DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA（SC） into nicked-circular DNA（NC）.The acti...DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA（SC） into nicked-circular DNA（NC）.The activity of these corroles follows an order of 4>3>2≈1>5.The photosensitized singlet oxygen（Φ;） quantum yield by these corroles also follows that same order,showing the photocleavage activity is related to the heavy atom effect of halogen atoms on corroles.展开更多
The reductive demetalation of manganese corroles was investigated in CH2Cl2/HCl （aqueous） solvent by using SnCl2 as reducing agent. It was found that the demetalation yields depend on the substituents of corrole mac...The reductive demetalation of manganese corroles was investigated in CH2Cl2/HCl （aqueous） solvent by using SnCl2 as reducing agent. It was found that the demetalation yields depend on the substituents of corrole macrocycle significantly. Electron- rich manganese corrole undergoes reductive demetalation more easily than electron-deficient ones. The isolated reductive demetalation yield of manganese 5,10,15-tris（phenyl）corrole in present system is moderate （46%）. As for electron-deficient Mn（Ⅲ） 5,10,15-tris（pentafluorophenyl）corrole, the acid-induced demetalation in HOAc-HESO4 （V/V = 3：1） is preferable with an isolated yield of 67%.展开更多
The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/P...The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G （TPC and TPP） or semiempirical PM3 （1, 2, 3, 4） optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 （helix parameters）, showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.展开更多
Seven electron-deficient A_2 B type H_3-triarylcorroles have been synthesized and characterized. The solvent dependence of the electronic absorption and magnetic circular dichroism（MCD） spectra and a series of TD-DF...Seven electron-deficient A_2 B type H_3-triarylcorroles have been synthesized and characterized. The solvent dependence of the electronic absorption and magnetic circular dichroism（MCD） spectra and a series of TD-DFT calculations have been used to analyze trends in the electronic structures. Significant differences are observed in the optical spectra when solvents of differing polarity are used,which can be assigned to the effect of NH-tautomerism.展开更多
The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density fun...The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density functional theory （DFT）. The results indicate that all these compounds have two conformers, one with C2 symmetry （denoted as Sl） is more stable than the other （denoted as $2, C1 symmetry） by 15.8-18.5 kJ/mol. The corrole macrocycles of these compounds show significant out-of-plane deformation. The enantiomerizations of the chiral S1 conformers were found to be a multi-step process with the $2 conformers as the intermediates. Electronic absorption spectra and electronic circular dichroism （ECD） of these compounds were calculated with time-dependent DFT. In comparison with H4Cor＋, the UV- Vis absorptions of meso-triaryl species are significantly red-shifted and their Q bands are enhanced due to the π-π conjugation between the aryl and corrole rings. Several neighboring electronic transitions were calculated with opposite signs in rotatory strengths, suggesting that ECD spectroscopy may be a useful tool in studying the electronic transitions of these compounds.展开更多
Corrole,a representative branch of porphyrin,has recently gained popularity.These molecules,viewed as ring‑contracted porphyrinoids containing direct pyrrole‑pyrrole linkages due to the absence of a meso‑carbon atom,e...Corrole,a representative branch of porphyrin,has recently gained popularity.These molecules,viewed as ring‑contracted porphyrinoids containing direct pyrrole‑pyrrole linkages due to the absence of a meso‑carbon atom,exhibit significant photo‑physicochemical properties that make them attractive for various applications.Herein,this review comprehensively discusses the remarkable properties of corrole complexes,as well as related structures and chelation properties.It further explores the biological applications of corrole complexes for in vivo imaging and anticancer therapy.Additionally,it addresses common research bottlenecks and challenges,providing insights into future potential applications in disease diagnosis and treatment.Generally,this review aims to illuminate the significance of corrole complexes and their promising biological applications.展开更多
Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction(OER)is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a...Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction(OER)is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin(Co-1-P) on carbon cloth(CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 m V. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.展开更多
Efficient and easily reproducible synthesis of sterically hindered multibrominated corroles is achieved via dipyrromethane-aldehyde condensation reaction in good yields.Boron trifluoride dietherate（BF_3-Et_2O） is fo...Efficient and easily reproducible synthesis of sterically hindered multibrominated corroles is achieved via dipyrromethane-aldehyde condensation reaction in good yields.Boron trifluoride dietherate（BF_3-Et_2O） is found to be the effective catalyst for cyclization reaction,giving corrole as the major product.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
基金supported by the National Natural Science Foundation of China(Nos.20771039,20625205, 20871122,20971046)National Key Foundation Research Development Project(973) Item of China(No. 2007CB815306)
文摘DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA（SC） into nicked-circular DNA（NC）.The activity of these corroles follows an order of 4>3>2≈1>5.The photosensitized singlet oxygen（Φ;） quantum yield by these corroles also follows that same order,showing the photocleavage activity is related to the heavy atom effect of halogen atoms on corroles.
