Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental an...Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.展开更多
Organic matrices play an important role in biomineralization process. In order to explore the effect of both meso-tetrakis (4-hydroxylphenyl) porphyrin (THPP) and hydrogels on calcium carbonate mineralization,and cons...Organic matrices play an important role in biomineralization process. In order to explore the effect of both meso-tetrakis (4-hydroxylphenyl) porphyrin (THPP) and hydrogels on calcium carbonate mineralization,and consequently synthesize functional materials based on porphyrin and calcium carbonate with tunable shapes and optical properties,a new kind of biomimetic mineralization system which combined THPP with three biopolymer hydrogels (gelatin,agarose and calcium alginate gels) was designed and investigated. A carbonate diffusion method based on the generation of CO2 by slow decomposition of ammonium hydrogen carbonate was adopted for calcium carbonate crystallization. The results show that both gelatin and alginate hydrogels exhibit the ability of stabilizing vaterite,while agarose only induces the formation of calcite. With participation of THPP in the mineralization environments,calcite is favored in all these hydrogels,while the crystal morphologies are greatly different from each other. These results indicate the perspective of THPP in regulating calcium carbonate crystallization and also provide a new strategy for fabricating advanced functional materials with controlled morphology and tunable optical properties based on calcium carbonate and THPP.展开更多
We describe in this paper the fabrication of two- and one-dimensional nanostructures with organic molecular beam epitaxy （OMBE） principle based on controlled selfassembly by using adsorbate-substrate and intennolecu...We describe in this paper the fabrication of two- and one-dimensional nanostructures with organic molecular beam epitaxy （OMBE） principle based on controlled selfassembly by using adsorbate-substrate and intennolecular interactions that are important in molecular fabrication. Cu（100） single crystal was used as substrate in fabricating molecular nanostructures. Scanning tunneling microscopy （STM） experiments confirmed that Zn-tetra- [3,5-di-t-butylphenyl]porphyrin-molecules can be used to fabricate both monolayer and molecular wire on Cu（100） surface simultaneously, and the latter is arranged on the terrace edges. We herein briefly discuss the selectivity in terms of a mechanism in which the highest occupied and lowest unoccupied molecular orbitals （HOMO and LUMO） of the molecules interact with the surface.展开更多
Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petrole...Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petroleum ether and ethyl acetate. Results show that each atropisomer could be successfully synthesized by controlling the acylation temperature at 0 ℃. They were characterized by 1H NMR, HRMS, IR, UV-Vis and Langmuir-Blodgett（LB） film analyses. Although the results of HRMS, IR, UV-Vis analyses indicate there is no remarkable difference among the atropisomers, the results of the 1H NMR and the mean molecular areas obtained by LB film technique imply that the atropisomers are significantly discrepant. The former shows that the chemical shifts of the methyl and amide protons of each atropisomer are distinct, while the later presents that the different atropisomer molecules can occupy the different surface areas at the air/water interface.展开更多
文摘Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.
基金Project supported by the Fundamental Research Funds for the Central Universities of ChinaProject (50573019) supported by the National Natural Science Foundation of ChinaProject (SKL2009-5) supported by Open Research Program of State Key Lab of Silicon Material,Zhejiang University,China
文摘Organic matrices play an important role in biomineralization process. In order to explore the effect of both meso-tetrakis (4-hydroxylphenyl) porphyrin (THPP) and hydrogels on calcium carbonate mineralization,and consequently synthesize functional materials based on porphyrin and calcium carbonate with tunable shapes and optical properties,a new kind of biomimetic mineralization system which combined THPP with three biopolymer hydrogels (gelatin,agarose and calcium alginate gels) was designed and investigated. A carbonate diffusion method based on the generation of CO2 by slow decomposition of ammonium hydrogen carbonate was adopted for calcium carbonate crystallization. The results show that both gelatin and alginate hydrogels exhibit the ability of stabilizing vaterite,while agarose only induces the formation of calcite. With participation of THPP in the mineralization environments,calcite is favored in all these hydrogels,while the crystal morphologies are greatly different from each other. These results indicate the perspective of THPP in regulating calcium carbonate crystallization and also provide a new strategy for fabricating advanced functional materials with controlled morphology and tunable optical properties based on calcium carbonate and THPP.
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 (B09-B7060040) and the National Natural Science Foundation of China (20643001)
文摘We describe in this paper the fabrication of two- and one-dimensional nanostructures with organic molecular beam epitaxy （OMBE） principle based on controlled selfassembly by using adsorbate-substrate and intennolecular interactions that are important in molecular fabrication. Cu（100） single crystal was used as substrate in fabricating molecular nanostructures. Scanning tunneling microscopy （STM） experiments confirmed that Zn-tetra- [3,5-di-t-butylphenyl]porphyrin-molecules can be used to fabricate both monolayer and molecular wire on Cu（100） surface simultaneously, and the latter is arranged on the terrace edges. We herein briefly discuss the selectivity in terms of a mechanism in which the highest occupied and lowest unoccupied molecular orbitals （HOMO and LUMO） of the molecules interact with the surface.
基金Supported by the National Natural Science Foundation of China(No.20806025)
文摘Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petroleum ether and ethyl acetate. Results show that each atropisomer could be successfully synthesized by controlling the acylation temperature at 0 ℃. They were characterized by 1H NMR, HRMS, IR, UV-Vis and Langmuir-Blodgett（LB） film analyses. Although the results of HRMS, IR, UV-Vis analyses indicate there is no remarkable difference among the atropisomers, the results of the 1H NMR and the mean molecular areas obtained by LB film technique imply that the atropisomers are significantly discrepant. The former shows that the chemical shifts of the methyl and amide protons of each atropisomer are distinct, while the later presents that the different atropisomer molecules can occupy the different surface areas at the air/water interface.
