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前言卟啉在生物化学、分析化学、药物化学等领域有着广泛研究和重要应用[1~3]。近年来虽然对卟啉类化合物的研究报道很多[4~6],但对卟啉在酸性介质中的研究很少。较早期的研究工作认为卟啉类化合物在酸性介质中仅以其二酸形式存在[7]。本文实验结果显示me... 相似文献
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The enthalpies of dissolution, transfer, and axial coordination for the Cd(II), Co(II), Mn(III), Fe(III), and Cr(III) complexes of tetraphenylporphine, H2(TPP), in nonpolar (C6H6, CCl4) and electron-donating solvents (DMF, DMSO, Py,c-C5H10NH) have been determined calorimetrically at 298.15 K. On the basis of thermogravimetrical data for the corresponding crystallosolvates the composition, thermal stability, and energy of intermolecular interaction of the metal-porphine complexes with pyridine have been calculated. Complexing in noncoordinating solvents brings about no radical change in the physicochemical characteristics of axial coordination which depend critically on the electron structure of the complex-forming metal.Translated fromfzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 846–850, May, 1993. 相似文献
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H_2TPP与AgNO_3在乙醇中的光反应 总被引:1,自引:0,他引:1
用紫外可见吸收光谱研究了 5,10 ,15,2 0 -四苯基卟啉 (H2 TPP)的乙醇溶液与AgNO3的乙醇溶液混合后 ,在光照条件下的化学反应。谱图显示H2 TPP发生络合反应 ,生成其二价银络合物Ag(Ⅱ )TPP。银胶能加快该反应的速度。 相似文献
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Sandeep Mishra Sarvpreet Kaur S. K. Tripathi C. G. Mahajan G. S. S. Saini 《Journal of Chemical Sciences》2006,118(4):361-369
We present here infrared absorption spectra of dithia tetraphenylporphine and its cation in the 450–1600 and 2900–3400 cm−1 regions. Most of the allowed IR bands are observed in pairs due to overallD
2h
point group symmetry of the molecule. The observed bands have been assigned to the porphyrin skeleton and phenyl ring modes.
Some weak bands, which are forbidden underD
2h
, also appear in the spectra due to the distortion of the molecule from planarity-caused by the out-of-plane positioned N
and S atoms. Increased intensity of some phenyl ring bands compared to free-base tetraphenylporphine is explained on the basis
of rotation of phenyl rings towards the mean molecular plane. Contrary to the point group symmetry of cation of dithia tetraphenylporphine,
certain bands are observed to be degenerate due to identical bonding arrangements in pyrrole rings of the cation 相似文献
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研究了四苯基卟啉类光敏剂在醇-酸体系中的光谱性质,以及在此体系中浓度、酸度、表面活性剂等因素对其光谱性质的影响,首次发现在醇-酸体系中四苯基卟啉类光敏剂的光谱性质发生改变,靠近红外区均有中强度吸收,它们在可见光波长的激发下能产生在近红外区的荧光峰,与硫酸比较而言,盐酸配制的醇-酸体系优于硫酸体系.醇与酸的配比最好选择10:1,酸的最佳浓度选择1mol·L-1.优选出四-(p-甲基苯基)卟啉和四-(p-甲氧基苯基)卟啉这两种光敏活性物质. 相似文献
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G. S. S. Saini Amit Sharma Sukhwinder Singh J. M. Abbas S. K. Tripathi Sarvpreet Kaur C. G. Mahajan H. H. Thanga A. L. Verma 《Journal of Raman spectroscopy : JRS》2007,38(12):1561-1569
We report a resonance Raman study on free‐base tetraphenylporphine (H2TPP) and its chemically prepared diacid dispersed in polymethylcyanoacrylate (PMCA). Photoexcitation of the neutral porphine by laser light leads irreversibly to the formation of the diacid, with the π‐cation radical as intermediate species. Resonance Raman (RR) spectra of the diacid dispersed in the polymer obtained with 441.6 nm in the wavenumber region of 100–1650 cm−1 are recorded. Wavenumbers with other excitation lines are also reported for the diacid species. Some bands assigned to out‐of‐plane vibrational modes and forbidden under ideal D2h symmetry are also observed in the resonance Raman spectra of the diacid. These bands arise from the out‐of‐plane distortions, which reduce the symmetry of the molecule. These findings are supported by the electronic absorption studies of the diacid in the polymer. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
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Wojciech Zielenkiewicz German L. Perlovich Galina E. Nikitina Alexander S. Semeykin 《Journal of solution chemistry》1996,25(2):135-153
Densities, apparent molar volumes and partial molar volumes of benzene solutions of tetraphenylporphine, H2TPP, tetraphenylporphine metallo-complexes, MTPP (where M=Ni,Cu,Zn,Pd,Ag, and Cd), and some substituted tetraphenylporphines H2T(i-R)PP (where i=2–4 and R=–Cl,–CH3,–OCH3) H2T(i-F)PP (where i-2,3), H2T(3-Br)PP, and H2T(3-I)PP were determined at 25°C. It was found that the partial molar volumes of the studied compounds correlate linearly with the first ionization potential of the corresponding metal atom. The calculated values of the surface and volume accessible to the solvent, and the solvent-excluded volume for different conformations of H2TPP, were compared with experimental data. The volume per molecule for different crystalline forms of H2TPP and MTPP were compared with the partial molar volumes of the corresponding compounds in benzene solutions. The correlation between the partial molar volumes of H2T(3-R)PP and their Van der Waals volumes are presented for R=–H, –F,–CH3,–Cl,–Br,–OCH3, and –I. The experimental data are rationalized in terms of differences in the conformational states of the molecules. 相似文献
9.
A new method for the detection of low oxygen concentration is proposed here. The system is based on the principle of enhancement of fluorescence yield of tetraphenylporphine (TPP) dye at λ=656 nm when excited by He-Cd laser at λ =441 nm in the presence of oxygen. The sensor head was fabricated by cladding the ARTON fiber core with the poly-4-methy1-1-pentene polymer matrix doped with TPP. The experimental results obtained indicate a good enhancement in the fluorescence when the sensor head is exposed to oxygen. The response was found to be linear and stable in the range of (100 ppm-1%) with the resolution of 0.01%. The sensor response was characterized by studying its response for change in temperature and is discussed below. 相似文献
10.
Saini GS Sharma S Kaur S Tripathi SK Mahajan CG 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):3070-3076
We present here the infrared absorption spectra of free-base tetraphenylporphine and its dication. Most of the allowed IR bands of porphyrin skeletal are observed in pairs due to two-fold symmetry of the free-base tetraphenylporphine. Observation of some new bands, disappearance of few bands in the IR spectrum of dication are interpreted on the basis of point group symmetry S4. Intensity change in the observed bands due to vibrational motion of the phenyl rings for dication is also explained on the basis of symmetry of dication. Sharing of electrons of the B(1u) orbitals by the two added protons are responsible for the shifts in the position of certain IR bands for dication. 相似文献