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11.
M. Liliana Graziano M. Rosaria Iesce Rachele Scarpati 《Journal of heterocyclic chemistry》1986,23(2):553-556
Phenylketene dimethylacetal ( 1 ) reacts with the α-diazoketones to give the dihydrofurans 6 . These compounds, as cyclic ortho esters, can undergo dealcoholation into the furans 2 and hydrolysis into the γ-ketoesters 3 and into the γ-ketoacids 4 . Cyclopropane acetal 8 , obtained starting from acetal 1 and ethyl diazoacetate, by heating leads quantitatively to functionalized ester 9 . These synthetic methods enlarge the sphere of applicability of the electron-rich alkene 1 as synthon in organic synthesis. 相似文献
12.
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
13.
Liliana Viciu 《Journal of solid state chemistry》2003,175(1):88-93
Mn-Cl sheets were inserted into the perovskite blocks of a double-layered Dion-Jacobson compound by ion exchange at low temperature (390°C). The Rietveld structural analysis of X-ray powder diffraction data (P4/mmm) indicates that the product, (MnCl)LaNb2O7, has the manganese coordinated by two apical oxygens from the perovskite layers and four in-plane chlorines within the interlayer space. On heating, this compound exhibits an exothermic transition between 650°C and 750°C that is consistent with metastability. Magnetic characterization shows Curie-Weiss behavior at higher temperatures (>200 K) with a magnetic moment corresponding to the presence of high-spin Mn2+ ion (S=5/2). At lower temperatures, antiferromagnetic interactions become significant and the broad maximum at 63 K reveals the 2-D character of the magnetic behavior. The susceptibility data, fit with the high temperature expansion for a Heisenberg square planar system, show a negative exchange interaction of J/k=−3.77 K. 相似文献
14.
Yaghmur A de Campo L Sagalowicz L Leser ME Glatter O 《Langmuir : the ACS journal of surfaces and colloids》2005,21(2):569-577
Self-assembled nanostructures, such as inverted type mesophases of the cubic or hexagonal geometry or reverse microemulsion phases, can be dispersed using a polymeric stabilizer, such as the PEO-PPO-PEO triblock copolymer Pluronic F127. The particles, which are described in the present study, are based on monolinolein (MLO)-water mixtures. When adding tetradecane (TC) to the MLO-water-F127 system at constant temperature, the internal nanostructure of the kinetically stabilized particles transforms from a Pn3m (cubosomes) to a H2 (hexosomes) and to a water-in-oil (W/O, L2) microemulsion phase (emulsified microemulsion (EME)). To our knowledge, this is the first time that the formation of stable emulsified microemulsion (EME) systems has been described and proven to exist even at room temperature. The same structural transitions can also be induced by increasing temperature at constant tetradecane content. The internal nanostructure of the emulsified particles is probed using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). At each investigated composition and temperature, the internal structure of the dispersions is observed to be identical to the corresponding structure of the nondispersed, fully hydrated bulk phase. This is clear evidence for the fact that the self-assembled inner particle nanostructure is preserved during the dispersion procedure. In addition, the internal structure of the particles is in thermodynamic equilibrium with the surrounding water phase. The internal structure of the dispersed, kinetically stabilized particles is a "real" and stable self-assembled nanostructure. To emphasize this fact, we denoted this new family of colloidal particles (cubosomes, hexosomes, and EMEs) as "ISASOMES" (internally self-assembled particles or "somes"). 相似文献
15.
Eimer GA Gómez Costa MB Pierella LB Anunziata OA 《Journal of colloid and interface science》2003,263(2):400-407
The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline. 相似文献
16.
A new sensitive and selective preconcentration-fluorimetric method for determination of terazosin based on its native fluorescence was developed. The analyte, initially present in aqueous matrix, was treated with an extractive non-ionic surfactant solution and separated by the clouding phenomenon. The optimum analytical conditions for terazosin assay were established. Under these conditions, linear calibration curves were obtained over the range of 1 × 10−5 to 7.0 μg mL−1 with detection and quantification limits of 1.11 × 10−5 and 3.7 × 10−5 μg mL−1, respectively. Additionally, the binding constant (KB) for the terazosin-PONPE 7.5 system was determined given a value of 1028 L mol−1. The developed coupled methodology, which thoroughly satisfies the typical requirements for pharmaceutical control processes, was proved to be appropriate for monitoring terazosin in actual pharmaceutical formulations and biological fluid sample. The results were validated by recovery test and by comparison with other reported methods, being highly satisfactory. 相似文献
17.
