A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP ...A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.展开更多
A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar...A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.展开更多
A series of novel quaternary mixed anion complexes of lanthanide containing 1,10 phenanthroline(phen) were synthesized from the water/ethanol solution with slightly acidic solution and characterized by elemental anal...A series of novel quaternary mixed anion complexes of lanthanide containing 1,10 phenanthroline(phen) were synthesized from the water/ethanol solution with slightly acidic solution and characterized by elemental analysis, IR and UV spectra, thermal analysis and single crystal X ray diffraction analysis. The crystal of [Ce(CH 3COO) 2(NO 3)(phen)] 2 belongs to monoclinic system, lattice type C centered, space group C 2/m, a =1 5444(6) nm, b =1 2273(5) nm, c =1 2776(5) nm, β =131 89(2)°, V =1 802(1) nm 3, Z =2, R =0 024, R w =0 032.展开更多
The anionic products from the reactions between metal(M=Ag, Au, Pd, Pt, Pb and Bi) vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas(Ar) were studied by means of a homemade reflectron t...The anionic products from the reactions between metal(M=Ag, Au, Pd, Pt, Pb and Bi) vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas(Ar) were studied by means of a homemade reflectron time-of-flight mass spectrometry(RTOF-MS). Experimental results show that the dominant products were [MmC6F6]^- complexes for the reactions ofAg, Au, Pd and Pt with C6F6, while the dominant products were [MmC6F5]^- complexes for the reactions of Pb and Bi with C6F6. The formation mechanisms of the products, including the adsorption of metal cluster anions on hexafluorobenzene and the C--F cleavage induced by metal cluster anions, were discussed.展开更多
Three new quaternary mixed anion complexes of lanthanides were prepared from thewater-ethanol solution under slightacidity condition and characterizedby elemental analysis, IR, UVspectrum and single crystal X-raydiffr...Three new quaternary mixed anion complexes of lanthanides were prepared from thewater-ethanol solution under slightacidity condition and characterizedby elemental analysis, IR, UVspectrum and single crystal X-raydiffraction analysis. The crystal ofLa(CCl3COO)2 (CH3COO) (phen)(H2O)·DMF]2 belongs to tricliniccrystal system, space group P1with a=1 .2510 (4) nm, b=1.3460(5) nm, c=1.0343 (3)nm, α=102.47(3)°, β=102.34(2)°, γ=113.82 (2)°, μ(MoKa) = 20.47 cm-1, Z= 1, Dc=1. 800 g·cm-3, F (000) =780. 00. The acetate tends to coordinate with the center ion as abridge and trichloroacetate has fourkinds of coordination modes, somany coordination modes were observed in their co-ligand system.展开更多
The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copo...The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copolymer obtained in toluene possessed muchhigher specific rotation than that in THF. These copolymers have shown a tendency to a random and a like alternating structure, respectively.展开更多
A privileged strategy has been developed for the precise construction of enantioenriched azaspiro polycyclic scaffolds.Structurally diverse azaspiro polycycles bearing multiple contiguous stereocenters are obtained wi...A privileged strategy has been developed for the precise construction of enantioenriched azaspiro polycyclic scaffolds.Structurally diverse azaspiro polycycles bearing multiple contiguous stereocenters are obtained with excellent results(up to 99:1 e.r.,>95:5 d.r.) via sequential enantioselective four-component Ugi reactions/post-Ugi transformations with substrates containing prerequisite functional groups in the presence of anionic stereogenic-at-cobalt(Ⅲ) complexes.展开更多
