- Synthesis and structure of five or six-coordinate manganese deuteroporphyrin-niacin dyads with intramolecular axial pyridine
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Deuteroporphyrin-niacin dyads with different chain lengths have been synthesized by modification of the propionate side chains of hemin. When a manganese ion was inserted into the porphyrin core, the UV spectral shift of manganese deuteroporphyrin-niacin dyads were experimentally demonstrated to mainly originate from the intramolecular coordination. In order to elaborate the intramolecular coordination, the spectra of single manganese porphyrin complexes in CH2Cl2 solution were measured and compared to that of the addition of axial ligands (pyridine and methyl nicotinate). Among all the synthetic dyads, the compounds of 2,7,12,18-tetramethyl-13,17-di(3- hydroxypropyl nicotinate) porphyrin and 2,7,12,18-tetramethyl-13,17-di(3- aminoethyl nicotinate) porphyrin manganese bearing the short chains did not show intramolecular coordination of the terminal base on the metal ion. Other three compounds of the niacin moiety indirectly bonded to the propionate side chains of manganese porphyrin through the diols linkage exhibited optical spectra characteristic of five or six-coordinate manganese complexes. These results indicate that the niacin groups' access to the Mn(III) center depended on the chain lengths.
- Sun, Chengguo,Hu, Bingcheng,Zhao, Donghui,Liu, Zuliang
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- Simple and efficient method for synthesis of metallodeutero-porphyrin derivatives bearing symmetrical disulphide bond
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A novel thiol-derivative porphyrin [2,7,12,18-tetramethyl-13,17-di(3- disulfidepropyl)porphyrin] bearing the symmetrical disulphide bond and its metal complexes have been successfully prepared by means of modification on naturally easily derived heme. The results are described by MS-MS and UV-vis spectroscopy.
- Sun, Cheng Guo,Hu, Bing Cheng,Zhou, Wei You,Xu, Shi Chao,Deng, Quan Zhi,Liu, Zu Liang
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- A facile synthesis of deuteroporphyrins derivatives under ultrasound irradiation
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A facile, efficient and general method for preparing deuteroporphyrin derivatives by using concentrated H2SO4 and alcohol under ultrasound irradiation has been developed. A series of new deuteroporphyrin derivatives bearing different propionic ester groups have been synthesized in good yields starting from readily accessible deuterohemin. The characterization of these compounds confirms the synthetic methodology. Compared with conventional methods, the main advantages of the present procedure are shorter reaction time and higher yields.
- Hu, Bingcheng,Zhou, Weiyou,Tang, Ying,Huang, Chengmei,Liu, Zuliang
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- PETROPORPHYRINS - II. THE PRESENCE OF PORPHYRINS WITH EXTENDED ALKYL SUBSTITUENTS
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The vanadyl porphyrins from Boscan oil (Cretaceous, W.Venezuela) were isolated as 3 fractions, and degraded to maleimides (1H-pyrrole-2,5-diones) by chromic acid.Analysis of the products by GC-MS, using multiple ion detection to enhance sensitivity, revealed a major homologous series of 3-Me components with n-alkyl side chains extending to C11, and a minor series with branched alkyl side chains, the Me branch being at C-1.The origin of the extended alkyl groups is discussed.
- Martin, J.,Quirke, E.,Shaw, George J.,Soper, Paul D.,Maxwell, James R.
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- Dynamic docking and electron transfer between Zn-myoglobin and cytochrome b5
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We present a broad study of the effect of neutralizing the two negative charges of the Mb propionates on the interaction and electron transfer (ET) between horse Mb and bovine cyt b5, through use of Zn-substituted Mb (ZnMb, 1) to study the phot
- Liang, Zhao-Xun,Nocek, Judith M.,Huang, Kai,Hayes, Ryan T.,Kurnikov, Igor V.,Beratan, David N.,Hoffman, Brian M.
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- Synthesis of tetrapyrrole nitrogen mustards with potential anti-tumor activities
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Eight porphyrin nitrogen mustards and six meso-tetraphenylporphin nitrogen mustards were synthesized. Most of the compounds possess both the chemotherapeutic and photochemotherapeutic effects on tumor.
