A novel compound, (HGly) 4[HPMo 12 O 40 ] 2·22H 2O, was synthesized and characterized by means of elemental analysis, IR and X ray diffraction. The compound crystallized in a monoclinic space group ...A novel compound, (HGly) 4[HPMo 12 O 40 ] 2·22H 2O, was synthesized and characterized by means of elemental analysis, IR and X ray diffraction. The compound crystallized in a monoclinic space group Cc with a =4 0060(0 8) nm, b =1 2527(0 3) nm, c =1 9930(0 4) nm, β =96 36(3)°, V =9 940(3) nm 3, Z =2, R 1=0 0576, wR 2 =0 1746. The anti tumor activity of this compound was tested in two human tumor cell lines in vitro .展开更多
Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel m...Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel method. The catalysts were characterized by EDX, BET, FTIR, UV-Vis DRS, XRD and the results indicate that such paratungstate-loaded catalysts maintained their heptatungstate structure in the anatase titania matrix up to 400 ℃. The catalysts were tested for the heterogeneous photodegradation of chlorobenzene in aqueous media and showed a better catalytic activity than P-25 TiO_ 2 because paratungstate can prevent the recombination of the holes and electrons produced during irradiation. Moreover, the paratungstate-loaded titania catalysts can resist the disaggregation during the photoirradiation and can be easily recycled from the aqueous suspensions after reactions.展开更多
The mechanism and dynamical properties for the reaction of HCCO radicals with NO were investigated theoretically. The minimum energy paths(MEP) of the reaction were calculated by using the density functional theory(DF...The mechanism and dynamical properties for the reaction of HCCO radicals with NO were investigated theoretically. The minimum energy paths(MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311+G ** level, and the energies along the MEP were further refined at the QCISD(T)/6-311+G ** level. It is found that the reaction mechanism of the title reaction involves three channels, producing HCNO+CO, HONC+CO and HCN+CO 2 products, respectively. Channel 1 is the most favorable path. The rate constant for channel 1 were calculated over a temperature range of 800—2500 K by using the canonical variational transition-state theory(CVT). The rate constant for the main path is negatively dependent on temperature, which is a characteristic of radical reactions with negative activation energy, and the variational effect for the rate constant calculation is small in the whole temperature range.展开更多
A novel 5-fluorouracil salt of 12-silicatungstic acid was synthesized and characterized by means of elemental analysis, IR, 1H NMR and 183W NMR spectra. The antitumor activity and toxicity of the complex have been eva...A novel 5-fluorouracil salt of 12-silicatungstic acid was synthesized and characterized by means of elemental analysis, IR, 1H NMR and 183W NMR spectra. The antitumor activity and toxicity of the complex have been evaluated both in vitro and in vivo.展开更多
Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/ 2-octanol/ water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confi...Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/ 2-octanol/ water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confirmed that the average sizes and shape of the BaLiF3 nanocrystals. The formation of BaLiF3 and particles size were strongly affected by water content. With increasing water content and reaction times, the size of the particle increases. Meanwhile, the solvent was also found to play a key role in the synthesis of the BaLiF3 nanocrystals.展开更多
A novel vanadate decamer, involving all vanadium atoms present in +5 oxidation and one formhydroxamic acid dimer cation readical, has been synthesized. The single-crystal X-ray diffraction shows that the orange crysta...A novel vanadate decamer, involving all vanadium atoms present in +5 oxidation and one formhydroxamic acid dimer cation readical, has been synthesized. The single-crystal X-ray diffraction shows that the orange crystal is formed in the triclinic system, space group Pi, a = 8. 4960 (17), b = 10.447 (2), c = 11.299 (2) A, α= 68. 82 (3)°,β= 87.35 (3)°, γ = 66.97(3)°. V = 855. 3(3) A3, Z = 8, R1 = 0. 0857, wR2=0. 2551. X-ray crystallographic and packing in superlattice studies showed that the crystal structure was constructed by electrostatic attraction of O-H…O hydrogen bonds between formhydroxamic acid dimer cation and decavanadate polyanion. Formhydroxamic acid dimer is got through controlling the condition of the reaction using formhydroxamic acid.展开更多
The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave po...The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave potential of the complexes indicated that the effect of the functionallization of POMs increased the oxidizing ability of the polyoxoanions. The inhibitory effects of the CpTi polyoxocomplexes on tumor cells are higher than those of the corresponding titanium polyoxocomplexes, and the toxicity of the former is lower than that of the latter. The oxygenation reactions of cyclohexene, styrene, trans stilbene and maleic acid with PhIO or hydrogen peroxide(30% aqueous solution) catalyzed respectively by Ti and CpTi polyoxocomplexes were compared.展开更多
