Two unusual one-dimensional(1-D) compounds,viz.[Co(Medpq)(QUI)·H2O]2n· 2.4nH2O 1 and [Cd(Medpq)(QUI)·H2O]n·nH2O 2,were synthesized by the combination of two different metallic salts and o...Two unusual one-dimensional(1-D) compounds,viz.[Co(Medpq)(QUI)·H2O]2n· 2.4nH2O 1 and [Cd(Medpq)(QUI)·H2O]n·nH2O 2,were synthesized by the combination of two different metallic salts and organic ligands,namely 2,3-pyridinedicarboxylic acid(H2QUI) and 2-methyldipyrido[3,2-f:2',3'-h]quinoxaline(Medpq) ligand.The compounds were characterized by elemental analyses,TG,fluorescent emission and single-crystal X-ray diffraction analyses.展开更多
Six new transition metal complexes, [Zn(HBTC)(PYTPY)]n·n PYTPY(1), [Cu(HBTC)(PYTPY)]n·n PYTPY(2), [Co(HBTC)(PYTPY)]n·n DMF(3), [Mn(HBTC)(PYTPY)]n·n DMF(4), [Cd(HBTC)(PYTP...Six new transition metal complexes, [Zn(HBTC)(PYTPY)]n·n PYTPY(1), [Cu(HBTC)(PYTPY)]n·n PYTPY(2), [Co(HBTC)(PYTPY)]n·n DMF(3), [Mn(HBTC)(PYTPY)]n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]n·2nH2O(5), and [Co(HBTC)(PYTPY)(H2O)2](6),(H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4'-(4-pyridyl)-2,2':6',2''-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.展开更多
An effective synthetic route for preparation of 2-chloro-6-fluorobenzonitrile, 2-chloro-6-fluorobenzamide and 2-chloro-6-fluorobenzoic acid has been described. It includes diazotization, fluorination, ammoxidation and...An effective synthetic route for preparation of 2-chloro-6-fluorobenzonitrile, 2-chloro-6-fluorobenzamide and 2-chloro-6-fluorobenzoic acid has been described. It includes diazotization, fluorination, ammoxidation and hydrolysis reactions.展开更多
Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terp...Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.展开更多
Enhancing the separation efficiency of photogenerated carriers is propitious for the promotion of photocatalytic hydrogen production from formic acid decomposition.Herein,MoS2/Zn3In2S6(MoS2/ZIS6)composite photocatalys...Enhancing the separation efficiency of photogenerated carriers is propitious for the promotion of photocatalytic hydrogen production from formic acid decomposition.Herein,MoS2/Zn3In2S6(MoS2/ZIS6)composite photocatalysts containing varying mass percentages of MoS2 were obtained by a straightforward synthetic method.The results confirmed that MoS2,as a cocatalyst,markedly promoted the photogenerated charge separation efficiency and visible light-driven hydrogen production activity of ZIS6(λ>400 nm).Specifically,the as-prepared 0.5%MoS2/ZIS6 photocatalyst exhibited the highest photocatalytic hydrogen production rate(74.25μmol·h^-1),which was approximately 4.3 times higher than that of ZIS6(17.47μmol·h^-1).The excellent performance of the 0.5%MoS2/ZIS6 photocatalyst may be due to the fact that MoS2 has a low Fermi energy level and can thus enrich photogenerated electrons from ZIS6,and furthermore reduce H+derived from formic acid,to form hydrogen.The structure and morphology of the MoS2/ZIS6 photocatalysts and the reactive species were determined by X-ray diffraction,transmission electron microscopy,and field emission scanning electron microscopy,among others;a plausible mechanistic rationale is discussed based on the results.展开更多
Aim and Method Comparative molecular field analysis (CoMFA), a threedimensional quantitative structure-activity relationship (3D-QSAR) method was applied to a novelseries of C-3 substituted 4, 6-dichloioindole-2-carbo...Aim and Method Comparative molecular field analysis (CoMFA), a threedimensional quantitative structure-activity relationship (3D-QSAR) method was applied to a novelseries of C-3 substituted 4, 6-dichloioindole-2-carboxylic acids to study the relationship betweentheir structure and the affinity for the glycine site of the NMDA receptor. Result Hie coefficientsof cross-validation q^2 and non cross-validation r^2 for the model established by the study are0.744 and 0.993, respectively, the value of variance ratio F is 261.343, and standard error estimate(SE) is 0.039. Conclusion These values indicate that the CoMFA model may have a good prediction forthe activity of C-3 substituted 4, 6-dichloroin-dole-2-carboxylic acids. As a consequence, thepredicted activity values of new designed compounds supports our conclusion from the model.展开更多
Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2, Mr=1349.08, triclinic, space group P, a=13.00(3), b=19.743(2), c=12.754(3)A, α=97.94(1), β=106.24(2), γ=91.66(1)°, V=3177(1)~3, Z=2, Dc=1.41gcm^(-3), λ(MoKα)=0.71069, ...Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2, Mr=1349.08, triclinic, space group P, a=13.00(3), b=19.743(2), c=12.754(3)A, α=97.94(1), β=106.24(2), γ=91.66(1)°, V=3177(1)~3, Z=2, Dc=1.41gcm^(-3), λ(MoKα)=0.71069, μ=18.92 cm^(-1), F(ooo)=1384, T=295K, final R=0.073 for 6504 observed reflections with Ⅰ>36(Ⅰ). There are two nonidentical binuclear molecules with different bridging connection patterns in a cell. One has four bridging carboxyl groups bound two Y(Ⅲ) ions and another only has two. The Y-Y distance is 4.196 for the former and 5.302 for the latter respectively.展开更多
A new coordination polymer {[Cd(C_(21)H_(14)N_6)(C_8H_4O_4)]·H_2O}_n(1) was synthesized by an elaborate design via the reaction of 3-(2,6-di(pyrazin-2-yl)pyridin-4-yl)-1H-indole(bppi),1,4-benzene-...A new coordination polymer {[Cd(C_(21)H_(14)N_6)(C_8H_4O_4)]·H_2O}_n(1) was synthesized by an elaborate design via the reaction of 3-(2,6-di(pyrazin-2-yl)pyridin-4-yl)-1H-indole(bppi),1,4-benzene-dicarboxylic acid(H2bdc) and cadmium(Ⅱ) nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012(4),b = 31.881(6),c = 19.808(4) ?,V = 12638(4) ?~3,Z = 16,C_(29)H_(20)CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^(-3),μ = 0.735 mm^(-1),F(000) = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections(I 〉 2σ(I)). The Cd(Ⅱ) centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd(Ⅱ) cations into a one-dimensional(1D) coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178(1) ?. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional(3D) structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ?~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.展开更多
In an effort to investigate the use of short peptide chains as carriers of new anti-tumor agents, we synthesized four tripeptide-cytotoxic agent conjugates: DMQ-MA-Lys(DMQ-MA)-Phe -Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Ile-Arg-...In an effort to investigate the use of short peptide chains as carriers of new anti-tumor agents, we synthesized four tripeptide-cytotoxic agent conjugates: DMQ-MA-Lys(DMQ-MA)-Phe -Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Ile-Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Val-Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Lys(Cbz)-Arg-Ome. The cytotoxic agent conjugated to the N-terminal and the xi -amino group of Lysine of the tripeptide is 2,6-dimethoxyhydroquinone-3-mercaptoacetic acid (DMQ-MA). The tripeptides were synthesized by coupling protected amino acid residues according to Pfp/DCC methods (Pfp: pentafluorophenol, DCC:N,N'-dicyclohexyl-carbodiimide) in solution. Agarose gel electrophoresis showed that these compounds can cleave supercoiled DNA into open-circular form in drug concentration as low as 4-50 mu M without H2O2 and UV irradiation. Further studies on their cytotoxicity for these conjugates are ongoing.展开更多
Proceeding from natural amino acid L-asparagine and commercially available aldehydes a stereoselective synthesis was developed of (2S,4S)-2-alkyl(aryl)-3-(3-sulfanylpropanoyl)-6-oxohexahy- dropyrimidine-4-carboxylic a...Proceeding from natural amino acid L-asparagine and commercially available aldehydes a stereoselective synthesis was developed of (2S,4S)-2-alkyl(aryl)-3-(3-sulfanylpropanoyl)-6-oxohexahy- dropyrimidine-4-carboxylic acids, potential antihypertensive drugs, inhibitors of the angiotensin converting enzyme.展开更多
文摘Two unusual one-dimensional(1-D) compounds,viz.[Co(Medpq)(QUI)·H2O]2n· 2.4nH2O 1 and [Cd(Medpq)(QUI)·H2O]n·nH2O 2,were synthesized by the combination of two different metallic salts and organic ligands,namely 2,3-pyridinedicarboxylic acid(H2QUI) and 2-methyldipyrido[3,2-f:2',3'-h]quinoxaline(Medpq) ligand.The compounds were characterized by elemental analyses,TG,fluorescent emission and single-crystal X-ray diffraction analyses.
基金Supported by the National Natural Science Foundation of China(No.21576112)Natural Science Foundation of Jilin Province(20150623024TC-19,20170520147JH)the Science and Technology Development Plan of Siping City(2015049)
文摘Six new transition metal complexes, [Zn(HBTC)(PYTPY)]n·n PYTPY(1), [Cu(HBTC)(PYTPY)]n·n PYTPY(2), [Co(HBTC)(PYTPY)]n·n DMF(3), [Mn(HBTC)(PYTPY)]n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]n·2nH2O(5), and [Co(HBTC)(PYTPY)(H2O)2](6),(H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4'-(4-pyridyl)-2,2':6',2''-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.
文摘An effective synthetic route for preparation of 2-chloro-6-fluorobenzonitrile, 2-chloro-6-fluorobenzamide and 2-chloro-6-fluorobenzoic acid has been described. It includes diazotization, fluorination, ammoxidation and hydrolysis reactions.