基金National Natural Science Foundation of China(Nos.20771039,20572027),Research Grant Council of Hong Kong.
文摘The reductive demetalation of manganese corroles was investigated in CH2Cl2/HCl （aqueous） solvent by using SnCl2 as reducing agent. It was found that the demetalation yields depend on the substituents of corrole macrocycle significantly. Electron- rich manganese corrole undergoes reductive demetalation more easily than electron-deficient ones. The isolated reductive demetalation yield of manganese 5,10,15-tris（phenyl）corrole in present system is moderate （46%）. As for electron-deficient Mn（Ⅲ） 5,10,15-tris（pentafluorophenyl）corrole, the acid-induced demetalation in HOAc-HESO4 （V/V = 3：1） is preferable with an isolated yield of 67%.
基金Supported by the NNSFC (20476034), Research Grants Council of Hongkong and SRF for ROCS, State Education Ministry
文摘The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G （TPC and TPP） or semiempirical PM3 （1, 2, 3, 4） optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 （helix parameters）, showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.
基金financially supported by the National Natural Science Foundation of China(No.21171076)Natural Science Foundation of Jiangsu Province(No.BK20160499)to XL and WZ and an NRF of South Africa CSUR grant(uid:93627)to JM
文摘Seven electron-deficient A_2 B type H_3-triarylcorroles have been synthesized and characterized. The solvent dependence of the electronic absorption and magnetic circular dichroism（MCD） spectra and a series of TD-DFT calculations have been used to analyze trends in the electronic structures. Significant differences are observed in the optical spectra when solvents of differing polarity are used,which can be assigned to the effect of NH-tautomerism.
文摘The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density functional theory （DFT）. The results indicate that all these compounds have two conformers, one with C2 symmetry （denoted as Sl） is more stable than the other （denoted as $2, C1 symmetry） by 15.8-18.5 kJ/mol. The corrole macrocycles of these compounds show significant out-of-plane deformation. The enantiomerizations of the chiral S1 conformers were found to be a multi-step process with the $2 conformers as the intermediates. Electronic absorption spectra and electronic circular dichroism （ECD） of these compounds were calculated with time-dependent DFT. In comparison with H4Cor＋, the UV- Vis absorptions of meso-triaryl species are significantly red-shifted and their Q bands are enhanced due to the π-π conjugation between the aryl and corrole rings. Several neighboring electronic transitions were calculated with opposite signs in rotatory strengths, suggesting that ECD spectroscopy may be a useful tool in studying the electronic transitions of these compounds.
文摘Corrole,a representative branch of porphyrin,has recently gained popularity.These molecules,viewed as ring‑contracted porphyrinoids containing direct pyrrole‑pyrrole linkages due to the absence of a meso‑carbon atom,exhibit significant photo‑physicochemical properties that make them attractive for various applications.Herein,this review comprehensively discusses the remarkable properties of corrole complexes,as well as related structures and chelation properties.It further explores the biological applications of corrole complexes for in vivo imaging and anticancer therapy.Additionally,it addresses common research bottlenecks and challenges,providing insights into future potential applications in disease diagnosis and treatment.Generally,this review aims to illuminate the significance of corrole complexes and their promising biological applications.
基金support from National Natural Science Foundation of China (Nos. 21773146 and 21902099)China Postdoctoral Science Foundation (No. 2018M631120)+2 种基金Shaanxi Province Postdoctoral Science Foundation (No. 2018BSHEDZZ107)Fundamental Research Funds for the Central Universities (Nos. GK202103045 and GK202103050)Research funds of Shaanxi Normal University, and the open fund of State Key Laboratory of Structural Chemistry。
文摘Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction(OER)is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin(Co-1-P) on carbon cloth(CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 m V. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.
基金support from National Natural Science Foundation of China(Nos.21171057 and 21371059)
文摘Efficient and easily reproducible synthesis of sterically hindered multibrominated corroles is achieved via dipyrromethane-aldehyde condensation reaction in good yields.Boron trifluoride dietherate（BF_3-Et_2O） is found to be the effective catalyst for cyclization reaction,giving corrole as the major product.
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.
基金supported by the National Natural Science Foundation of China(20971046,21171057,61178037,11004256)Natural Science Foundation of Guangdong Province,China(10351064101000000)+1 种基金Open Fund of the State Key Laboratory of Optoelectronic Materials and Technologies(SunYat-Sen University),ChinaAppropriative Researching Fund for Professors and Doctors,Guangdong University of Education,China(10ARF14)~~
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.