The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity o...The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity of the electrolytic solution consisting of Li_3PW_ 12O_ 40 and PC/DME mixing solvent(1/2.5, volume ratio) is up to 7.2×10 -2 S/cm, being higher than that of LiClO_4 as the electrolyte. The all-lithium salts were used as electrolytes in secondary lithium-ion batteries. The discharge capacity of the PAS/Li batteries with Li_3PW_ 12O_ 40 electrolyte solutions reaches to 148 (mA·h)/g and the cyclic life is up to 380 times, much better than those of commercialized products with LiClO_4 and LiAsF_6 as electrolytes.展开更多
A new polyoxovanadate cluster, [NH_3(CH_2)_2NH_2(CH_2)_2NH_3]_4[VⅤ_6VⅣ_ 12O_ 42(PO_4)](PO_4)·2H_2O, has been synthesized and characterized by means of elemental analysis, IR spectrometry, EPR spectrometry, TG a...A new polyoxovanadate cluster, [NH_3(CH_2)_2NH_2(CH_2)_2NH_3]_4[VⅤ_6VⅣ_ 12O_ 42(PO_4)](PO_4)·2H_2O, has been synthesized and characterized by means of elemental analysis, IR spectrometry, EPR spectrometry, TG analysis and single crystal X-ray diffraction. This compound crystallizes in a monoclinic space group C2/c with a= 2.3912(5) nm, b=1.3002(3) nm, c=2.0172(4) nm, β=105.75(3)°, V=6.036(2) nm3, Z=2, R_1=0.0572, wR_2=0.1476. It has a superKeggin structure with a Keggin unit capped by six [VO_5] moieties on the pits on every side of the Keggin unit. The anti-tumor activity of the compound was estimated in three human tumor cell lines in vitro.展开更多
Keggin anions behave differently from each other when they react with nucleic acids. The molybdenum series exhibits oxidative cleavage activity towards AMP and DNA. The mechanism of AMP damage and DNA cleavage caused ...Keggin anions behave differently from each other when they react with nucleic acids. The molybdenum series exhibits oxidative cleavage activity towards AMP and DNA. The mechanism of AMP damage and DNA cleavage caused by the molybdenum series is mainly oxidation and the oxidation sites are on the ribose parts other than on the adenine parts, while the hydrolysis probably makes significant contributions to the cleavage of DNA and to the damage of AMP caused by the tungsten series.展开更多
Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by...Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by means of 1H NMR, IR, UV. By the method of ab initio HF and density functional theory (DFT) B3LYP, the geometric structures of the reagent intermediate, the product and its isomer were optimized and their total energies were calculated. The properties for the frontier molecular orbitals and the rules for energy distribution were analyzed systematically. It was shown that the energy of the nitrogen alkyl compound is lower than that of the oxy alkyl compound and the former is stable than the latter . This result is in accordance with the fact that 6 chloro 2 diethylaminoethyl 3(2H) pyridazinone is synthesized by the reaction of \{6 chloride \}2 diethylaminoethyl 3(2H) pyridazinone and 2 diethylaminoethyl chloride.展开更多
The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1,10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltamm...The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1,10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient D c and rate constant k s of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.展开更多
The geometrical structures of 2 (2 hydroxyphenyl) pyridine(PP) and its protonation states were optimized by means of the B3LYP/6 31G(d) method. For all the selected systems, the existence of H bond is in favor of ...The geometrical structures of 2 (2 hydroxyphenyl) pyridine(PP) and its protonation states were optimized by means of the B3LYP/6 31G(d) method. For all the selected systems, the existence of H bond is in favor of the stability of the systems. On the basis of the optimized geometrical structures, their electronic spectrum properties were studied by time dependent density functional theory(TD DFT) methosd via a hybrid function of B3LYP and 6 31G(d) basis set. The TD DFT calculation result predicts the absorption spectrum of PP at 324 nm(3.82 eV), which is in very good agreement with the experimental value of 322 nm( 3.85 eV ) determined in solvent chloroform. The absorption spectra of the two protonation states both exert a red shift in various pH media.展开更多
A new method for synthesis of 3-azido-3-deoxyxylofuranoside was described. D-ribose was methylated, then treated with methanesulfonyl chloride to give II. II was selectively replaced by benzoate at the 5-position to...A new method for synthesis of 3-azido-3-deoxyxylofuranoside was described. D-ribose was methylated, then treated with methanesulfonyl chloride to give II. II was selectively replaced by benzoate at the 5-position to give III. All these processes gave good yields. III was treated with sodium azide to afford IV, whose structure was determined by 1H NMR and 13C NMR.展开更多
A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ~ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiato...A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ~ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiator and stannous octanoate as a catalyst at 110 ℃ for 48 h. The molecular length of the PCL pre-polymer(BB) could be adjusted by controlling the molar ratio of the ethylene glycol initiator to ε-caprolactone monomer. The structure and the composition of the block copolymer were determined by the weight ratio of the monomer glycolide(A) to PCL pre-polymer(BB). The block copolymers were characterized by ~ 1H NMR, GPC, DSC and X-ray. The results confirm the successful synthesis of an ABBA block copolymer.展开更多
基金Supported by National Natural Science Foundation of China(No.2 0 1710 10 ) .