- Chen, Zhi-Long,Wan, Wei-Qin,Chen, Jing-Rong,Zhao, Fang,Xu, De-Yu
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- Benzoylation at the meso position of a zinc(II) deuteroporphyrin
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By short treatment of zinc(II) deuteroporphyrin-IX dimethyl ester with benzoic anhydride/SnCl4, a mixture of benzoylated derivatives was obtained from which a tribenzoyl derivative with benzoyl groups at the 2, 4, and γ-meso positions could be isolated in low yield. Except for the known Vilsmeier formylation, this constitutes the first example of a Friedel-Crafts acylation taking place at the meso position of a porphyrin chelate. The expected lack of regioselectivity of this reaction, even at low conversion rates, and the difficulty to separate the products limit, of course, its synthetic value for the preparation of the particular benzoyl derivatives. This limitation cannot be overcome by starting with a completely β-substituted porphyrin or with a symmetrically substituted porphyrin, since attempts to benzoylate Zn(II) mesoporphyrin-IX dimethyl ester lead exclusively to demetallation. However, these findings add to the knowledge of the fundamental properties of porphyrin reactivity. A rationalization based on calculations at a semiempirical level, which are in acceptable agreement with the experimental results, is presented.
- Vazquez, Jordi,Gonzalez, Maria M.,Marti, Cristina,Nonell, Santi,Trull, Francesc R.
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- Protonation-deprotonation equilibria in tetrapyrroles Part 4: Mono- and diprotonations of deutero-, hemato-, meso-, and protoporphyrin IX dimethyl esters in methanolic hydrochloric acid
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The N-protonations in the deutero, hemato, meso and protoporphyrin IX dimethyl esters (DME) were investigated by spectrophotometric titrations using HCl as the acid and methanol as the solvent. Two spectroscopically different protonated species were observed for each porphyrin DME in addition to the neutral form. These were assigned to the N-protonated monocation and dication. There were no difficulties encountered in observing the monocation formation in the HCl-MeOH system. Very sharp isosbestic points were characteristic of each protonation stage. The pK3 values for the porphyrins in the above order were 3.23, 4.70, 2.93 and 3.37; the pK4 values were 2.48, 2.62, 2.41 and 2.64, respectively. For all porphyrins studied, no further spectral changes were observed after the dication was completely formed. This was interpreted as indicating that the formation of more highly protonated species is not possible in fullydelocalized porphyrins possessing the 18 π-electron [18]diazaannulene delocalization pathway. When the titration was performed on the free dicarboxylic acid porphyrins, aggregation obscured the first protonation step and no clear monocation spectrum could be distinguished. However, also in that case the titration ended up to a UVvis spectrum typical of the dication and the effect of aggregation on the pK4 values was negligible. The UVvis spectrometric parameters are given for the neutral forms and for the protonated species of the porphyrin DMEs. The results are discussed in terms of the NH tautomerization connected to the π-electron delocalization pathway (aromaticity), which tends to hinder outofplane distortions in the porphyrin plane, and in terms of solvation and counterion stabilization of the protonated forms.
- Hynninen, Paavo H.
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p. 385 - 395
(2015/05/20)
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- Synthesis and catalytic properties of a series of cobalt porphyrins as cytochrome P450 model: The effect of substituents on the catalytic activity
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A series of cobalt porphyrins derived from hemin was prepared as cytochrome P450 models. Effects of substituents at the cobalt deuteroporphyrin-propionate side chains are investigated in oxidation of toluene with air to benzaldehyde and benzyl alcohol without the use of solvent and sacrificial co-reductant. The catalytic activity of cobalt porphyrins depends on the type of substituents. When the electron-withdrawing groups like -Cl, -Br, were introduced into the double propionate side chains, they can increase the catalyst stability and selectivity to benzaldehyde. In comparison with these electron-withdrawing groups, the electron-donor groups, such as -CH3, -S-S- and -NH 2 groups, can improve their catalytic activities. Moreover, the electron-donor group containing an unpaired electron (such as -S-S-, -NH 2) is benefit for improving its catalytic efficiency and promoting the electron delivery. It can be concluded that the double propionate side chains in the deuteroporphyrin complex may participate in oxidation process and effect electron transfer from the high-valent metalloporphyrin species to the substrate.
- Hu, Bingcheng,Sun, Chengguo,Deng, Quanzhi,Liu, Zuliang
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p. 345 - 352
(2013/07/26)
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- Rapid aerobic oxidation of alcohols to carbonyl compounds with dioxygen using metallodeuteroporphyrin dimethyl esters as catalysts in the presence of isobutylaldehyde
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A facile biomimetic method for rapid oxidation of alcohols to carbonyl compounds using dioxygen as the primary oxidant catalyzed by metallodeuteroporphyrin dimethyl ester [M(DPDME)] in acetonitrile as the reaction solvent and isobutylaldehyde as cocatalyst has been investigated. Among the M(DPDME) catalysts, where M = Fe(III), Co(II), Mn(III), Ni(II), Cu(II), and Zn(II), cobalt porphyrin was found to be the most active and effective catalyst. The catalytic system was widely used in the oxidation of various alcohols and especially exhibited excellent activity for oxidation of aromatic alcohols under mild conditions. Moreover, M(DPDME) was prepared from an improved facile method by chemical modification of natural hemin and an alternative mechanism for the aerobic oxidation of alcohols has been proposed and discussed.
