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51.
Queiroz MJ Abreu AS Ferreira PM Oliveira MM Dubest R Aubard J Samat A 《Organic letters》2005,7(22):4811-4814
[structure: see text] A new photochromic thieno-2H-chromene alpha-amino acid derivative was prepared by C-N palladium-catalyzed cross-coupling of a bromothieno-2H-chromene with the aminated aromatic side chain of the methyl ester of a N,N-diprotected amino acid. Its good photochromic properties demonstrated by flash photolysis and continuous irradiation indicate a possible application in ophthalmic lenses. It may also be inserted into peptides to give photoinduced reversible structural changes. 相似文献
52.
It has been shown by Olshanetsky and Perelomov that the Toda molecule equations associated with any Lie groupG describe special geodesic motions on the Riemannian non-compact symmetric space which is the quotient of the normal real form ofG, G
N, by its maximal compact subgroup. This is explained in more detail and it is shown that the fundamental Poisson bracket relation involving the Lax operatorA and leading to the Yang-Baxter equation and integrability properties is a direct consequence of the fact that the Iwasawa decomposition forG
N endows the symmetric space with a hidden group theoretic structure.Supported by CNP
q
(Brasil) 相似文献
53.
Pedro A. Fernandes Elsa S. Henriques Vineet Pande Maria. J. Ramos Ana R. R. Maia André A. S. Almeida Bruno F. B. Silva Carla M. S. Ribeiro César F. B. Ribeiro David S. M. Ribeiro Diana A. P. Fonseca Eva M. S. Cunha Filipe R. N. C. Maia Joana A. A. Pereira João P. G. Pacheco Joaquim A. A. D. Ferreira Liliana R. C. Matos Manuel A. B. P. Pinto Maria C. S. Borges Paulo J. C. R. Magalhães Pedro F. R. D. Teixeira Pedro N. B. C. Veloso Ricarte J. F. Ferreira Sandro S. Gomes Tiago F. Barros Tiago S. J. T. Selão Virgínia M. M. C. Fernandes 《Theoretical chemistry accounts》2005,113(4):197-204
We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-12,14 -prostaglandin J2 (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs. 相似文献
54.
55.
The optimization of lead hydride generation in aqueous ethanolic media and the influence on its generation of the wine components, both white and red, have been studied. These interferences were overcome by careful control of the parameters affecting hydride generation and the procedure was applied to the determination of Pb in wines. The method is fast, accurate and sensitive and can be used to quantify 24 ppb of Pb in wines. 相似文献
56.
Fernando Ferreira 《Tetrahedron letters》2004,45(33):6287-6290
Oligonucleotides protected with N-(trimethylsilylethoxycarbonyl) (Teoc) and P-(trimethylsilylethanol) (Tse) groups were synthesized and deprotected by a single ZnBr2 treatment. Teoc group stabilized dA against depurination. This strategy was applied to the synthesis of base-sensitive oligonucleotide prodrugs bearing S-acetyl-2-thioethyl (Sate) phosphotriesters. 相似文献
57.
Ferreira CM Guedes da Silva MF Fraústo da Silva JJ Pombeiro AJ Kukushkin VY Michelin RA 《Inorganic chemistry》2001,40(6):1134-1142
The dialkylcyanamide complexes cis-[PtCl(NCNR(2))(PPh(3))(2)][BF(4)] 1 and cis-[Pt(NCNR(2))(2)(PPh(3))(2)][BF(4)](2) 2 (R = Me or Et) have been prepared by treatment of a CH(2)Cl(2) solution of cis-[PtCl(2)(PPh(3))(2)] with the appropriate dialkylcyanamide and one or two equivalents of Ag[BF(4)], respectively. Compounds 2 can also be obtained from 1 by a similar procedure. Their reaction with oximes, HON=CR'R' ' (R'R' ' = Me(2) or C(4)H(8)), in CH(2)Cl(2) and in the presence of Ag[BF(4)] or Cu(CH(3)COO)(2), leads to the novel type of azametallacycles cis-[Pt(NH=C(ON=CR'R")-NR2)(PPh3)2][BF4]2 4 upon an unprecedented coupling of the organocyanamides with oximes, in a process that proceeds via the mixed oxime-organocyanamide species cis-[Pt(NCNR(2))(HON=CR'R' ')(PPh(3))(2)][BF(4)](2) 3, and is catalyzed by either Ag(+) or Cu(2+) which activate the ligating organocyanamide by Lewis acid addition to the amide group. In contrast, in the organonitrile complexes cis-[Pt(NCR)(2)(PPh(3))(2)][BF(4)](2) 5 (R = C(6)H(4)OMe-4 or Et), obtained in a similar way as 2 (but by using NCR instead of the cyanamide), the ligating NCR is not activated by the Lewis acid and does not couple with the oximes. The spectroscopic properties of those complexes are reported along with the molecular structures of 2b (R = Et), 4a1 (R = Me, R'R' ' = Me(2)), and 4b1 (R = Et, R'R' ' = Me(2)), as established by X-ray crystallography which indicates that in the former complex the amide-N-atoms are trigonal planar, whereas in the latter (4a1 and 4b1) the five-membered rings are planar with a localized N=C double bond (imine group derived from the cyanamide) and the exocyclic amide and alkylidene groups (in 4b1) are involved in two intramolecular H-bonds to the oxygen atom of the ring. 相似文献
58.
