag(DPEphos)-(dppe)]SCN(2)(DPEphos = bis[2-(diphenylphosphino)phenyl]ether, dppe = bis(diphenylphosphino)ethane) are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821(12), b = 12.6620(11), c = 36.025(3) ?, β = 112.633(2)°, V = 6265.7(9) ?3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F(000) = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections(I 〉 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021(13), b = 12.6100(11), c = 35.920(3) A, β = 112.852(2)°, V = 6220.2(9) A3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F(000) = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections(I 〉 2σ(I)). In mono-nuclear complexes 1 and 2, the Ag(I) atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals(doublets or triplets) which can be attributed to the coupling of the 107,109Ag–31P(from DPEphos or dppe ligand). All the emission peaks of these complexes are attributed to ligand-centered(π-π*) transitions.
基金financially supported by the National Natural Science Foundation of China(Nos.50903078,21274134)New Century Excellent Talents in Universities(No.NCET-11-0473)
文摘Synthesis and electrochemical polymerization of 9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene (EO-F) into poly[9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene] (EO-PF) films are reported. The boron trifluoride diethyl etherate electrolyte enables facile preparation of EO-PF films at lower potential compared to LiCIOa/MeCN and the electrochemical polymerizations are discussed. The EO-PF shows good electrochemical behavior and can be dissolved in solvents such as DMSO and THF. The solubility of EO-PF in THF is 2 mg.mL-1 and the number average molecular weight is 35300 with a polydispersity index of 1.65. The side chains on C9 position of the monomer maintain unchanged aRer electrooxidation into corresponding polymer. The EO-PF dissolved in THF under 365 nm ultraviolet light is sky blue light emitting with the Commission Internationale de L'Eclairage-CIE coordinates of (0.19, 0.15). The electropolymerized EO-PF is used for the first time in chemosensing metal ions, demonstrating fluorescence quenching for Mn2+ and Fe3+ while fluorescence enhancement for Cr6+ ions.
文摘The photoinduced electron-transfer reaction of N,N,N′,N′-tetra-(p-methylphenyl)-4,4′-diamino-1,1′-diphenyl ether (TPDAE) and fullerenes (C 60/C 70) by nanosecond laser flash photolysis occurred in benzonitrile. Transient absorption spectral measurements were carried out during 532 nm laser flash photolysis of a mixture of the fullerenes (C 60/C 70) and TPDAE. The electron transfer from the TPDAE to excited triplet state of the fullerenes (C 60/C 70) quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C 60/C 70) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes (C 60/C 70) and radical cations of TPDAE are expected to appear.
文摘In order to find novel herbicidal active compounds, a series of N-(2,2-dimethyl-7-alkoxy-2,3-dihydro- benzofuran-5-yl)-2-(4-arylxoyphenoxy)propionamides was designed, prepared and evaluated for their herbicidal activity. Bioassay results showed that most of the title compounds had excellent and selective herbicidal activity against the monocotyledonous grasses. In particular, compounds lg and lm showed 100% inhibition against the growth of three monocotyledonous grasses under both postemergence and preemergence treatments at the dose of 2250 g/hm2 (1 hm2= 104 m2), and could be used as lead compounds for further development of novel potential herbicidal agents.