Scanning tunneling microscopy （STM） and scanning tunneling spectroscopy （STS） were performed on monolayer film of NiTPP supported on Au（111） under ultrahigh vacuum （UHV） conditions. The constant current STM im...Scanning tunneling microscopy （STM） and scanning tunneling spectroscopy （STS） were performed on monolayer film of NiTPP supported on Au（111） under ultrahigh vacuum （UHV） conditions. The constant current STM images show remarkable bias dependence. High resolution STM data clearly show the individual NiTPP molecules and allow easy differentiation between NiTPP and CoTPP reported before. Scanning tunneling spectra, as a function of molecule-tip separation, were acquired over a range of tip motion of 0.42 nm. Spectra do not show the variation in band splitting with tip distance. It appears for molecules such as NiTPP that the average potential at the molecule is essentially the same at the same metal substrate. For molecules of the height of NiTPP, the scanning tunneling spectra should give reliable occupied and unoccupied orbital energies over a wide range of tip-molecule distances.展开更多
A nest-like architectures(ZnO NAs)were prepared onto the conductive glass(ITO)by hydrothermal method.A metal-free porphyrin,tetraphenylporphyrin(H2TPP),was synthesized via Adler method.Zn ions with Zn-unsaturated coor...A nest-like architectures(ZnO NAs)were prepared onto the conductive glass(ITO)by hydrothermal method.A metal-free porphyrin,tetraphenylporphyrin(H2TPP),was synthesized via Adler method.Zn ions with Zn-unsaturated coordination bonds on the surface of ZnO NAs were used as a template,and also H2TPP was used as"molecular fragments".Zinc tetraphenylporphyrin(ZnTPP)molecules were obtained on the surface of ZnO NAs by in-situ method.ZnO NAs direct provides of zinc source makes ZnTPP stably coated on the surface of ZnO NAs nanosheet,formed a tight composite materials(ZnTPP/ZnO NAs).Due toZnTPP with four phenyls in meso position,the surface of ZnTPP/ZnO NAs was with hydrophobic property.In the photocatalytic experiment,the degradation selectivity for phenol(hydrophobicity)in the mixture of phenol and rhodamine B(hydrophily)was increased under visible irradiation.展开更多
Fifteen rare earth-tetraphenylporphyrin(RE-TPP)complexes were directly prepared by mixing equal molar concentrations of RE(ClO_4)_3 and H_2TPP in acetone media.The electrochemical behaviors of these com- plexes and th...Fifteen rare earth-tetraphenylporphyrin(RE-TPP)complexes were directly prepared by mixing equal molar concentrations of RE(ClO_4)_3 and H_2TPP in acetone media.The electrochemical behaviors of these com- plexes and the influence of dissolved oxygen were investigated by voltammetry.Althrough there are some differ- ence between the behaviors of light and heavy rare earth-porphyrins,the central RE ions of the all fifteen com- plexes were reduced from tervalent to divalent state,meanwhile the dissovled oxygen was reduced as superoxide ion O^-.which readily combined with the complex forming peroxide additive complex such as RE-TPP·O^(2-)_2.展开更多
A new dye-staining method for protein assay is described.The reaction between TPPS_4 and protein molecule causes a shift in the absorption of TPPS_4 from 435 nm to 488nm.The absorbance at 488 nm is proportional to the...A new dye-staining method for protein assay is described.The reaction between TPPS_4 and protein molecule causes a shift in the absorption of TPPS_4 from 435 nm to 488nm.The absorbance at 488 nm is proportional to the concentration of protein.The range of Beer's law was 1-5 ug/ml and the Sandell's sensitivity was 0.0087 ug/cm^2.展开更多
The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound ...The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound has been characterized by UV-vis., IR, MSI MS and 1H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative.The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenylporphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.展开更多
The geometries of tetraphenylporphyrin which is a kind of important porphyrin derivatives, and its N-protonated diacid are calculated with AM1 MO method under symmetry restriction. The configurational changes and thei...The geometries of tetraphenylporphyrin which is a kind of important porphyrin derivatives, and its N-protonated diacid are calculated with AM1 MO method under symmetry restriction. The configurational changes and their effects on molecular aggregation are discussed by means of structure analysis, charge population analysis and frontier orbital analysis.展开更多
