[Synthesis of asymmetric tetraarylporphyrins and its ytterbium complexes].

The synthesis of asymmetric meso-aryl-substituted porphyrins containing three 4-methoxycarbonylphenyl groups, and as a forth substituent 4-hydroxyphenyl or 4-hydroxy-3- methoxyphenyl radicals, or the isomeric 3- and 4-pyridyl substituents is described. O-alkyl derivatives of 4-hydroxyl residue are obtained. The ytterbium complexes ofthese porphyrins were synthesized and studied their luminescence spectral properties were studied. A significant difference in the lifetimes of the excited state ofytterbium complexes of esters and acids of asymmetric porphyrins is demonstrated.

[Synthesis of tetrasubstituted porphyrins by interaction of 5-aryldipyrromethanes with 4-substituted benzaldehydes].

Synthesis of tetraphenyl-substituted porphyrins with tret-butyl and methoxycarbonyl groups in meso-aryl radicals is described. It is shown that, during the condensation of dipyrromethanes with substituted benzaldehydes, a rearrangement occurs with the formation of a mixture of isomeric porphyrins. The character of these rearrangements depends on the position of substituents in the starting compounds.

[Synthesis and luminescent spectral characteristics of porphyrin complexes with platinum group metals].

The synthesis of natural and synthetic porphyrin complexes with Pt, Pd, Rh, and Ru is reported. Their electronic absorption spectra, phosphorescence spectra, and lifetimes at room temperature both in the presence and in the absence of oxygen were studied. It has been shown that the variation of the nature of the central metal atom and of the substituents in pyrrole and phenyl rings allows the obtaining of metalloporphyrins with various phosphorescence excitation and phosphorescing emission spectra at room temperature. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2008, vol. 34, no. 2; see also http://www.maik.ru.

[Formylation of metallocomplexes of tetra-meso-(para- and meta-methoxyphenyl)porphyrines].

The Vilsmeier formylation of metallocomplexes of isomeric meta- and para-methoxy-substituted tetraphenylporphyrines has was been studied. Formyl derivatives of meta-isomers were shown to form cyclization products not only in solutions, but also in the the solid state. The ability to undergo such transformations decreases in the trend following order: Co > Cu > Ni > Pd > Pt.

[Boradiazaindacene dyes for technology of biological microchips].

A number of boradiazaindacene dyes containing a carboxyl group separated from a fluorophore by two methylene units were synthesized. The compounds have narrow spectral bands with absorption maxima at 480-530 nm and fluorescence maxima at 500-550 nm. Succinimide esters of these compounds and the corresponding fluorescent-labeled olgionucleotides were also prepared. Boradiazaindacene dyes can be used as fluorescent labels for oligonucleotides for analysis of melting curves of duplexes on microchips either by themselves or in combination with Texas Red. They can also be applied for labeling primers for polymerase chain reaction.

[Formylation of porphyrin platinum complexes].

The formylation reaction of platinum complexes of beta-unsubstituted porphyrins was studied. The interaction of deuteroporphyrin IX derivatives with the Vilsmeyer reagent led to the selective formylation of their macrocycles in the beta position. The resulting formyl derivatives of the porphyrins are of interest for fluorescent immunoassay.

[Synthesis of conjugates of bovine serum albumin with water-soluble ytterbium porphyrins]. / Sintez kon''iugatov bych'ego syvorotochnogo al'bumina s vodorastvorimym itterbiebym porfirinom.

The ytterbium complex of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin was synthesized as an IR-fluorescent label and covalently bound to bovine serum albumin. The resulting conjugate fluoresces at 985 nm and is of interest for use in IR-fluorescent tumor diagnostic, immunoassay, and energy transfer studies. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2004, vol. 30, no. 1; see also http://www.maik.ru.

[Optical and photoelectrochemical properties of Langmuir films of a Zn-complex of ethioporphyrin II]. / Opticheskie i fotoélektrokhimicheskie svoistva lengmiurovskikh plenok Zn kompleksa étioporfirina II.

The optical and photoelectrochemical properties of Zn ethioporphyrin II (ZnEP) Langmuir films deposited on an SnO2-optically transparent electrode were investigated. Absorption and fluorescence spectra were utilized to control the film structure. The main three factors, in our opinion, act on the photovoltage, namely, film thickness, ZnEP aggregate formation and the total ZnEP concentration in the monolayer. It was shown that the photopotential decreases as the amount of ZnEP aggregates in the film decreases, and the photopotential increases with surface pressure transferred to the SnO2 layer; the maximum photopotential is registered in films consisting of three and five layers.

[Fluorescence of meso-tetrakis(4-(carboxy)phenyl)porphine covalently bound to oligonucleotides d(CG)5 and d(TA)5]. / Fluorestsentsiia mezo-tetrakis(4-(karboksi)fenyl)porfina, kovalentno sviazanogo s oligonukleotidami d(CG)5 i d(TA)5.

The amino-reactive derivative of tetraphenylporphine meso-tetrakis[4-(carboxy)phenyl]porphine (TCPP) was synthesized, which is characterized by a high molar absorption coefficient (epsilon 416 = 36,500 M-1.cm-1). TCPP was covalently attached to oligonucleotides d(CG)5 [d(CG)5-TCPP] and d(TA)5 [d(TA)5-TCPP]. The spectral characteristics of these complexes were studied in 0.01 M phosphate buffer, pH 7 at 23 degrees C. UV-visible absorption spectra of these complexes have a clearly pronounced Soret band at (414 +/- 1) nm for d(CG)5-TCPP and at (412 +/- 1) nm for d(TA)5-TCPP. The fluorescence spectra of these complexes have maxima at (648 +/- 2) nm for d(CG)5-TCPP and at (658 +/- 2) nm for d(TA)5-TCPP. In this study we also determined fluorescence quantum yields q and fluorescence lifetimes tau [q = 0.099 +/- 0.011, tau = (9.0 +/- 0.3) ns for d(CG)5-TCPP and q = 0.080 +/- 0.011, tau = (8.7 +/- 0.3) ns for d(TA)5-TCPP]. A temperature rise from 5 to 50 degrees C produced only slight (within 23%) emission changes in both samples studied. Taking into account: a) high fluorescence yields (q), b) weak dependence of q on temperature, c) weak q dependence of q on the oligonucleotide type, we conclude that TCPP may be used as a sensitive fluorescence label in DNA studies.

[Biosynthesis and use of coproporphyrins and uroporphyrins and their metal complexes in immune analysis and diagnostic methods]. / Biosintez i primenenie koproporfirinov i uroporfirinov i ikh metallokompleksov v immnoanalize i diagnostike.

Methods of synthesis of coproporphyrin and uroporphyrin by using bacteria of the genus Arthrobacter are proposed. Metal complexes of coproporphyrin and uroporphyrin with Pt, Pd, and Zn were synthesized. Their structures were identified by spectrophotometry, IR spectrometry, 1H-NMR, mass spectrometry, and HPLC. Data showing the possibility to use coproporphyrin III-metal complexes as luminophores for fluorescence detection of tumors. The current and prospective uses of metal complexes of water-soluble natural porphyrins in advanced immunofluorescence assays are discussed.

[Halogenation in a series of metallocomplexes of porphyrin]. / Galogenirovanie v riadu metallokompleksov porfirinov.

We found that thionyl chloride can chlorinate porphyrin complexes with transient metals (Pd, Ni, or Cu) at the free beta- and meso-positions of the porphyrin macrocycle. A more prolonged or rigorous treatment also causes the chlorination of side alkyl substituents, mainly, methyl groups.