[Ru (bpy)_3]^(2+)/MCM-41 composite material obtained by loading tris(2, 2' - bipyridine)ruthenium(Ⅱ) ([Ru (bpy)_3]^(2+) ) in siliceous mesoporous MCM-41 was characterized by X-ray powder diffraction, UV-Vis absor...[Ru (bpy)_3]^(2+)/MCM-41 composite material obtained by loading tris(2, 2' - bipyridine)ruthenium(Ⅱ) ([Ru (bpy)_3]^(2+) ) in siliceous mesoporous MCM-41 was characterized by X-ray powder diffraction, UV-Vis absorption and emission spectroscopies. The absorption spectrum of [Ru(bpy)_3]^(2+) /MCM-41 is similar to that of [Ru (bpy)_3]^(2+) aqueous solution, whereas its emission spectrum exhibits hypsochromic shift compared to the solution spectrum. On the other hand, the peak position of the emission spectrum of [Ru(bpy)_3]^(2+)/MCM-41 shifts towards longer wavelength when the loading amount increases.展开更多
Tris （2, 2′-bipyridine） ruthenium （Ⅱ） （Ru（bpy）3^2＋） dichloride was successfully immobilized into the galleria of layered gamma zirconium phosphate （γ-ZrP） preintercalated by butyl amine（BA）. The compou...Tris （2, 2′-bipyridine） ruthenium （Ⅱ） （Ru（bpy）3^2＋） dichloride was successfully immobilized into the galleria of layered gamma zirconium phosphate （γ-ZrP） preintercalated by butyl amine（BA）. The compounds showed extended luminescence lifetime of about four times of unimmobilized metal complex.展开更多
A polymer, [NiL（bipy）·2H2O]n（1, bipy = 4,4ˊ-bipyridine）, has been acquired by the reaction of Ni（OAc）2·4H2O with N,Nˊ-bis（2-hydroxyl-5-fluorobenzyl）-2-hydrxylpropane dii- mine in the presence of 4,...A polymer, [NiL（bipy）·2H2O]n（1, bipy = 4,4ˊ-bipyridine）, has been acquired by the reaction of Ni（OAc）2·4H2O with N,Nˊ-bis（2-hydroxyl-5-fluorobenzyl）-2-hydrxylpropane dii- mine in the presence of 4,4ˊ-bipyridine. X-ray crystallographic analysis shows that it is comprised of a mononuclear Ni（Ⅱ） complex [NiL] linked by 4,4ˊ-bipyridine. Its crystal crystallizes in the orthorhombic system, space group C2/c with a = 22.595（3）, b = 18.395（2）, c = 15.434（2） , V = 6155（1）3, Dc = 1.259 g/cm-3, Z = 8, Mr = 583.23, F（000） = 2416.0, μ（MoKa） = 0.681 mm-1, S = 1.049, R = 0.0512 and wR = 0.1108 for 6032 observed reflections（I 〉 2σ（I））. There are water hexamers in the complex. A weak overall ferromagnetic behavior has been evaluated by Curie-Weiss rule and by the formula of alternating ferro-ferromagnetic coupling in one-dimensional Ni（Ⅱ） chain, which gives g = 2.005（1） and J1 = 0.31（3） cm-1.展开更多
A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） an...A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.展开更多
The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) 2+ 3 is used to determine 1.0×10 -8 \|1.0×10 -5 mol/L thiourea. The ...The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) 2+ 3 is used to determine 1.0×10 -8 \|1.0×10 -5 mol/L thiourea. The limit of detection is 9.8×10 -9 mol/L and the relative standard deviation is 1.1% for a 1.0×10 -5 mol/L thiourea solution ( n =10). The method was applied satisfactorily to the determination of thiourea.展开更多
13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a...13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a direction consistent with that expected from the electron withdrawing ability of the substituent.展开更多
