912 resultados para Ardouin, C. (18..-18..) -- Portraits
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Guanylyl cyclase C (GC-C) is predominantly expressed in intestinal epithelial cells and serves as the receptor for the gastrointestinal hormones guanylin and uroguanylin, and the heat-stable enterotoxin, the causative agent for Travellers' Diarrhea. Activation of GC-C results in an increase in intracellular levels of cGMP, which can regulate fluid and ion secretion, colon cell proliferation, and the gut immune system. This review highlights recent findings arising from studies in the GC-C knockout mouse, along with enigmatic results obtained from the first descriptions of human disease caused by mutations in the GC-C gene. We provide some insight into these new findings and comment on areas of future study, which may enhance our knowledge of this evolutionarily conserved receptor and signaling system. (C) 2012 Federation of European Biochemical Societies. Published by Elsevier B. V. All rights reserved.
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The reaction of the low valent metallocene(II) sources Cp'Ti-2(eta(2)-Me3SiC2SiMe3) (Cp' = eta(5)-cyclopentadienyl, 1a or eta(5)-pentamethylcyclopentadienyl, 1b) with different carbodiimide substrates RN=C=NR' 2-R-R' (R = t-Bu; R' = Et; R = R' = i-Pr; t-Bu; SiMe3; 2,4,6-Me-C6H2 and 2,6-i-Pr-C6H3) was investigated to explore the frontiers of ring strained, unusual four-membered heterometallacycles 5-R. The product complexes show dismantlement, isomerization, or C-C coupling of the applied carbodiimide substrates, respectively, to form unusual mono-, di-, and tetranuclear titanium(III) complexes. A detailed theoretical study revealed that the formation of the unusual complexes can be attributed to the biradicaloid nature of the unusual four-membered heterometallacycles 5-R, which presents an intriguing situation of M-C bonding. The combined experimental and theoretical study highlights the delicate interplay of electronic and steric effects in the stabilization of strained four-membered heterometallacycles, accounting for the isolation of the obtained complexes.
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Structural characterizations using XRD and C-13 NMR spectroscopy of two rodlike mesogens consisting of (i) three phenyl ring core with a polar cyano terminal and (ii) four phenyl ring core with flexible dodecyl terminal chain are presented. The three-ring-core mesogen with cyano terminal exhibits enantiotropic smectic A phase while the four-ring mesogen reveals polymesomorphism and shows enantiotropic nematic, smectic C, and tilted hexatic phases. The molecular organization in the three-ring mesogen is found to be partial bilayer smectic Ad type, and the interdigitation of the molecules in the neighboring layers is attributed to the presence of the polar terminal group. For the four-ring mesogen, the XRD results confirm the existence of the smectic C and the tilted hexatic mesophases. A thermal variation of the layer spacing across the smectic C phase followed by a discrete jump at the transition to the tilted hexatic phase is also observed. The tilt angles have been estimated to be about 45 degrees in the smectic C phase and about 40 degrees in tilted hexatic phase. C-13 NMR results indicate that in the mesophase the molecules are aligned parallel to the magnetic field. From the C-13-H-1 dipolar couplings determined from the 2D experiments, the overall order parameter for the three-ring mesogen in its smectic A phase has been estimated to be 0.72 while values ranging from 0.88 to 0.44 have been obtained for the four-ring mesogen as it passes from the tilted hexatic to the nematic phase. The orientations of the different rings of the core unit with respect to each other and also with respect to the long axis of the molecule have also been obtained.
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Monosubstituted gamma(4)-residues (gamma(4)Leu, gamma(4)Ile, and gamma(4)Val) form helices even in short homooligomeric sequences. C-14 helix formation is established by X-ray diffraction in homooligomeric (gamma)(n) tetra-, hexa- and decapeptide sequences demonstrating the high propensity of gamma residues, with proteinogenic side chains, to adopt locally folded conformations.
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Unconstrained gamma(4) amino acid residues derived by homologation of proteinogenic amino acids facilitate helical folding in hybrid (alpha gamma)(n) sequences. The C-12 helical conformation for the decapeptide, Boc-Leu-gamma(4)(R)Val](5)-OMe, is established in crystals by X-ray diffraction. A regular C-12 helix is demonstrated by NMR studies of the 18 residue peptide, Boc-Leu-gamma(4)(AR)Val](9)-OMe, and a designed 16 residue (alpha gamma)(n) peptide, incorporating variable side chains. Unconstrained (alpha gamma)(n) peptides show an unexpectedly high propensity for helical folding in long polypeptide sequences.