Alessandro Pezzella Liliana Lista Alessandra Napolitano Marco d’Ischia 《Tetrahedron letters》2005,46(20):3541-3544
A one-pot procedure for the preparation of catecholestrogens in over 90% yield is reported, involving oxygenation of 17β-estradiol or estrone with o-iodoxybenzoic acid (IBX) followed by reduction with methanolic NaBH4. The procedure, which was extended to the o-hydroxylation of a number of representative phenols in good-to-high yields, expands significantly the scope of phenolic oxidation mediated by IBX. 相似文献
18.
Marcella Massacesi Rosalba Pinna Gerolamo Devoto Ermanno Barni Piero Savarino Liliana Strinna Erre 《Transition Metal Chemistry》1984,9(9):351-355
Summary Complexes of general formula MLmCl2 · nH2O, where M=cobalt(II) or nickel(II); L=2-(4-methyl, 2-pyridyl)-benzimidazole (mpbi), 2-(4-methyl, 2-pyridyl)benzothiazole (mpbt), 2-(4-methyl, 2-pyridyl)benzoxazole (mpbo), 2-(4-methyl, 2-quinolyl)benzoxazole (mqbo), or 2-(4-methyl, 8-quinolyl)benzoxazole (mqbo); m=1,2; n=0–3, were prepared and characterized by t.g.a., conductance and magnetic measurements, i.r. and diffuse-reflectance electronic spectra.All the ligands behave as bidentate and coordinate through the pyridine- and isoxazole-nitrogen atoms.The nickel complexes have distorted octahedral or fivecoordinate structures. The cobalt complexes arepseudo-tet- rahedral except Co(mpbo)2Cl2·2H2O where the metal is six-coordinate. 相似文献
19.
Paleari R Ceriotti F Azzario F Maccioni L Galanello R Mosca A 《Bioelectrochemistry (Amsterdam, Netherlands)》2004,62(2):175-179
An immunologically mediated pathway has been largely accepted to be one of the mechanisms involved in the clearance of senescent or prematurely damaged RBC. According to this pathway, RBC removal is mediated by binding of naturally occurring IgG to clustered integral membrane proteins, followed by complement deposition. The validation of an immunoenzymatic method for the detection of RBC-bound autologous IgG is presented. The use of RBC-bound IgG as an index related to red cell age was evaluated by measuring IgG binding in RBC treated with the clustering agent ZnCl2, in density fractionated RBC and in a selected group of patients expected to have an altered RBC life span. The immunoenzymatic method for IgG detection resulted to be reproducible (CV = 3.4%). IgG binding to in vitro clustered RBC was found to be enhanced to a very great extent, about 20 times higher with respect to untreated RBC. A slight but significant increase (about 1.8-fold) in membrane-bound IgG was observed in the highest density fraction of normal RBC, which constituted 1% of the total cells. A significantly greater number of RBC-bound IgG was measured in splenectomized beta-thalassemia intermedia patients and in subjects with secondary decreases in the C3 complement fraction concentration. 相似文献
20.
Juan Bisceglia María B. García Rosana Massa María L. Magri Mariana Zani Gabriel O. Gutkind Liliana R. Orelli 《Journal of heterocyclic chemistry》2004,41(1):85-90
A method is described for the synthesis of bis(3‐aryl‐1‐hexahydropyrimidinyl)methanes 1, by condensation of N‐aryl‐1,3‐propanediarnines 2 with formaldehyde. The reaction mechanism involves N‐arylhexahydropyrimidines 3 as intermediates. Such compounds can also be prepared efficiently by a methylene exchange reaction between bis‐hexahydropyrimidines 1 and the corresponding diamines 2. The antimicrobial activity of compounds 1 was evaluated by the disk diffusion method and some of them showed moderate to good growth inhibition activity. 相似文献