The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2...The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.展开更多
The photochemical reaction of sulfur dioxide(SO2) with tetraphenylporphyrin magnesium(MgTPP) has been investigated in dichloromethane(CH2Cl2) solution at room temperature with illumination by visible light.Conventiona...The photochemical reaction of sulfur dioxide(SO2) with tetraphenylporphyrin magnesium(MgTPP) has been investigated in dichloromethane(CH2Cl2) solution at room temperature with illumination by visible light.Conventional fluorescence,UV-vis,and MS spectral analyses showed that under these conditions,SO2 was initially photochemically fixed by MgTPP to form a 1:1 molecular adduct.On continued irradiation and maintaining the flow of SO2,MS and XRD results showed that MgTPP is remarkably effective in the photochemical reduction of SO2 to sulfide(S2).The kinetics of the photochemical reaction of MgTPP with SO2 was studied in a SO2-saturated solution.Under irradiation,the reaction follows pseudo first order kinetics for MgTPP,having a half-life decreasing from 106 to 57 min as the illumination intensity is increased from 350 to 600 Lm.This investigation of the photochemical fixation and reduction of SO2 by MgTPP is of key interest in elucidating fundamental photochemical reaction mechanisms associated with porphyrins in the presence of SO2 ;furthermore,the analysis of the photochemical reaction may offer new opportunities for the fixation and reduction of SO2 to less harmful species.展开更多
2-(4-Pyridyl)imino nitroxide and tetraphenylporphyrin zinc(Ⅱ) formed a stable complex by noncovalent bonding in a nonpolar solution.Nicotine displaced 2-(4-pyridyl)imino nitroxide when it was added to a solution of 2...2-(4-Pyridyl)imino nitroxide and tetraphenylporphyrin zinc(Ⅱ) formed a stable complex by noncovalent bonding in a nonpolar solution.Nicotine displaced 2-(4-pyridyl)imino nitroxide when it was added to a solution of 2-(4-pyridyl)imino nitrox-ide-tetraphenylporphyrin zinc(Ⅱ).The fluorescence intensity of tetraphenylporphyrin zinc(Ⅱ) was altered by sequentially addition of 2-(4-pyridyl)imino nitroxide and nicotine.This was used to develop a new method for detection of nicotine.展开更多
基金This work was supported by the Excellent Scientist Program of South China University of Technology (324-D60090), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry and the National Natural Science Foundation of China (20643001).
文摘Scanning tunneling microscopy （STM） and scanning tunneling spectroscopy （STS） were performed on monolayer film of NiTPP supported on Au（111） under ultrahigh vacuum （UHV） conditions. The constant current STM images show remarkable bias dependence. High resolution STM data clearly show the individual NiTPP molecules and allow easy differentiation between NiTPP and CoTPP reported before. Scanning tunneling spectra, as a function of molecule-tip separation, were acquired over a range of tip motion of 0.42 nm. Spectra do not show the variation in band splitting with tip distance. It appears for molecules such as NiTPP that the average potential at the molecule is essentially the same at the same metal substrate. For molecules of the height of NiTPP, the scanning tunneling spectra should give reliable occupied and unoccupied orbital energies over a wide range of tip-molecule distances.
文摘A nest-like architectures(ZnO NAs)were prepared onto the conductive glass(ITO)by hydrothermal method.A metal-free porphyrin,tetraphenylporphyrin(H2TPP),was synthesized via Adler method.Zn ions with Zn-unsaturated coordination bonds on the surface of ZnO NAs were used as a template,and also H2TPP was used as"molecular fragments".Zinc tetraphenylporphyrin(ZnTPP)molecules were obtained on the surface of ZnO NAs by in-situ method.ZnO NAs direct provides of zinc source makes ZnTPP stably coated on the surface of ZnO NAs nanosheet,formed a tight composite materials(ZnTPP/ZnO NAs).Due toZnTPP with four phenyls in meso position,the surface of ZnTPP/ZnO NAs was with hydrophobic property.In the photocatalytic experiment,the degradation selectivity for phenol(hydrophobicity)in the mixture of phenol and rhodamine B(hydrophily)was increased under visible irradiation.