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Insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(mu-Br)](2) with various alkynes in CH2Cl2 under ambient conditions afforded diinserted eight-membered palladacycles, (kappa(2)(C,N):eta(2)(C=C)-PdBr] (1-11), in high yield (76-96%), while insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(Lewis base)Br] (VI-XI), with various alkynes under the aforementioned conditions afforded monoinserted six-membered palladacycles, kappa(2)(C,N)-Pd(Lewis base)Br] (12-21), in high yield (81-91%) except for 14 (23%). The insertion reaction of VI with 2 equiv of dimethyl acetylenedicarboxylate (DMAD) and the insertion reaction of 12 with 1 equiv of DMAD in CH2Cl2 under ambient conditions resulted in the formation of a diinserted zwitterionic five-membered palladacycle, kappa(2)(C,C)Pd(2,6-lutidine)Br] (22), in 76% and 70% yields, respectively. Palladacycle 22 upon reaction with AgOTf in wet MeCN afforded the ionic palladacycle kappa(2)(C,C)Pd(2,6-lutidine)(H2O)]OTf] (23) in 78% yield. The ring size of the ``kappa(2)(C,N)Pd]'' unit in the structurally characterized diinserted palladacycles (1 center dot 2CH(2)Cl(2)center dot H2O, 2, 5, and 7), and monoinserted palladacycles (17, 18, and 20 center dot C7H8 H2O) is smaller than that anticipated for mono- and diinserted palladacycles, and this feature is mainly ascribed to the proclivity of III-XI to undergo ring contraction cum amine-imine tautomerization upon alkyne insertion. Palladacycle 22 represents the first diinserted product obtained in alkyne insertion reactions of kappa(2)(C,N)Pd(Lewis base)X] type palladarycles. The molecular structure of 22 center dot H2O determined by X-ray diffraction indicates that the positive charge on the guanidinium moiety is balanced by the negative charge on the palladium atom and thus represents the first structurally characterized zwitterionic palladacycle to be reported in alkyne insertion chemistry. Plausible mechanisms of formation of 12-21 and 22 have been outlined. The presence of more than one species in solution for some of the palladacycles in the series 1-7 and 12-21 was explained by invoking the C-N single-bond rotation of the CN3 unit of the guanidine moiety, while this process in conjunction with Pd-N(lutidine) bond rotation was invoked to explain the presence of four isomers of 15, as studied with the aid of variable-concentration H-1 NMR experiments carried out for 14 and 15.
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This paper presents the first microwave spectroscopic investigation on hexafluoroisopropanol (HFIP). A pulsed nozzle Fourier transform microwave spectrometer has been used to determine the rotational constants for HFIP as A = 2105.12166(18) MHz, B = 1053.99503(12) MHz, and C = 932.33959(13) MHz. In addition, five isotopologues of HFIP have been observed experimentally to determine the accurate structure of HFIP. The observed spectrum could be assigned to the most stable conformer of HFIP, called antiperiplanar. Available spectroscopic information and ab initio calculations on five prototype molecules helped in exploring the torsional behavior of molecules having a CF3-C-CF3 group. Two-dimensional potential energy surfaces have been analyzed for all molecules, which explained the presence/absence of doubling in the rotational transitions. With the help of natural bond orbital (NBO) analysis, reasons for the conformational preference of HFIP have been explained.