The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structu...The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2 units. The copper atom,located on the crystallographic twofold axis,is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions,and two dihydrogen phosphate oxygen atoms at the axial positions,forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca . 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm,respectively. The two-dimensional networks are stacked parallelly on each other along c -axis to give an extended three-dimensional channel network with an interlayer distance of ca . 0.5030 nm. Crystal data: triclinic,space group P -_1,a =1.0253(2) nm,b =1.4501(3) nm,c =0.79715(16) nm, α =97.91(3)°,β = 90.99(3)° ,γ =85.54(3)°,V =1.1703(4) nm 3,Z =2,R =0.0892,wR =0.2451.展开更多
A new ruthenium polypyridine complex, [Ru(phen) 2(pMIP)] 2+(phen=1,10-phenanthroline, pMIP=2-(4-methylphenyl)imidazo phenanthroline), was synthesized and characterized by elementary analysis, MS and 1H NMR. Spectrosco...A new ruthenium polypyridine complex, [Ru(phen) 2(pMIP)] 2+(phen=1,10-phenanthroline, pMIP=2-(4-methylphenyl)imidazo phenanthroline), was synthesized and characterized by elementary analysis, MS and 1H NMR. Spectroscopic methods have been carried out on the interaction mechanism of the Ru (Ⅱ) complex with yeast tRNA systematically. The experimental results indicate that the complex binds to yeast tRNA with an intercalative mode possibly, and interacts with yeast tRNA enantioselectively. The experimental results also suggest that spectroscopic method is effective on studying the interaction mechanism of Ru (Ⅱ) complexes with RNA. Information obtained from the study is potentially useful in the design of new RNA-targeting drugs.展开更多
Two enantiomerically pure polypyridyl ruthenium(Ⅱ) complexes Δ- and Λ-[Ru(bpy) 2HPIP](PF 6) 2{HPIP=2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline} were synthesized and characterized. DNA-binding studies indi...Two enantiomerically pure polypyridyl ruthenium(Ⅱ) complexes Δ- and Λ-[Ru(bpy) 2HPIP](PF 6) 2{HPIP=2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline} were synthesized and characterized. DNA-binding studies indicated that both enantiomers bound to calf thymus DNA by intercalation, the Δ- enantiomer exhibited a stronger binding affinity than the Λ- enantiomer. Upon irradiation at 302 nm, both enantiomers were found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form Ⅰ to the open circular form Ⅱ, but the Δ-enantiomer exhibited a higher cleaving efficiency for DNA due to the different binding affinities to DNA. The cleaving mechanisms for Δ- and Λ-[Ru(bpy) 2HPIP] 2+ were identical, the hydroxyl radical(OH ·) was likely to be the reactive specie responsible for the cleavage of plasmid pBR 322, and the photoreduction of Ru(Ⅱ) complex with concomitant hydroxide oxidation was the important step in the DNA cleavage reaction.展开更多
基金the National Natural Science Foundation of China!(No. 29771013 and No. 29725101 )
文摘[Ru (bpy)_3]^(2+)/MCM-41 composite material obtained by loading tris(2, 2' - bipyridine)ruthenium(Ⅱ) ([Ru (bpy)_3]^(2+) ) in siliceous mesoporous MCM-41 was characterized by X-ray powder diffraction, UV-Vis absorption and emission spectroscopies. The absorption spectrum of [Ru(bpy)_3]^(2+) /MCM-41 is similar to that of [Ru (bpy)_3]^(2+) aqueous solution, whereas its emission spectrum exhibits hypsochromic shift compared to the solution spectrum. On the other hand, the peak position of the emission spectrum of [Ru(bpy)_3]^(2+)/MCM-41 shifts towards longer wavelength when the loading amount increases.
基金This work was supported by the National Science Foundation of China(Nos.20475004,and 20271004).
文摘Tris （2, 2′-bipyridine） ruthenium （Ⅱ） （Ru（bpy）3^2＋） dichloride was successfully immobilized into the galleria of layered gamma zirconium phosphate （γ-ZrP） preintercalated by butyl amine（BA）. The compounds showed extended luminescence lifetime of about four times of unimmobilized metal complex.