The paramagnetic cis dioxo molybdenum(V) complex, [NH 2~CH 2~CH 2~NH 3] 3[Mo VO 2(HNC 6H 4O) 2] was obtained by the reaction of tetra butyl ammonium β octamolybdate with o aminophenol a...The paramagnetic cis dioxo molybdenum(V) complex, [NH 2~CH 2~CH 2~NH 3] 3[Mo VO 2(HNC 6H 4O) 2] was obtained by the reaction of tetra butyl ammonium β octamolybdate with o aminophenol and ethylenediamine in the mixed solvent of CH 3OH and CH 3CN, and characterized by IR, NMR, EPR spectroscopy and X ray diffraction analysis. The determination of single crystal X ray analysis revealed that the central Mo V ion metal center exhibits distorted octahedral coordination with cis dioxo o aminophenol. The EPR spectra of both the complex and flavoenzyme show similarly. Thus it suggests that the complex anion [Mo VO 2(HNC 6H 4O) 2] 3- and flavoenzyme have related structure feature.展开更多
The treatment of microglial BV-2 cells with sodium arsenate(As(V):0.1-400 μmol/L — 48 hr)induces a dose-dependent response.The neurotoxic effects of high concentrations of As(V)(100,200 and 400 μmol/L) are...The treatment of microglial BV-2 cells with sodium arsenate(As(V):0.1-400 μmol/L — 48 hr)induces a dose-dependent response.The neurotoxic effects of high concentrations of As(V)(100,200 and 400 μmol/L) are characterized by increased levels of mitochondrial complexesⅠ,Ⅱ,and Ⅳ followed by increased superoxide anion generation.Moreover,As(V) triggers an apoptotic mode of cell death,demonstrated by an apoptotic SubG1 peak,associated with an alteration of plasma membrane integrity.There is also a decrease in transmembrane mitochondrial potential and mitochondrial adenosine triphosphate ATP.It is therefore tempting to speculate that As(V) triggers mitochondrial dysfunction,which may lead to defective oxidative phosphorylation subsequently causing mitochondrial oxidative damage,which in turn induces an apoptotic mode of cell death.展开更多
Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to b...Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan–metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan–Fe( Ⅲ) complex prepared by sulfate salts exhibited the best adsorption efficiency(100%) for various dyes in very short time duration(10 min), and its maximum adsorption capacity achieved 349.22 mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan–metal complex. SO4^(2-) ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process.Additionally, the p H sensitivity and the sensitivity of ionic environment for chitosan–metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan–metal complex can help not only in optimizing its use but also in designing new chitosan–metal based complexes.展开更多
文摘A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.
基金Supported by the Open Fund Project innovation platform of Key Laboratory of Higher Educational Institutions of Hunan Province(GN16K01)Scientific&Technological Projects of Hengyang(2016KL03)+1 种基金Aid programs for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincethe Key Discipline of Hunan Province,Project funding for research and innovation experiment of university students in Hunan Province
文摘A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.
文摘A series of novel quaternary mixed anion complexes of lanthanide containing 1,10 phenanthroline(phen) were synthesized from the water/ethanol solution with slightly acidic solution and characterized by elemental analysis, IR and UV spectra, thermal analysis and single crystal X ray diffraction analysis. The crystal of [Ce(CH 3COO) 2(NO 3)(phen)] 2 belongs to monoclinic system, lattice type C centered, space group C 2/m, a =1 5444(6) nm, b =1 2273(5) nm, c =1 2776(5) nm, β =131 89(2)°, V =1 802(1) nm 3, Z =2, R =0 024, R w =0 032.
基金Supported by the National Natural Science Foundation of China(No.20433080).
文摘The anionic products from the reactions between metal(M=Ag, Au, Pd, Pt, Pb and Bi) vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas(Ar) were studied by means of a homemade reflectron time-of-flight mass spectrometry(RTOF-MS). Experimental results show that the dominant products were [MmC6F6]^- complexes for the reactions ofAg, Au, Pd and Pt with C6F6, while the dominant products were [MmC6F5]^- complexes for the reactions of Pb and Bi with C6F6. The formation mechanisms of the products, including the adsorption of metal cluster anions on hexafluorobenzene and the C--F cleavage induced by metal cluster anions, were discussed.
