The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensio...The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.展开更多
Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been c...Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.展开更多
Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen...Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen)Cl 2 and BzPheH 2 in water at pH～9, with their structures determined by X ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe= N benzoyl β phenylalaninate dianion). In the complex \[Pd(phen)(BzPhe N,O)\]·4H 2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. \[Pd(bipy)(BzPhe N,O)\] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.展开更多
The interaction between palladium(II)-chlorpromazine hydrochloride and sodium tungstate was investigated by ultravioletvisible absorption,resonance Rayleigh scattering(RRS),second-order scattering(SOS)and frequency do...The interaction between palladium(II)-chlorpromazine hydrochloride and sodium tungstate was investigated by ultravioletvisible absorption,resonance Rayleigh scattering(RRS),second-order scattering(SOS)and frequency doubling scattering (FDS)spectroscopy.In pH 5.3 Britton-Robinson(BR)buffer medium,chlorpromazine hydrochloride(CPZ)reacted with Pd(II) to form 2:1 cationic chelate,which further reacted with Na2WO4 to form a 1:1 ternary ion-association complex ([Pd(CPZ)2]·WO4).As a result,the signal intensities of RRS,SOS and FDS were enhanced greatly,and the enhancements of scattering were proportional to the CPZ concentration in a certain range.Their maximum wavelengths were located at 310 nm, 570 nm and 391 nm,respectively and the detection limits(3)were 1.6 ng/mL(RRS method),3.2 ng/mL(SOS method)and 5.6 ng/mL(FDS method).The optimum reaction conditions,the influences of coexisting substances and analytical application were mainly investigated by RRS method due to its highest sensitivity.A highly sensitive,simple,rapid and new method had been proposed to determine CPZ in the pharmaceutical form and residue of CPZ in pork.In addition,the Gibbs free energy change(△Gf)of ion-association reaction was computed by using B3LYP/3-21g*/LanL2dz method.The formation of ion-association and the reasons for the enhancement of RRS were also discussed.展开更多
The complexes [Pd(phen)(aa)]Cl.3H2O, where phen is 1,10-phenanthroline and aa is the anion of glycine (gly), .DL-alanine (ala), DL-serine (ser) or DL-asparagine (asn), were synthesized and characterized by spectroscop...The complexes [Pd(phen)(aa)]Cl.3H2O, where phen is 1,10-phenanthroline and aa is the anion of glycine (gly), .DL-alanine (ala), DL-serine (ser) or DL-asparagine (asn), were synthesized and characterized by spectroscopies. The NMR signals were assigned completely on the basis of the double irradiation, 1H-1H COSY and 1H-13C COSY techniques. In the 1H NMR spectra of phen in the complexes, the signals of 2-H and 9-H show upfield shifts 0.8-1 ppm, while the signals of 4-H and 3-H show downfield shifts or almost no shift, as compared to the free phen ligand, and the signal of 4-H appears in the lowest field. The signals of ring B which is trans to the carboxyl group show significant upfield shifts as compared to those of ring A. The probable structures were described on the basis of a metal-non-bonded hydrogen interaction, trons effect and ligand-ligand interaction. There may exist three conformation isomers in the [Pd(phen)(asn)]Cl.3H2O complex at room temperature. The preferred conformation isomer is about 75% in terms of the relative peak areas in the a-CH part of the spectra.展开更多