- Sun, Chengguo,Hu, Bingcheng,Liu, Zuliang
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experimental part
p. 295 - 303
(2012/07/28)
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- PORPHYRIN LINKED METRONIDAZOLE AGAINST GUM DISEASE: PORPHYROMONAS GINGIVALIS
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The present invention relates generally to targeted molecular agents (TMAs) directed to a particular organism or group of organisms and uses thereof. More particularly, the present invention provides TMAs having a targeting moiety which comprises a natural or induced auxotrophic requirement of the particular organism as a vehicle for directing an agent linked to the moiety to be delivered to the target organism. The TMAs of the present invention are useful for targeting molecules such as antimicrobial agents and diagnostic agents to selected organisms.
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Page/Page column 30-31; 58
(2008/06/13)
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- New Syntheses and Reactions of Some Halogenated Porphyrins
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Efficient syntheses of 2,4-dibromo- and 2,4-diiododeuteroporphyrin IX have been carried out by treating zinc(II) 2,4-bis(chloromercurio)deuteroporphyrin IX dimethyl ester (2) with bromine or iodine.Unavoidable mesochlorination occurs when 2 is treated with chlorine and with other free-radical chlorinating agents.Regioselective meso-chlorination and peripheral (β) bromination are shown to occur from brief treatment of copper(II) deuteroperphyrin IX or β-unsubstituted a,c-biladienes with the corresponding copper(II) halide in refluxing dimethylformamide.Protoporphyrin IX has been synthesized by vinylation of 2 via ethylene/LiPdCl3 (35percent yield), with vinyl bromide and Wilkinson's catalyst (63percent), or from 2,4-dibromodeuteroporphyrin IX with ethenyltributylstannane/(Ph3P)4Pd0 (85percent).
- Minnetian, Ohannes M.,Morris, Ian K.,Snow, Kevin M.,Smith, Kevin M.
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p. 5567 - 5574
(2007/10/02)
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- Synthesis and Reactivity of 131,132,171,172-Tetradehydrodeuteroporphin
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Die 13,17-Propionsaeure-methylester-Seitenketten des Deuteroporphyrin-dimethylesters (1a) wurden mit Phenylselenobromid zu 1b dehydriert.Die 12,18-Methylgruppen tauschten in Deuteriomethanol mit Natriummethoxid Wasserstoff gegen Deuterium aus.
- Fuhrhop, Juergen-Hinrich,Lehmann, Thomas
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p. 1386 - 1389
(2007/10/02)
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- Manipulation of Vinyl Groups in Protoporphyrin IX: Introduction of Deuterium and Carbon-13 Labels for Spectroscopic Studies
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Using commercially available hemin (5) as the starting material, routes for preparation of monovinyl deuterated (27), monovinyl carbon-13 enriched (41,42), and divinyl carbon-13 enriched (43,44) derivatives of protoporphyrin IX dimethyl ester (1) are described.The monovinyl carbon-13 enriched porphyrins 41 and 42 were obtained by way of a previously reported Wittig reaction on Spirographis and iso-Spirographis porphyrin dimethyl esters 28 and 39, respectively.A new efficient partial synthesis of Spirographis porphyrin dimethyl ester (28) from deuteroporphyrin IX dimethyl ester (7) is reported, and in this the key formyl group at the 2 position is inserted by way of a Vilsmeier reaction employing a hindered amide.
- Smith, Kevin M.,Fujinari, Eugene M.,Langry, Kevin C.,Parish, Daniel W.,Tabba, Hani D.
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p. 6638 - 6646
(2007/10/02)
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- Carbon-5 Regiospecific Synthesis of Deuteroporphyrin IX
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Benzyl 3-(ethoxycarbonyl)-4-methyl-2-pyrrolecarboxylate was formylated with dimethylformamide (DMF)-phosphorous oxychloride, and the 5-formylpyrrole was obtained in 50percent yield.It was reduced with sodium borohydride to the alcohol, which was condensed with benzyl 3-methyl-4-(ethoxycarbonyl)-2-pyrrolecarboxylate to afford dibenzyldipyrrylmethane in good yield.The latter was transformed into its 5,5'-diformyl derivative which when condensed with bis-4-methylpyrryl>methane afforded the 3,8-bis(ethoxycarbonyl)deuteroporphyrin IX dimethyl ester in 40percent yield.Decarboxylation of the latter in hot hydrochloric acid gave deuteroporphyrin IX (isolated as its dimethyl ester) in 50percent yield.
- Rezzano, Irene,Buldain, Graciela,Frydman, Benjamin
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p. 3059 - 3063
(2007/10/02)
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