基金the financial support from the National Natural Science Foundation of China(21171135)Hubei Provincial Science & Technology Department(2011BFA020)Hubei Independent Innovation Base(HBIR07)
文摘A polymer, [NiL（bipy）·2H2O]n（1, bipy = 4,4ˊ-bipyridine）, has been acquired by the reaction of Ni（OAc）2·4H2O with N,Nˊ-bis（2-hydroxyl-5-fluorobenzyl）-2-hydrxylpropane dii- mine in the presence of 4,4ˊ-bipyridine. X-ray crystallographic analysis shows that it is comprised of a mononuclear Ni（Ⅱ） complex [NiL] linked by 4,4ˊ-bipyridine. Its crystal crystallizes in the orthorhombic system, space group C2/c with a = 22.595（3）, b = 18.395（2）, c = 15.434（2） , V = 6155（1）3, Dc = 1.259 g/cm-3, Z = 8, Mr = 583.23, F（000） = 2416.0, μ（MoKa） = 0.681 mm-1, S = 1.049, R = 0.0512 and wR = 0.1108 for 6032 observed reflections（I 〉 2σ（I））. There are water hexamers in the complex. A weak overall ferromagnetic behavior has been evaluated by Curie-Weiss rule and by the formula of alternating ferro-ferromagnetic coupling in one-dimensional Ni（Ⅱ） chain, which gives g = 2.005（1） and J1 = 0.31（3） cm-1.
基金Supported by the Natural Science Foundation of Zhejiang Province (Y407301)
文摘A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.
文摘The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) 2+ 3 is used to determine 1.0×10 -8 \|1.0×10 -5 mol/L thiourea. The limit of detection is 9.8×10 -9 mol/L and the relative standard deviation is 1.1% for a 1.0×10 -5 mol/L thiourea solution ( n =10). The method was applied satisfactorily to the determination of thiourea.
文摘13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a direction consistent with that expected from the electron withdrawing ability of the substituent.
文摘The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2 units. The copper atom,located on the crystallographic twofold axis,is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions,and two dihydrogen phosphate oxygen atoms at the axial positions,forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca . 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm,respectively. The two-dimensional networks are stacked parallelly on each other along c -axis to give an extended three-dimensional channel network with an interlayer distance of ca . 0.5030 nm. Crystal data: triclinic,space group P -_1,a =1.0253(2) nm,b =1.4501(3) nm,c =0.79715(16) nm, α =97.91(3)°,β = 90.99(3)° ,γ =85.54(3)°,V =1.1703(4) nm 3,Z =2,R =0.0892,wR =0.2451.
文摘A new ruthenium polypyridine complex, [Ru(phen) 2(pMIP)] 2+(phen=1,10-phenanthroline, pMIP=2-(4-methylphenyl)imidazo phenanthroline), was synthesized and characterized by elementary analysis, MS and 1H NMR. Spectroscopic methods have been carried out on the interaction mechanism of the Ru (Ⅱ) complex with yeast tRNA systematically. The experimental results indicate that the complex binds to yeast tRNA with an intercalative mode possibly, and interacts with yeast tRNA enantioselectively. The experimental results also suggest that spectroscopic method is effective on studying the interaction mechanism of Ru (Ⅱ) complexes with RNA. Information obtained from the study is potentially useful in the design of new RNA-targeting drugs.
文摘Two enantiomerically pure polypyridyl ruthenium(Ⅱ) complexes Δ- and Λ-[Ru(bpy) 2HPIP](PF 6) 2{HPIP=2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline} were synthesized and characterized. DNA-binding studies indicated that both enantiomers bound to calf thymus DNA by intercalation, the Δ- enantiomer exhibited a stronger binding affinity than the Λ- enantiomer. Upon irradiation at 302 nm, both enantiomers were found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form Ⅰ to the open circular form Ⅱ, but the Δ-enantiomer exhibited a higher cleaving efficiency for DNA due to the different binding affinities to DNA. The cleaving mechanisms for Δ- and Λ-[Ru(bpy) 2HPIP] 2+ were identical, the hydroxyl radical(OH ·) was likely to be the reactive specie responsible for the cleavage of plasmid pBR 322, and the photoreduction of Ru(Ⅱ) complex with concomitant hydroxide oxidation was the important step in the DNA cleavage reaction.
