双脂肪胺钌卟啉的合成、结构表征和晶体结构

本文讨论了一系列双脂肪胺钌卟啉配合物，包括Ru(^Ⅱ)(Por)(H₂NR)₂和Ru(^Ⅱ)(Por)(HNR₂)₂［Por=四苯基卟啉(TPP)，中位-四(对甲苯基)卟啉(TTP)，中位-四(对氯苯基)卟啉(4-Cl-TPP);R=叔丁基，异丙基，环己基，正辛基，正十二烷基，R′=甲基和乙基］的合成，结构表征和晶体结构测定。钌羰基卟啉与间-氯过苯甲酸的反应混合物用过量的脂肪胺处     

High-performance thin-layer chromatography of metal complexes ofmeso-tetrakis(p-tolyl)porphyrin on cellulose and silica gel

Summary The migration behavior of metal complexes ofmeso-tetrakis(p-tolyl)porphyrin (TTP) are studied in HPTLC systems with cellulose and silica gel thin-layers and various organic solvents of relatively low polarity. The mobility of the metal complex tends to increase in the following orders of its central-metal elements: on cellulose, Mg(II)<Zn(II)<V(IV)<(H)<Pd(II)< Ni(II)Cu(II); on silica gel, Mg(II)<V(IV)<Zn(II)= (H)<Ni(II)Pd(II)Cu(II). Recommendable phase system for the separation of metal-TTP complexes is a combination of silica gel thin-layer with a carbon disulfide-m-xylene mixture though the complexes of Ni, Cu and Pd are not completely resolved.     

超高灵敏显色剂meso-四(4-氯苯基)卟啉与钴反应的分光光度法研究

本文研究了新显色剂meso-四(4-氯苯基)卟啉与钴的反应条件。在表面活性剂存在下,90℃恒温加热15min,试剂与钴形成稳定的1:1配合物。λ_(max)=420nm,ε_(420)=7.94×10~5L·mol~(-1)·cm~(-1),0～3.2μgCo/25ml符合比尔定律,为目前已报道的分光光度法测定钴最灵敏的方法。用来测定维生素B_(12)针剂中微量钴,结果满意。     

Synthesis of A2B2 type cis-doubly N-confused porphyrins from N-confused dipyrromethanes

A₂B₂ type of cis-doubly N-confused porphyrins (cis-N₂CP) bearing 2,6-dichloro-, 2-nitro-, 3-nitro-, and 4-nitro-phenyl groups and pentafluorophenyl groups at meso-positions were synthesized by the condensation of aryl-substituted N-confused dipyrromethanes and pentafluorobenzaldehyde. The complexation of rare high oxidation states of metals, Cu(III) and Ag(III), was demonstrated.     

高分子担载卟啉及其金属络合物研究进展

本文介绍了高分子担载卟啉及其金属络合物在模拟细胞色素Ｐ－４５０，光学灭菌材料，阴离子载体及光敏化学材料等领域的最新研究进展。     

The electrocatalytic reactions of adenine, guanine, H2O, H2O2, N2H4, and l -cysteine catalyzed by poly(Ni(4-TMPyP)) film-modified electrodes

Electrochemical preparation of poly(nickel tetrakis(N-methyl-4-pyridyl)porphyrin) tetratosylate (poly-Ni(4-TMPyP)) produces stable and electrochemically active films in strong and weak basic aqueous solutions. These films were produced on glassy carbon and gold electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of poly(Ni(4-TMPyP)) films. The electrochemical properties of poly(Ni(4-TMPyP)) films indicate that the redox process was confined in to the immobilized film. The electrochemical quartz crystal microbalance results showed an ion exchange reaction for the redox couple. The polymer films showed one new redox couple when transferred to strong and weak basic aqueous solutions and the formal potential was found to be pH dependent. The electrocatalytic oxidation of H₂O by a nickel tetrakis(N-methyl-4-pyridyl)porphyrin film-modified electrode was also performed. The mechanism of oxygen evolution was determined by cyclic voltammetry, chronoamperometry and rotating ring disc electrode methods. The oxygen evolution was determined by a bicatalyst system using hemoglobin, and iron tetrakis (N-methyl-2-pyridyl)porphyrin as catalyst to detect the oxygen by electrocatalytic reduction. The electrocatalytic oxidations of adenine, guanine, H₂O₂, N₂H₄, NH₂OH, and l-cysteine by the film-modified electrode obtained from water-soluble nickel porphyrin were also investigated.     

One-step synthesis of some polyfluoroalkylated 1,3-benzodioxoles, 4H-l,3-benzodioxins anddibenzo[d,f] [l,3]dioxepins

Several polyfluoroalkylated heterocyclic compounds containing methylenedioxy group such as 2-(F-alkyl) substituted 1,3-benzodioxole, piperonal, 4H-1,3-benzodioxin, 1,3-dioxolane and 6-(F-alkyl) substituted dibenzo[d,f][1,3]dioxepin have been prepared through double Michael-addition reactions of 2,2-dihydropolyfluoroalkanoates with the corresponding diphenols or diols in high yields.     

Synthesis, Characterization and Weak Intramolecular Interactions of Porphyrins Bearing Nucleobases

5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by ^1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. ^1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.     

Porphyrazines: synthesis,properties, application

The data on the synthesis, properties, and practical application of porphyrazines (tetraazaporphines), the nearest structural analogs of porphyrins and phthalocyanines, have been systematized.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2320–2336, December, 1995.This work was financially supported by the Russian Government and the International Science Foundation (Grant No. MEY300).     

Effects of some Nitrogen Bases on the Oxygenation of Tetralin with Sodium Periodate Catalyzed by Manganese（Ⅲ）meso- Tetraphenylporphyrin as a Model Compound of Cytochrome P-450

The effect of some nitrogen bases on the oxygenation of tetralin by sodium periodate, catalyzed by Mn（TPP）OAc, was evaluated. A series of eight bases, including imidazole, pyridine, and quinuclidine, was used. Binding of axial ligand to the four-coordinate Mn（Ⅲ）-center influenced the efficiency and selectivity of the catalytic oxygenation system.