文摘Three new quaternary mixed anion complexes of lanthanides were prepared from thewater-ethanol solution under slightacidity condition and characterizedby elemental analysis, IR, UVspectrum and single crystal X-raydiffraction analysis. The crystal ofLa(CCl3COO)2 (CH3COO) (phen)(H2O)·DMF]2 belongs to tricliniccrystal system, space group P1with a=1 .2510 (4) nm, b=1.3460(5) nm, c=1.0343 (3)nm, α=102.47(3)°, β=102.34(2)°, γ=113.82 (2)°, μ(MoKa) = 20.47 cm-1, Z= 1, Dc=1. 800 g·cm-3, F (000) =780. 00. The acetate tends to coordinate with the center ion as abridge and trichloroacetate has fourkinds of coordination modes, somany coordination modes were observed in their co-ligand system.
文摘The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copolymer obtained in toluene possessed muchhigher specific rotation than that in THF. These copolymers have shown a tendency to a random and a like alternating structure, respectively.
基金supported by the National Natural Science Foundation of China (92156022)the Anhui Provincial Natural Science Funds (1908085J07,1908085QB79,2308085MB44,2308085QB44)the Shen-Nong Scholar Program of Anhui Agricultural University。
文摘A privileged strategy has been developed for the precise construction of enantioenriched azaspiro polycyclic scaffolds.Structurally diverse azaspiro polycycles bearing multiple contiguous stereocenters are obtained with excellent results(up to 99:1 e.r.,>95:5 d.r.) via sequential enantioselective four-component Ugi reactions/post-Ugi transformations with substrates containing prerequisite functional groups in the presence of anionic stereogenic-at-cobalt(Ⅲ) complexes.
基金theNaturalScienceFoundationofBeijingProvince (No .2 0 12 0 0 5 )theNaturalScienceFoundationofEduca tionalMinistryofBeijing
文摘The paramagnetic cis dioxo molybdenum(V) complex, [NH 2~CH 2~CH 2~NH 3] 3[Mo VO 2(HNC 6H 4O) 2] was obtained by the reaction of tetra butyl ammonium β octamolybdate with o aminophenol and ethylenediamine in the mixed solvent of CH 3OH and CH 3CN, and characterized by IR, NMR, EPR spectroscopy and X ray diffraction analysis. The determination of single crystal X ray analysis revealed that the central Mo V ion metal center exhibits distorted octahedral coordination with cis dioxo o aminophenol. The EPR spectra of both the complex and flavoenzyme show similarly. Thus it suggests that the complex anion [Mo VO 2(HNC 6H 4O) 2] 3- and flavoenzyme have related structure feature.
基金supported by grants from the University of Bourgogne(Dijon,France)the University of Monastir(Monastir,Tunisia)
文摘The treatment of microglial BV-2 cells with sodium arsenate(As(V):0.1-400 μmol/L — 48 hr)induces a dose-dependent response.The neurotoxic effects of high concentrations of As(V)(100,200 and 400 μmol/L) are characterized by increased levels of mitochondrial complexesⅠ,Ⅱ,and Ⅳ followed by increased superoxide anion generation.Moreover,As(V) triggers an apoptotic mode of cell death,demonstrated by an apoptotic SubG1 peak,associated with an alteration of plasma membrane integrity.There is also a decrease in transmembrane mitochondrial potential and mitochondrial adenosine triphosphate ATP.It is therefore tempting to speculate that As(V) triggers mitochondrial dysfunction,which may lead to defective oxidative phosphorylation subsequently causing mitochondrial oxidative damage,which in turn induces an apoptotic mode of cell death.
基金supported by the National Natural Science Foundation of China (No. 21407021)the Shanghai Yang-Fan Program of Science and Technology Commission of Shanghai (No. 14YF1405000)+1 种基金the National Key Research and Development Program of China (No. 2016YFC0400501)the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program
文摘Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan–metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan–Fe( Ⅲ) complex prepared by sulfate salts exhibited the best adsorption efficiency(100%) for various dyes in very short time duration(10 min), and its maximum adsorption capacity achieved 349.22 mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan–metal complex. SO4^(2-) ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process.Additionally, the p H sensitivity and the sensitivity of ionic environment for chitosan–metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan–metal complex can help not only in optimizing its use but also in designing new chitosan–metal based complexes.