This work demonstrates the feasibility and power of electrophilic substitution on the peripheral carbon atoms of triarylcorroles as a synthetic tool to new derivatives. The large difference in the reactivity of the various carbon atoms on the macrocycle was shown to be of electronic rather than steric origin. A careful choice of reagents and a delicate control of reaction conditions allowed the selective syntheses of novel derivatives, in all of which substitution took place selectively in only the directly joined pyrrole rings of the macrocycle. This was proven by a combination of X-ray crystallography of the various products and detailed analysis of their NMR spectra.
Major advances over the last few years have facilitated the synthesis of a large variety of meso-only substituted corroles that display interesting catalytic, therapeutic and photophysical properties. This work is the first to study extensively the NMR spectral characteristics of both metallated and non-metallated triarylcorroles in various organic solvents and provide guidelines for easy and reliable assignments of 1D 1H spectra from trends of J coupling constants and chemical shifts. An excellent correlation is found between C=C bond lengths derived from 3J(H,H) values and experimental lengths determined by x-ray crystallography of the same molecules. The nuclear Overhauser effect provides a robust 1D 1H NMR tool for determining the selectivity of electrophilic substitutions. Variable-temperature NMR and isotopic labelling reveal a single preferred tautomerization state and unsymmetric ring orientations at -70 degrees C. The beta-pyrrole protons demonstrate long-range heteronuclear couplings with the coordination core (15N) and with the ortho-19F nuclei of the meso-carbon aryl rings. In sum, application of multinuclear magnetic resonance to corroles and their metal complexes, through the compilation of chemical shifts and J couplings and the recognition of trends therein, provides basic information essential to reliable spectral assignments. Additionally, the conclusions drawn about the structures of corroles and the electron densities at various positions of the corrole macrocycle resulting from the application of high-resolution NMR techniques are of importance to an in-depth understanding of the molecular interactions and processes of this relatively new and rapidly expanding class of compounds.
Gallium(III) corroles are closed-shell analogs of zinc(II) porphyrins. These intensely fluorescent molecules can be modified readily to tune their solubility and photophysical properties. A water-soluble gallium corrole has been synthesized and investigated in depth; it binds tightly to human serum albumin, opening the possibility of using corroles as therapeutic agents as well as probes of biological structures.
The ginger combination is as effective as diclofenac but safer in treating OA, being without effect on the stomach mucosa. The increased mucosal PGs synthesis in the ginger group supports an increased mucosa-protective potential. VAS; visual analogue scale, 0-100 mm.
The preparation and spectroscopic properties of a series of metallocorroles with polar head groups CHO and CH = C ( CN )( COOH ) are reported, as well as the X-ray crystal structure of 5,10,15-tris(pentafluorophenyl)corrolatoaluminium(III)bispyridine (triclinic space group (P-1) with unit cell parameters: a = 9.426(1) Å; b = 13.202(1) Å; c = 19.936(1) Å; α = 74.19(1)°; β = 78.47(1)°; γ = 75.75(1)°; V = 2289.57(8) Å3). Amphiphilic aluminium(III) and gallium(III) corroles exhibit electronic absorption (Soret peaks between 410 and 448 nm; Q-bands between 584 and 638 nm) and fluorescence (band maxima between 634 and 706 nm) at lower energies than their hydrophobic analogs.
ABSTRACT:The influence of small rings annulated to aromatic rings is usually additive. However, in some systems the behavior is nonadditive, for example, in tricarbonyliron-cyclobutadienobenzene versus tris(tricarbonylironcyclobutadieno)benzene. A study of dimethylenecyclobutabenzene, 1,3-bis(dimethylenecyclobuta)benzene, tris(dimethylenecyclobuta)benzene, and their bora, imino, and oxo derivatives is presented. The behavior of these systems ranges from an almost perfect additivity (in the bora derivatives) to nonadditive behavior (in the oxo derivatives) where the single ring annulated system shows a negative difference between the bonds endocyclic and exocyclic to the annulated small ring (negative R; anti-Mills-Nixon distortion), the doubly annulated system shows R = 0, and the triply annulated system shows positive R (Mills-Nixon distortion). The geometrical properties of the systems are analyzed in terms of the strain, bond curvature, and electronegativity of the exocyclic substituent. These atomic and σ properties are found to be responsible for the structural properties whereas π factors are of minor or no importance.
Обследовали 100 больных с ожирением. Регулируемое бандажирование желудка (РБЖ) было выполнено 20 пациентам, рукавная резекция желудка (РРЖ)-40 больным и гастрошунтирование (ГШ)-40 больным. Контрольную группу составили 10 практически здоровых людей. В сыворотке крови иммуноферментным методом определяли концентрацию витаминов В 1 , В 2 , В 5 , В 6 , В 9 , В 12 , С, D, ниацина, биотина и ретинол-связывающего белка (РСБ) до операции и через 1 год после хирургического лечения. Выявлено значительное снижение витаминов С, В 6 , В 5 , D и РСБ как до, так и после бариатрических операций (БО). Более половины больных, перенесших РРЖ, имели также исходное снижение уровня ниацина. Через год после проведения БО (РБЖ, РРЖ, ГШ) число больных с дефицитом этих витаминов сохранялось прежним либо увеличивалось. ГШ не оказало существенного влияния на концентрацию фолиевой кислоты, витаминов В 2 , В 12 , В 1 и биотина. У un-ta.-Bulletin of North Caucasian federal university. 2014;1(40):83-85. 4. Luk'janenko E. V. Ispol'zovanie NO-soderzhashhikh vozdushno-plazmennykh potokov v kompleksnom lechenii peritonita: avtoref. dis. … kand. med.nauk. M. 2006. 24 p. 5. Marakhonich L. A., Pekshev A. V. Infekcija v khirurgii-problema sovremennojj mediciny: sb. tez. 3-jj Vsearmejj. konf. s mezhdunar. uchastiem.-Infection in surgery-problem of modern medicine: collection of theses of third army conference.
Обследовали 100 больных с ожирением. Регулируемое бандажирование желудка (РБЖ) было выполнено 20 пациентам, рукавная резекция желудка (РРЖ)-40 больным и гастрошунтирование (ГШ)-40 больным. Контрольную группу составили 10 практически здоровых людей. В сыворотке крови иммуноферментным методом определяли концентрацию витаминов В 1 , В 2 , В 5 , В 6 , В 9 , В 12 , С, D, ниацина, биотина и ретинол-связывающего белка (РСБ) до операции и через 1 год после хирургического лечения. Выявлено значительное снижение витаминов С, В 6 , В 5 , D и РСБ как до, так и после бариатрических операций (БО). Более половины больных, перенесших РРЖ, имели также исходное снижение уровня ниацина. Через год после проведения БО (РБЖ, РРЖ, ГШ) число больных с дефицитом этих витаминов сохранялось прежним либо увеличивалось. ГШ не оказало существенного влияния на концентрацию фолиевой кислоты, витаминов В 2 , В 12 , В 1 и биотина. У un-ta.-Bulletin of North Caucasian federal university. 2014;1(40):83-85. 4. Luk'janenko E. V. Ispol'zovanie NO-soderzhashhikh vozdushno-plazmennykh potokov v kompleksnom lechenii peritonita: avtoref. dis. … kand. med.nauk. M. 2006. 24 p. 5. Marakhonich L. A., Pekshev A. V. Infekcija v khirurgii-problema sovremennojj mediciny: sb. tez. 3-jj Vsearmejj. konf. s mezhdunar. uchastiem.-Infection in surgery-problem of modern medicine: collection of theses of third army conference.
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