文摘A novel compound, (HGly) 4[HPMo 12 O 40 ] 2·22H 2O, was synthesized and characterized by means of elemental analysis, IR and X ray diffraction. The compound crystallized in a monoclinic space group Cc with a =4 0060(0 8) nm, b =1 2527(0 3) nm, c =1 9930(0 4) nm, β =96 36(3)°, V =9 940(3) nm 3, Z =2, R 1=0 0576, wR 2 =0 1746. The anti tumor activity of this compound was tested in two human tumor cell lines in vitro .
文摘Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel method. The catalysts were characterized by EDX, BET, FTIR, UV-Vis DRS, XRD and the results indicate that such paratungstate-loaded catalysts maintained their heptatungstate structure in the anatase titania matrix up to 400 ℃. The catalysts were tested for the heterogeneous photodegradation of chlorobenzene in aqueous media and showed a better catalytic activity than P-25 TiO_ 2 because paratungstate can prevent the recombination of the holes and electrons produced during irradiation. Moreover, the paratungstate-loaded titania catalysts can resist the disaggregation during the photoirradiation and can be easily recycled from the aqueous suspensions after reactions.
文摘The mechanism and dynamical properties for the reaction of HCCO radicals with NO were investigated theoretically. The minimum energy paths(MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311+G ** level, and the energies along the MEP were further refined at the QCISD(T)/6-311+G ** level. It is found that the reaction mechanism of the title reaction involves three channels, producing HCNO+CO, HONC+CO and HCN+CO 2 products, respectively. Channel 1 is the most favorable path. The rate constant for channel 1 were calculated over a temperature range of 800—2500 K by using the canonical variational transition-state theory(CVT). The rate constant for the main path is negatively dependent on temperature, which is a characteristic of radical reactions with negative activation energy, and the variational effect for the rate constant calculation is small in the whole temperature range.
文摘A novel 5-fluorouracil salt of 12-silicatungstic acid was synthesized and characterized by means of elemental analysis, IR, 1H NMR and 183W NMR spectra. The antitumor activity and toxicity of the complex have been evaluated both in vitro and in vivo.
文摘Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/ 2-octanol/ water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confirmed that the average sizes and shape of the BaLiF3 nanocrystals. The formation of BaLiF3 and particles size were strongly affected by water content. With increasing water content and reaction times, the size of the particle increases. Meanwhile, the solvent was also found to play a key role in the synthesis of the BaLiF3 nanocrystals.
文摘A novel vanadate decamer, involving all vanadium atoms present in +5 oxidation and one formhydroxamic acid dimer cation readical, has been synthesized. The single-crystal X-ray diffraction shows that the orange crystal is formed in the triclinic system, space group Pi, a = 8. 4960 (17), b = 10.447 (2), c = 11.299 (2) A, α= 68. 82 (3)°,β= 87.35 (3)°, γ = 66.97(3)°. V = 855. 3(3) A3, Z = 8, R1 = 0. 0857, wR2=0. 2551. X-ray crystallographic and packing in superlattice studies showed that the crystal structure was constructed by electrostatic attraction of O-H…O hydrogen bonds between formhydroxamic acid dimer cation and decavanadate polyanion. Formhydroxamic acid dimer is got through controlling the condition of the reaction using formhydroxamic acid.
基金Supported by the National Natural Science Foundation of China(No.39970 82 4 )
文摘The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave potential of the complexes indicated that the effect of the functionallization of POMs increased the oxidizing ability of the polyoxoanions. The inhibitory effects of the CpTi polyoxocomplexes on tumor cells are higher than those of the corresponding titanium polyoxocomplexes, and the toxicity of the former is lower than that of the latter. The oxygenation reactions of cyclohexene, styrene, trans stilbene and maleic acid with PhIO or hydrogen peroxide(30% aqueous solution) catalyzed respectively by Ti and CpTi polyoxocomplexes were compared.