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Although several factors have been suggested to contribute to thermostability, the stabilization strategies used by proteins are still enigmatic. Studies on a recombinant xylanase from Bacilllus sp. NG-27 (RBSX), which has the ubiquitous (beta/alpha)(8)-triosephosphate isomerase barrel fold, showed that just a single mutation, V1L, although not located in any secondary structural element, markedly enhanced the stability from 70 degrees C to 75 degrees C without loss of catalytic activity. Conversely, the V1A mutation at the same position decreased the stability of the enzyme from 70 degrees C to 68 degrees C. To gain structural insights into how a single extreme N-terminus mutation can markedly influence the thermostability of the enzyme, we determined the crystal structure of RBSX and the two mutants. On the basis of computational analysis of their crystal structures, including residue interaction networks, we established a link between N-terminal to C-terminal contacts and RBSX thermostability. Our study reveals that augmenting N-terminal to C-terminal noncovalent interactions is associated with enhancement of the stability of the enzyme. In addition, we discuss several lines of evidence supporting a connection between N-terminal to C-terminal noncovalent interactions and protein stability in different proteins. We propose that the strategy of mutations at the termini could be exploited with a view to modulate stability without compromising enzymatic activity, or in general, protein function in diverse folds where N and C termini are in close proximity. Database The coordinates of RBSX, V1A and V1L have been deposited in the PDB database under the accession numbers 4QCE, 4QCF, and 4QDM, respectively
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El presente experimento fue realizado en la Estación Experimental La Compañía, San Marcos, departamento de Carazo, durante la época de postrera del año 1991 con el fin de evaluar el efecto de diferentes dosis de fertilizante y densidades de siembra sobre la cenosis de las malezas, el crecimiento y rendimiento del frijol común. Los tratamientos, consistieron en combinar tres dosis de fertilizante de la fórmula 1846-0 (Testigo, 1 y 2 qq/mz de fertilizante) con tres densidades de siembra (15, 30 y 45 semillas/m2). Los resultados obtenidos en este trabajó muestran que bajo las condiciones en las que fue realizado el experimento, la aplicación de 2 qq/mz del fertilizante y una densidad de siembra de 45 semillas/m2, produjo la menor abundancia y cobertura de malezas. A dosis de 1 qq/mz y densidad de 30 semillas/m2 se obtuvo el menor peso seco de malezas. Durante el ciclo del cultivo la mayor diversidad de especies se registró en la clase monocotiledónea. En cuanto al cultivo, aun cuando se observó una ligera tendencia a disminuir el rendimiento a medida que aumentó la dosis de fertilizante aplicada no hubo diferencias. En el caso de las densidades, se obtuvo el mayor número de ramas y vainas con 15 semillas/m2 y el mayor número de plantas, peso de mil granos y rendimiento con 45 semillas/m2, aunque en todos los casos las diferencias fueron mínimas.
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<正> 由国际理论与应用力学联合会(IUTAM)召开的4年一次的第18届国际理论与应用力学大会(ICTAM-18),于1992年8月22—28日在以色列海法市的以色列工业学院举行。大会选定的3个主题是:固体与结构力学中的不稳定性;海面力学与海气相互作用;生物力学。设置主题分会的目的是对力学中的某些重要领域做综合介绍,以强调这领域的重要性,或对新领域起提倡作用。
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El presente estudio consistió en la caracterización de la población de Coragyps atratus Bechstein (Zopilote) para diseñar estrategias de manejo y control de la especie que disminuyan los riesgo de peligro aviario en la zona de influencia del Aeropuerto Internacional Augusto C. Sandino en el municipio de Managua en un área de 1086.86 km2. Se emplearon diferentes métodos para la toma de datos que incluyeron conteos y observaciones por medios terrestres y aéreos. Los resultados obtenidos permiten determinar para cada población su comportamiento durante el día e identificación de la existencia de dos colonias principales de zopilotes; una en el sector Oeste del municipio de Managua correspondiente a las lagunas de Asososca y Nejapa, en la cual se estimaron 4384 individuos y otra en el sector Este, colindante con el municipio de Tipitapa con un estimado de 4,201 individuos. El patrón de desplazamiento en el sector Este fue de forma aleatoria contraria al sector Oeste que fue de forma gregaria con una trayectoria de vuelo que incluye el triángulo Nejapa – Chureca – Ciudad Sandino. La altura media a las que fueron observados los zopilotes en el sector Este fue de 261.18 m y 496.33 m en el sector Oeste siendo las horas de la mañana entre las 04:30am a las 12:00md las que reflejan mayor actividad en ambas colonias. Las aerovías más afectadas son las aerovías de salida o de llegada Nor-Este y las aerovías de llegada Nor-Oeste y Sur-Oeste, debido a su intersección con los sitios de alimentación de las aves. La disponibilidad de alimentos en cantidades suficientes parece ser el factor más importante que explica la permanencia de éstas aves en ambos sectores.
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Condena os que se declaram favoráveis ao retorno da capital do país para o Rio de Janeiro.
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Apoia o movimento em favor da representação política para o Distrito Federal, frisando que a primeira manifestação a esse respeito, na Cmara dos Deputados, foi de sua autoria.
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Coleção de editais de concursos públicos reunidos pela Coordenação de Relacionamento Pesquisa e Informação do Centro de Documentação da Cmara dos Deputados.