A novel palladium（II） complex [（TMEDA）Pd（anca）2].2DMSO （1, TMEDA = N,N,N＇,N＇-tetramethylethylethylenediamine, anca = anthracene-9-carboxylic acid） was synthesized and characterized by single-crystal X-ray di...A novel palladium（II） complex [（TMEDA）Pd（anca）2].2DMSO （1, TMEDA = N,N,N＇,N＇-tetramethylethylethylenediamine, anca = anthracene-9-carboxylic acid） was synthesized and characterized by single-crystal X-ray diffraction, 1H NMR, UV-Vis and fluorescence spectroscopy. The cell belongs to orthorhombic Aba2 space group with a = 19.698（7）, b = 21.045（7） c = 9.062（3） A, Z = 4, V= 3757（2） A3, C40H46N206PdS2, Mr = 821.31, D, = 1.452 g/cm3, F（000） = 1704, the final R = 0.0272, wR = 0.0667 and GOOF = 0.999. Complex 1 exhibits an interesting distorted clip-shaped molecular configuration which is stabilized by intramolecular C-H...O hydrogen bonds. The cells are packed into a 3D supramolecular structure based on the intermolecular C-H...zr interactions which further construct the tubular channels serving as guest molecular channels to include the DMSO solvent molecules inside. Furthermore, the spectroscopic properties of 1 were also investigated.展开更多
Nonplatinummetal complexes of[Pd(L^(1))Cl_(2)](C1),[Rh(L^(1))Cl_(3)(DMSO)](C2),[Pd(L^(2))Cl_(2)](C3),and[Rh(L^(3))Cl_(3)(DMSO)](C4)with isoquinoline derivatives have been prepared and characterized.C1-C4 exhibited hig...Nonplatinummetal complexes of[Pd(L^(1))Cl_(2)](C1),[Rh(L^(1))Cl_(3)(DMSO)](C2),[Pd(L^(2))Cl_(2)](C3),and[Rh(L^(3))Cl_(3)(DMSO)](C4)with isoquinoline derivatives have been prepared and characterized.C1-C4 exhibited higher in vitro anticancer activity and lower toxicity than the corresponding ligands and cisplatin against HepG2 cells.The mechanistic studies revealed that C1 arrested the cell cycle at S-phase by regulation of cyclin and cyclin-dependent kinases.C1 was accumulated in mitochondria,which increased the generation of reactive oxygen species(ROS)and endoplasmic reticulum(ER)-stress response through mitochondrial dysfunction.Moreover,C1 stimulated Ca^(2+)release,activated the caspase cascade,and triggered mitochondria-mediated apoptosis.The in vivo studies of C1 demonstrated higher safety than cisplatin and effective tumor growth inhibition.C1 is a potential anticancer drug candidate.展开更多
基金supported by the National Natural Science Foundation of China and the Doctoral Special Grant from the State Education Commission of China.
文摘The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.
基金Project supported by the Natural Science Foundation of Zhejiang ProvinceChina
文摘Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.
基金theNaturalScienceFoundationofZhejiangProvince (No .2 980 6 8)
文摘Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen)Cl 2 and BzPheH 2 in water at pH～9, with their structures determined by X ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe= N benzoyl β phenylalaninate dianion). In the complex \[Pd(phen)(BzPhe N,O)\]·4H 2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. \[Pd(bipy)(BzPhe N,O)\] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.
基金financial support for this study by the National Natural Science Foundation of China (20875078) Chongqing Municipal Key Laboratory on Luminescence and Real-Time Analysis (CSTC 2006CA8006)
文摘The interaction between palladium(II)-chlorpromazine hydrochloride and sodium tungstate was investigated by ultravioletvisible absorption,resonance Rayleigh scattering(RRS),second-order scattering(SOS)and frequency doubling scattering (FDS)spectroscopy.In pH 5.3 Britton-Robinson(BR)buffer medium,chlorpromazine hydrochloride(CPZ)reacted with Pd(II) to form 2:1 cationic chelate,which further reacted with Na2WO4 to form a 1:1 ternary ion-association complex ([Pd(CPZ)2]·WO4).As a result,the signal intensities of RRS,SOS and FDS were enhanced greatly,and the enhancements of scattering were proportional to the CPZ concentration in a certain range.Their maximum wavelengths were located at 310 nm, 570 nm and 391 nm,respectively and the detection limits(3)were 1.6 ng/mL(RRS method),3.2 ng/mL(SOS method)and 5.6 ng/mL(FDS method).The optimum reaction conditions,the influences of coexisting substances and analytical application were mainly investigated by RRS method due to its highest sensitivity.A highly sensitive,simple,rapid and new method had been proposed to determine CPZ in the pharmaceutical form and residue of CPZ in pork.In addition,the Gibbs free energy change(△Gf)of ion-association reaction was computed by using B3LYP/3-21g*/LanL2dz method.The formation of ion-association and the reasons for the enhancement of RRS were also discussed.