基金Supported by the Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
文摘Enhancing the separation efficiency of photogenerated carriers is propitious for the promotion of photocatalytic hydrogen production from formic acid decomposition.Herein,MoS2/Zn3In2S6(MoS2/ZIS6)composite photocatalysts containing varying mass percentages of MoS2 were obtained by a straightforward synthetic method.The results confirmed that MoS2,as a cocatalyst,markedly promoted the photogenerated charge separation efficiency and visible light-driven hydrogen production activity of ZIS6(λ>400 nm).Specifically,the as-prepared 0.5%MoS2/ZIS6 photocatalyst exhibited the highest photocatalytic hydrogen production rate(74.25μmol·h^-1),which was approximately 4.3 times higher than that of ZIS6(17.47μmol·h^-1).The excellent performance of the 0.5%MoS2/ZIS6 photocatalyst may be due to the fact that MoS2 has a low Fermi energy level and can thus enrich photogenerated electrons from ZIS6,and furthermore reduce H+derived from formic acid,to form hydrogen.The structure and morphology of the MoS2/ZIS6 photocatalysts and the reactive species were determined by X-ray diffraction,transmission electron microscopy,and field emission scanning electron microscopy,among others;a plausible mechanistic rationale is discussed based on the results.
文摘Aim and Method Comparative molecular field analysis (CoMFA), a threedimensional quantitative structure-activity relationship (3D-QSAR) method was applied to a novelseries of C-3 substituted 4, 6-dichloioindole-2-carboxylic acids to study the relationship betweentheir structure and the affinity for the glycine site of the NMDA receptor. Result Hie coefficientsof cross-validation q^2 and non cross-validation r^2 for the model established by the study are0.744 and 0.993, respectively, the value of variance ratio F is 261.343, and standard error estimate(SE) is 0.039. Conclusion These values indicate that the CoMFA model may have a good prediction forthe activity of C-3 substituted 4, 6-dichloroin-dole-2-carboxylic acids. As a consequence, thepredicted activity values of new designed compounds supports our conclusion from the model.
文摘Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2, Mr=1349.08, triclinic, space group P, a=13.00(3), b=19.743(2), c=12.754(3)A, α=97.94(1), β=106.24(2), γ=91.66(1)°, V=3177(1)~3, Z=2, Dc=1.41gcm^(-3), λ(MoKα)=0.71069, μ=18.92 cm^(-1), F(ooo)=1384, T=295K, final R=0.073 for 6504 observed reflections with Ⅰ>36(Ⅰ). There are two nonidentical binuclear molecules with different bridging connection patterns in a cell. One has four bridging carboxyl groups bound two Y(Ⅲ) ions and another only has two. The Y-Y distance is 4.196 for the former and 5.302 for the latter respectively.
基金supported by the National Natural Science Foundation of China(Nos.21571118&21271121)
文摘A new coordination polymer {[Cd(C_(21)H_(14)N_6)(C_8H_4O_4)]·H_2O}_n(1) was synthesized by an elaborate design via the reaction of 3-(2,6-di(pyrazin-2-yl)pyridin-4-yl)-1H-indole(bppi),1,4-benzene-dicarboxylic acid(H2bdc) and cadmium(Ⅱ) nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012(4),b = 31.881(6),c = 19.808(4) ?,V = 12638(4) ?~3,Z = 16,C_(29)H_(20)CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^(-3),μ = 0.735 mm^(-1),F(000) = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections(I 〉 2σ(I)). The Cd(Ⅱ) centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd(Ⅱ) cations into a one-dimensional(1D) coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178(1) ?. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional(3D) structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ?~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.
文摘In an effort to investigate the use of short peptide chains as carriers of new anti-tumor agents, we synthesized four tripeptide-cytotoxic agent conjugates: DMQ-MA-Lys(DMQ-MA)-Phe -Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Ile-Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Val-Arg-Ome, DMQ-MA-Lys(DMQ-MA)-Lys(Cbz)-Arg-Ome. The cytotoxic agent conjugated to the N-terminal and the xi -amino group of Lysine of the tripeptide is 2,6-dimethoxyhydroquinone-3-mercaptoacetic acid (DMQ-MA). The tripeptides were synthesized by coupling protected amino acid residues according to Pfp/DCC methods (Pfp: pentafluorophenol, DCC:N,N'-dicyclohexyl-carbodiimide) in solution. Agarose gel electrophoresis showed that these compounds can cleave supercoiled DNA into open-circular form in drug concentration as low as 4-50 mu M without H2O2 and UV irradiation. Further studies on their cytotoxicity for these conjugates are ongoing.
文摘Proceeding from natural amino acid L-asparagine and commercially available aldehydes a stereoselective synthesis was developed of (2S,4S)-2-alkyl(aryl)-3-(3-sulfanylpropanoyl)-6-oxohexahy- dropyrimidine-4-carboxylic acids, potential antihypertensive drugs, inhibitors of the angiotensin converting enzyme.