M. G. Ferreira Da Silva J. M. Fernàndez Navarro 《Journal of Sol-Gel Science and Technology》1994,2(1-3):895-901
The effect of thermal treatment on the structural incorporation of Cr2O3 in xCr2O3·(100 – x)SiO2 and 5R
n
O·xCr2O3·(95 – x)SiO2 (where x=0.01–1 mol.% and R=Li, Na and Ca) gel glasses was studied by optical absorption spectrophotometry, DTA-TG, XRD and electron microscopy.Samples heat treated at 60°C have green color due to the presence of Cr3+ in octahedral coordination. The optical transmission, and color (yellow, orange or ambar), of the samples heat treated between 200 and 700°C prove that Cr3+ (octahedrally coordinated) and Cr6+ (tetrahedrally coordinated) are both present. Segregation of Cr2O3 take place at temperatures above 800°C.In reducing conditions the gel glasses were green due to the presence of a high content of Cr3+ ions. Samples containing Li or Na show crystalline phases at temperatures below 850°C. 相似文献
59.
Maurício Cavicchioli Antonio Carlos Massabni Luciana Rebelo Guilherme Eduardo Ernesto Castellano Armando Paduan-Filho Ana Maria da Costa Ferreira 《Transition Metal Chemistry》2007,32(3):355-361
Structural, electrochemical and spectroscopic data of a new dinuclear copper(II) complex with (±)-2-(p-methoxyphenoxy)propionic acid are reported. The complex {tetra-μ-[(±)-2-(p-methoxyphenoxy)propionato-O,O′]-bis(aqua)dicopper(II)} crystallizes in the monoclinic system, space group P21/n with a = 14.149(1) ?, b = 7.495(1) ?, c = 19.827(1) ?, β = 90.62(1) and Z = 4. X-ray diffraction data show that the two copper(II) ions are held together through four carboxylate bridges, coordinated
as equatorial ligands in square pyramidal geometry. The coordination sphere around each copper ion is completed by two water
molecules as axial ligands. Thermogravimetric data are consistent with such results. The ligand has an “L” type shape due
to the angle formed by the β-carbon of the propionic chain and the linked p-methoxyphenoxy group. This conformation contributes to the occurrence of a peculiar structure of the complex. The complex
retains its dinuclear nature when dissolved in acetonitrile, but it decomposes into the corresponding mononuclear species
if dissolved in ethanol, according to the EPR measurements. Further, cyclic voltammograms of the complex in acetonitrile show
that the dinuclear species maintains the same structure, in agreement with the EPR data in this solvent. The voltammogram
shows two irreversible reduction waves at E
pc = −0.73 and −1.04 V vs. Ag/AgCl assigned to the Cu(II)/Cu(I) and Cu(I)/Cu° redox couples, respectively, and two successive oxidation waves at E
pa =− 0.01 and +1.41 V vs. Ag/AgCl, assigned to the Cu°/Cu(I) and Cu(I)/Cu(II) redox couples, respectively, in addition to the oxidation waves of the
carboxylate ligand. 相似文献
60.
Erik G.P. da Silva Ana Carolina do N. Santos Antnio C.S. Costa Dalva M. da N. Fortunato Ndia M. Jos Maria G.A. Korn Walter N.L. dos Santos Srgio L.C. Ferreira 《Microchemical Journal》2006,82(2):159-162
In the present work, a slurry sampling flame atomic absorption spectrometric method to determine directly manganese and zinc in powdered chocolate samples is proposed. The optimization step was performed using univariate methodology involving the following factors: nature and concentration of the acid solution, sonication time, and particle size. The established conditions led to the use of a sample mass of 150 mg, 2.0 mol L− 1 nitric acid solution, sonication time of 15 min, and a slurry volume of 50 mL. This method allows the determination of manganese and zinc with detection limit of 52 and 61 ng g− 1, respectively, and a precision expressed as relative standard deviation (RSD) of 2.6% and 3.2% (both, n = 10) for contents of manganese and zinc of 52.4 and 100.0 μg g− 1, respectively. The proposed method was applied for determination of manganese and zinc in five powdered chocolate samples. In these, the manganese content varied from 42.8 to 52.7 and from 88.6 to 102.4 μg g− 1 of zinc. The analytical results were compared with the results obtained by analysis of these samples after digestion using open vessel and acid bomb digestion procedures and determination using FS-FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results. 相似文献