基金Project supported by the National Natural Science Foundation of China,Doctoral Foundation ofInstitution of High Education and Research Foundation of the State Key Laboratory of Coordination Chemistry,Nanjing University.
文摘The complexes [Pd(phen)(aa)]Cl.3H2O, where phen is 1,10-phenanthroline and aa is the anion of glycine (gly), .DL-alanine (ala), DL-serine (ser) or DL-asparagine (asn), were synthesized and characterized by spectroscopies. The NMR signals were assigned completely on the basis of the double irradiation, 1H-1H COSY and 1H-13C COSY techniques. In the 1H NMR spectra of phen in the complexes, the signals of 2-H and 9-H show upfield shifts 0.8-1 ppm, while the signals of 4-H and 3-H show downfield shifts or almost no shift, as compared to the free phen ligand, and the signal of 4-H appears in the lowest field. The signals of ring B which is trans to the carboxyl group show significant upfield shifts as compared to those of ring A. The probable structures were described on the basis of a metal-non-bonded hydrogen interaction, trons effect and ligand-ligand interaction. There may exist three conformation isomers in the [Pd(phen)(asn)]Cl.3H2O complex at room temperature. The preferred conformation isomer is about 75% in terms of the relative peak areas in the a-CH part of the spectra.
基金supported by the National Natural Science Foundation of China(No.91127039,51073171)Natural Science Foundation of Beijing(No.2112018)
文摘A novel palladium（II） complex [（TMEDA）Pd（anca）2].2DMSO （1, TMEDA = N,N,N＇,N＇-tetramethylethylethylenediamine, anca = anthracene-9-carboxylic acid） was synthesized and characterized by single-crystal X-ray diffraction, 1H NMR, UV-Vis and fluorescence spectroscopy. The cell belongs to orthorhombic Aba2 space group with a = 19.698（7）, b = 21.045（7） c = 9.062（3） A, Z = 4, V= 3757（2） A3, C40H46N206PdS2, Mr = 821.31, D, = 1.452 g/cm3, F（000） = 1704, the final R = 0.0272, wR = 0.0667 and GOOF = 0.999. Complex 1 exhibits an interesting distorted clip-shaped molecular configuration which is stabilized by intramolecular C-H...O hydrogen bonds. The cells are packed into a 3D supramolecular structure based on the intermolecular C-H...zr interactions which further construct the tubular channels serving as guest molecular channels to include the DMSO solvent molecules inside. Furthermore, the spectroscopic properties of 1 were also investigated.
基金This work was supported by the National Natural Science Foundation of China(grant no.21431001)IRT_16R15,and Natural Science Foundation of Guangxi Province of China(grant nos.2016GXNSFGA380005 and AD17129007)as well as the“BAGUI Scholar”program of Guangxi Province of China.
文摘Nonplatinummetal complexes of[Pd(L^(1))Cl_(2)](C1),[Rh(L^(1))Cl_(3)(DMSO)](C2),[Pd(L^(2))Cl_(2)](C3),and[Rh(L^(3))Cl_(3)(DMSO)](C4)with isoquinoline derivatives have been prepared and characterized.C1-C4 exhibited higher in vitro anticancer activity and lower toxicity than the corresponding ligands and cisplatin against HepG2 cells.The mechanistic studies revealed that C1 arrested the cell cycle at S-phase by regulation of cyclin and cyclin-dependent kinases.C1 was accumulated in mitochondria,which increased the generation of reactive oxygen species(ROS)and endoplasmic reticulum(ER)-stress response through mitochondrial dysfunction.Moreover,C1 stimulated Ca^(2+)release,activated the caspase cascade,and triggered mitochondria-mediated apoptosis.The in vivo studies of C1 demonstrated higher safety than cisplatin and effective tumor growth inhibition.C1 is a potential anticancer drug candidate.
