Strong magneto chiral effects in absorption of phenylalanine bridged chiral zinc bis porphyrin O,O C 2 Phe C 2 (TPP) 2Zn 2 were demonstrated through the comparison of natural circular dichroism and magnetic circular d...Strong magneto chiral effects in absorption of phenylalanine bridged chiral zinc bis porphyrin O,O C 2 Phe C 2 (TPP) 2Zn 2 were demonstrated through the comparison of natural circular dichroism and magnetic circular dichroism spectra of enantiomers. Magneto chiral circular dichroism spectra expressed as difference between the absorption coefficients of the left circularly polarized and right circularly polarized light are given. The observed intensive magneto chiral effect was suggested to be related with the chiral exciton coupling between two zinc porphyrin chromophores of the enantiomers. [WT5HZ]展开更多
10-(2-Hydroxylphenyl)-5,15-bis(pentafluorophenyl) corrole([STHZ]1) was found to have a remarkable photocytotoxicity on nasopharyngeal carcinoma(NPC) cell line(Chang C.K.et al.,Proc SPIE,2006,Vol.6139,p268).To explore ...10-(2-Hydroxylphenyl)-5,15-bis(pentafluorophenyl) corrole([STHZ]1) was found to have a remarkable photocytotoxicity on nasopharyngeal carcinoma(NPC) cell line(Chang C.K.et al.,Proc SPIE,2006,Vol.6139,p268).To explore the heavy-atom effect on corrole photosensitizer,an exact analogue of corole [STHZ]1[STBZ] with the modification of two heavy iodine atoms on its 10-phenyl group,10-(2-hydroxyl-3,5-diiodophenyl)-5,15-bis(pentafluorophenyl)corrole(2),were synthesized.Surprisingly,the photocytoxicity of corrole 2 on NPC cell dropped sharply as compared to corole 1.It exhibited no significant PDT cytotoxicity even if its concentration reached 2 μmol/L.This may be caused by the lowering of its singlet oxygen quantum yield in PDT, although the intersystem crossing of corrole 2 could be enhanced by iodine heavy-atom effect as indicated by the strong decrease of its fluorescence emission.展开更多
Several Mn(Ⅲ)10-(hydroxylphenyl)-5,15-bis(pentafluoro-phenyl)corroles with the hydroxyl at ortho-,meta-and para-position of 10-phenyl group were used as the catalysts in the oxidative cleavage of plasmid DNA in the p...Several Mn(Ⅲ)10-(hydroxylphenyl)-5,15-bis(pentafluoro-phenyl)corroles with the hydroxyl at ortho-,meta-and para-position of 10-phenyl group were used as the catalysts in the oxidative cleavage of plasmid DNA in the presence of H2O2.The catalytic system was composed of 10 μL 0.5 mg/mL pC DNA 6 in TE buffer solution(pH=8.0,4.0×10-2 mol/L Tris,1.0×10-3 mol/L EDTA),10 μL 1.0×10-5 mol/L Mn(Ⅲ)corrole in DMSO and 10 μL 0.3% H2O2.After 8 h incubation at room temperature,significant oxidative DNA damage could be observed with the ortho-hydroxyl Mn(Ⅲ)corrole showing a better activity as detected by agarose-gel electrophoresis.Plasmid DNA was completely damaged after 12 h incubation.These observations show Mn(Ⅲ)corrole can be used as an artificial model of nuclease.展开更多
Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-sco...Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.展开更多
Homogeneous solution of poor soluble aza bridged bis phenanthroline macrocyclic compound(H 2HAPP) was obtained by adding K 2CO 3 to its trifluoroacetate in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)= 1∶1] solution. C...Homogeneous solution of poor soluble aza bridged bis phenanthroline macrocyclic compound(H 2HAPP) was obtained by adding K 2CO 3 to its trifluoroacetate in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)= 1∶1] solution. Coordination reaction between H 2HAPP and metal ion Zn(Ⅱ) in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)=1∶1] solvent was studied by UV Vis spectroscopic method, which indicated 1∶1 complexing between H 2HAPP and Zn(II) ion occurred easily in such a homogeneous system at room temperature. And the formation of ZnHAPP complex was further confirmed by FAB MS and 1H NMR spectra.展开更多
文摘Strong magneto chiral effects in absorption of phenylalanine bridged chiral zinc bis porphyrin O,O C 2 Phe C 2 (TPP) 2Zn 2 were demonstrated through the comparison of natural circular dichroism and magnetic circular dichroism spectra of enantiomers. Magneto chiral circular dichroism spectra expressed as difference between the absorption coefficients of the left circularly polarized and right circularly polarized light are given. The observed intensive magneto chiral effect was suggested to be related with the chiral exciton coupling between two zinc porphyrin chromophores of the enantiomers. [WT5HZ]
基金supported by the National Natural Science Foundation of China(20971046,21171057,61178037,11004256)State Key Laboratory of Optoelectronic Materials and Technologies of Sun Yat-Sen University,China~~
文摘10-(2-Hydroxylphenyl)-5,15-bis(pentafluorophenyl) corrole([STHZ]1) was found to have a remarkable photocytotoxicity on nasopharyngeal carcinoma(NPC) cell line(Chang C.K.et al.,Proc SPIE,2006,Vol.6139,p268).To explore the heavy-atom effect on corrole photosensitizer,an exact analogue of corole [STHZ]1[STBZ] with the modification of two heavy iodine atoms on its 10-phenyl group,10-(2-hydroxyl-3,5-diiodophenyl)-5,15-bis(pentafluorophenyl)corrole(2),were synthesized.Surprisingly,the photocytoxicity of corrole 2 on NPC cell dropped sharply as compared to corole 1.It exhibited no significant PDT cytotoxicity even if its concentration reached 2 μmol/L.This may be caused by the lowering of its singlet oxygen quantum yield in PDT, although the intersystem crossing of corrole 2 could be enhanced by iodine heavy-atom effect as indicated by the strong decrease of its fluorescence emission.
文摘Several Mn(Ⅲ)10-(hydroxylphenyl)-5,15-bis(pentafluoro-phenyl)corroles with the hydroxyl at ortho-,meta-and para-position of 10-phenyl group were used as the catalysts in the oxidative cleavage of plasmid DNA in the presence of H2O2.The catalytic system was composed of 10 μL 0.5 mg/mL pC DNA 6 in TE buffer solution(pH=8.0,4.0×10-2 mol/L Tris,1.0×10-3 mol/L EDTA),10 μL 1.0×10-5 mol/L Mn(Ⅲ)corrole in DMSO and 10 μL 0.3% H2O2.After 8 h incubation at room temperature,significant oxidative DNA damage could be observed with the ortho-hydroxyl Mn(Ⅲ)corrole showing a better activity as detected by agarose-gel electrophoresis.Plasmid DNA was completely damaged after 12 h incubation.These observations show Mn(Ⅲ)corrole can be used as an artificial model of nuclease.
文摘Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.
文摘Homogeneous solution of poor soluble aza bridged bis phenanthroline macrocyclic compound(H 2HAPP) was obtained by adding K 2CO 3 to its trifluoroacetate in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)= 1∶1] solution. Coordination reaction between H 2HAPP and metal ion Zn(Ⅱ) in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)=1∶1] solvent was studied by UV Vis spectroscopic method, which indicated 1∶1 complexing between H 2HAPP and Zn(II) ion occurred easily in such a homogeneous system at room temperature. And the formation of ZnHAPP complex was further confirmed by FAB MS and 1H NMR spectra.