基金Project supported by National Natural Science Foundation of China
文摘Fifteen rare earth-tetraphenylporphyrin(RE-TPP)complexes were directly prepared by mixing equal molar concentrations of RE(ClO_4)_3 and H_2TPP in acetone media.The electrochemical behaviors of these com- plexes and the influence of dissolved oxygen were investigated by voltammetry.Althrough there are some differ- ence between the behaviors of light and heavy rare earth-porphyrins,the central RE ions of the all fifteen com- plexes were reduced from tervalent to divalent state,meanwhile the dissovled oxygen was reduced as superoxide ion O^-.which readily combined with the complex forming peroxide additive complex such as RE-TPP·O^(2-)_2.
文摘A new dye-staining method for protein assay is described.The reaction between TPPS_4 and protein molecule causes a shift in the absorption of TPPS_4 from 435 nm to 488nm.The absorbance at 488 nm is proportional to the concentration of protein.The range of Beer's law was 1-5 ug/ml and the Sandell's sensitivity was 0.0087 ug/cm^2.
文摘The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound has been characterized by UV-vis., IR, MSI MS and 1H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative.The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenylporphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.
基金ACKNOWLEDGMENTS This work was supported by the ＂Western Light＂ Visiting Scholar Plan, the Program for New Century Excellent Talents in University （No.NCET-12-1017）, the Program for Grassland Excellent Talents of Inner Mongolia Autonomous Region, the Inner Mengolia Science Technology Plan, the Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region （No.NJYT-12-B13）, the Natural Science Foundation of Inner Mongolia Autonomous Region （No.2011BS0601, China）, the Inner Mongolia Talented People Development Fund, and Yongfeng Boyuan Industry Co., Ltd. Jiangxi Province, China.
文摘铈(III ) tetraphenylporphyrin 硝酸盐 Ce (TPP ) NO3 被使用 mesotetraphenylporphyrin (TPP ) 和 Ce (NO3 ) 综合敭瑮污瀠潲散吗？
文摘The geometries of tetraphenylporphyrin which is a kind of important porphyrin derivatives, and its N-protonated diacid are calculated with AM1 MO method under symmetry restriction. The configurational changes and their effects on molecular aggregation are discussed by means of structure analysis, charge population analysis and frontier orbital analysis.
基金Project supported by the National Natural Science Foundation of China （No. 29872033）.
文摘The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.
基金supported by the Foundation of Inner Mongolia Autonomous Region’s Educational Commission(NJZZ11068)the School Scientific Research Fund (ZD201004,Inner Mongolia University of Technology,China)Yongfeng Boyuan Industry Co.,Ltd. (Jiangxi Province,China)
文摘The photochemical reaction of sulfur dioxide(SO2) with tetraphenylporphyrin magnesium(MgTPP) has been investigated in dichloromethane(CH2Cl2) solution at room temperature with illumination by visible light.Conventional fluorescence,UV-vis,and MS spectral analyses showed that under these conditions,SO2 was initially photochemically fixed by MgTPP to form a 1:1 molecular adduct.On continued irradiation and maintaining the flow of SO2,MS and XRD results showed that MgTPP is remarkably effective in the photochemical reduction of SO2 to sulfide(S2).The kinetics of the photochemical reaction of MgTPP with SO2 was studied in a SO2-saturated solution.Under irradiation,the reaction follows pseudo first order kinetics for MgTPP,having a half-life decreasing from 106 to 57 min as the illumination intensity is increased from 350 to 600 Lm.This investigation of the photochemical fixation and reduction of SO2 by MgTPP is of key interest in elucidating fundamental photochemical reaction mechanisms associated with porphyrins in the presence of SO2 ;furthermore,the analysis of the photochemical reaction may offer new opportunities for the fixation and reduction of SO2 to less harmful species.
基金supported by the National Natural Science Foundation of China (20802090)
文摘2-(4-Pyridyl)imino nitroxide and tetraphenylporphyrin zinc(Ⅱ) formed a stable complex by noncovalent bonding in a nonpolar solution.Nicotine displaced 2-(4-pyridyl)imino nitroxide when it was added to a solution of 2-(4-pyridyl)imino nitrox-ide-tetraphenylporphyrin zinc(Ⅱ).The fluorescence intensity of tetraphenylporphyrin zinc(Ⅱ) was altered by sequentially addition of 2-(4-pyridyl)imino nitroxide and nicotine.This was used to develop a new method for detection of nicotine.