文摘The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity of the electrolytic solution consisting of Li_3PW_ 12O_ 40 and PC/DME mixing solvent(1/2.5, volume ratio) is up to 7.2×10 -2 S/cm, being higher than that of LiClO_4 as the electrolyte. The all-lithium salts were used as electrolytes in secondary lithium-ion batteries. The discharge capacity of the PAS/Li batteries with Li_3PW_ 12O_ 40 electrolyte solutions reaches to 148 (mA·h)/g and the cyclic life is up to 380 times, much better than those of commercialized products with LiClO_4 and LiAsF_6 as electrolytes.
文摘A new polyoxovanadate cluster, [NH_3(CH_2)_2NH_2(CH_2)_2NH_3]_4[VⅤ_6VⅣ_ 12O_ 42(PO_4)](PO_4)·2H_2O, has been synthesized and characterized by means of elemental analysis, IR spectrometry, EPR spectrometry, TG analysis and single crystal X-ray diffraction. This compound crystallizes in a monoclinic space group C2/c with a= 2.3912(5) nm, b=1.3002(3) nm, c=2.0172(4) nm, β=105.75(3)°, V=6.036(2) nm3, Z=2, R_1=0.0572, wR_2=0.1476. It has a superKeggin structure with a Keggin unit capped by six [VO_5] moieties on the pits on every side of the Keggin unit. The anti-tumor activity of the compound was estimated in three human tumor cell lines in vitro.
文摘Keggin anions behave differently from each other when they react with nucleic acids. The molybdenum series exhibits oxidative cleavage activity towards AMP and DNA. The mechanism of AMP damage and DNA cleavage caused by the molybdenum series is mainly oxidation and the oxidation sites are on the ribose parts other than on the adenine parts, while the hydrolysis probably makes significant contributions to the cleavage of DNA and to the damage of AMP caused by the tungsten series.
基金Supported by the National Natural Science Foundation of China(No. 2 0 16 2 0 0 5 ) .
文摘Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by means of 1H NMR, IR, UV. By the method of ab initio HF and density functional theory (DFT) B3LYP, the geometric structures of the reagent intermediate, the product and its isomer were optimized and their total energies were calculated. The properties for the frontier molecular orbitals and the rules for energy distribution were analyzed systematically. It was shown that the energy of the nitrogen alkyl compound is lower than that of the oxy alkyl compound and the former is stable than the latter . This result is in accordance with the fact that 6 chloro 2 diethylaminoethyl 3(2H) pyridazinone is synthesized by the reaction of \{6 chloride \}2 diethylaminoethyl 3(2H) pyridazinone and 2 diethylaminoethyl chloride.
文摘The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1,10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient D c and rate constant k s of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.
基金Supported by the Excellent Young Teachers Program of MOETrans- century Program me Foundation for the Talentsby the State Education Ministry and Excellent Youth Foundation of Jilin Province
文摘The geometrical structures of 2 (2 hydroxyphenyl) pyridine(PP) and its protonation states were optimized by means of the B3LYP/6 31G(d) method. For all the selected systems, the existence of H bond is in favor of the stability of the systems. On the basis of the optimized geometrical structures, their electronic spectrum properties were studied by time dependent density functional theory(TD DFT) methosd via a hybrid function of B3LYP and 6 31G(d) basis set. The TD DFT calculation result predicts the absorption spectrum of PP at 324 nm(3.82 eV), which is in very good agreement with the experimental value of 322 nm( 3.85 eV ) determined in solvent chloroform. The absorption spectra of the two protonation states both exert a red shift in various pH media.
基金This paper was supported by the fund of Hengdian Group, Zhejiang.
文摘A new method for synthesis of 3-azido-3-deoxyxylofuranoside was described. D-ribose was methylated, then treated with methanesulfonyl chloride to give II. II was selectively replaced by benzoate at the 5-position to give III. All these processes gave good yields. III was treated with sodium azide to afford IV, whose structure was determined by 1H NMR and 13C NMR.
文摘A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ~ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiator and stannous octanoate as a catalyst at 110 ℃ for 48 h. The molecular length of the PCL pre-polymer(BB) could be adjusted by controlling the molar ratio of the ethylene glycol initiator to ε-caprolactone monomer. The structure and the composition of the block copolymer were determined by the weight ratio of the monomer glycolide(A) to PCL pre-polymer(BB). The block copolymers were characterized by ~ 1H NMR, GPC, DSC and X-ray. The results confirm the successful synthesis of an ABBA block copolymer.