987 resultados para solution structures


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A principal feature of the crystal structures of tRNAs is an L-shaped tertiary conformation in which the aminoacyl acceptor stem and the anticodon stem are approximately perpendicular. However, the anticodon-acceptor interstem angle has not been precisely quantified in solution for any tRNA. Such a determination would represent an important test of the predicted global conformation of tRNAs in solution. To this end, we have constructed a yeast tRNA(Phe) heteroduplex RNA molecule in which the anticodon and acceptor stems of the tRNA have each been extended by approximately 70 base pairs. A comparison of the rotational decay times of the heteroduplex molecule and a linear control yields an interstem angle of 89 +/- 4 degrees in 4 mM magnesium chloride/100 microM spermine hydrochloride, essentially identical to the corresponding angle observed in the crystal under similar buffer and temperature conditions. The current approach is applicable to the study of a wide variety of RNA molecules that possess elements of nonhelical structure.

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A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

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Both the current economic situation in the construction sector and the continuous normative changes in the building area imply the use of new methodologies to enhance students’ competences in the degree of Building Engineer. The aim of this paper is to present, analyse and discuss the development of constructive workshops as a new teaching methodology used in the subject of Construction of Structures I at the University of Alicante to complement the constructive and technical knowledge acquired by our students and to enhance their communicative and representation skills essential for their professional practice in the future. The used methodology is based on the development of three-dimensional construction details (in groups of 3 or 4 students) to be shown in two A1-pannels exposed in the corridors of the Polytechnic School. Thus, students’ work approaches constructive problems in a global way by discussing simultaneously with teachers and other groups about the most suitable solution on each case. This contribution has multiperspective results and improves criticism of students in different areas, encouraging new learning strategies and active participation. What is more, on-line information and web applications have been used to prepare and organize this kind of workshops, allowing students to use new technologies as a complementary learning methodology. In conclusion, the use of these new workshops in the Degree of Building Engineer stimulates an interactive class versus a traditional lecture where the participative groups´ attitude and the development of oral presentations dissolve the traditional boundaries regarding public communication skills of the students in the Degree.

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Thesis (Ph.D.)--University of Washington, 2016-06

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New tin(IV) complexes of empirical formula, Sn(NNS)I-3 (NNS = anionic forms of the 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate) have been prepared and characterized by a variety of physico-chemical techniques. In the solid state, the Schiff bases exist as the thione tautomer but in solution and in the presence of tin(IV) iodide they convert to the thiol tautomer and coordinate to the tin atom in their deprotonated thiolate forms. The structures of the free ligand, Hqaldsbz and its triiodotin(IV) complex, [Sn(qaldsbz)I-3] have been determined by X-ray diffraction. The complex, [Sn(qaldsbz)I-3] has a distorted octahedral structure with the Schiff base coordinated to the tin atom as a uninegatively charged tridentate chelating agent via the quinoline nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. The three iodo ligands are coordinated meridionally to the tin atom. The distortion from an ideal octahedral geometry of [Sn(qaldsbz)I-3] is attributed to the restricted bite size of the tridentate Schiff base ligand. (C) 2004 Elsevier Ltd. All rights reserved.

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The muO-conotoxins are an intriguing class of conotoxins targeting various voltage-dependent sodium channels and molluscan calcium channels. In the current study, we have shown MrVIA and MrVIB to be the first known peptidic inhibitors of the transient tetrodotoxin-resistant (TTX-R) Na+ current in rat dorsal root ganglion neurons, in addition to inhibiting tetrodotoxin-sensitive Na+ currents. Human TTX-R sodium channels are a therapeutic target for indications such as pain, highlighting the importance of the muO-conotoxins as potential leads for drug development. Furthermore, we have used NMR spectroscopy to provide the first structural information on this class of conotoxins. MrVIA and MrVIB are hydrophobic peptides that aggregate in aqueous solution but were solubilized in 50% acetonitrile/water. The three-dimensional structure of MrVIB consists of a small beta-sheet and a cystine knot arrangement of the three-disulfide bonds. It contains four backbone loops between successive cysteine residues that are exposed to the solvent to varying degrees. The largest of these, loop 2, is the most disordered part of the molecule, most likely due to flexibility in solution. This disorder is the most striking difference between the structures of MrVIB and the known delta- and omega-conotoxins, which along with the muO-conotoxins are members of the O superfamily. Loop 2 of omega-conotoxins has previously been shown to contain residues critical for binding to voltage-gated calcium channels, and it is interesting to speculate that the flexibility observed in MrVIB may accommodate binding to both sodium and molluscan calcium channels.

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A large number of macrocyclic miniproteins with diverse biological activities have been isolated from the Rubiaceae, Violaceae, and Cucurbitaceae plant families in recent years. Here we report the three-dimensional structure determined using H-1 NMR spectroscopy and demonstrate potent insecticidal activity for one of these peptides, kalata B2. This peptide is one of the major components of an extract from the leaves of the plant Oldenlandia affinis. The structure consists of a distorted triple-stranded beta-sheet and a cystine knot arrangement of the disulfide bonds and is similar to those described for other members of the cyclotide family. The unique cyclic and knotted nature of these molecules makes them a fascinating example of topologically complex proteins. Examination of the sequences reveals that they can be separated into two subfamilies, one of which contains a larger number of positively charged residues and has a bracelet-like circularization of the backbone. The second subfamily contains a backbone twist due to a cis-peptidyl-proline bond and may conceptually be regarded as a molecular Mobius strip. Kalata B2 is the second putative member of the Mobius cyclotide family to be structurally characterized and has a cis-peptidyl-proline bond, thus validating the suggested name for this subfamily of cyclotides. The observation that kalata B2 inhibits the growth and development of Helicoverpa armigera larvae suggests a role for the cyclotides in plant defense. A comparison of the sequences and structures of kalata B1 and B2 provides insight into the biological activity of these peptides.

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Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO7 decahedra and NbO6 octahedra in the reactant Nb2O5, yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb2O5 powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na2Nb2O6 center dot(2)/3H2O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO3 Cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb2O5. This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO6 octahedra, and then the microporous fibers crystallize and grow by assembling NbO6 octahedra or clusters of NbO6 octahedra and NaO6 units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

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Local structures around host Ce and dopant Y cations in 10 mol% Y2O3 doped ceria solid solutions have been investigated by room and high temperature EXAFS spectroscopy. The results show that the local structures around the Cc cation in doped ceria samples are similar to that in the fluorite CeO2 structure though the coordination numbers of Ce-O tend to be smaller than 8. The local structures around Y cation, however, are significantly different from those around Ce cation, and show more resemblance to that around Y cation in the C-type Y2O3 Structure. A more accurate description of the local structures around Y cation in doped ceria was given by analyzing Y-K edge EXAFS spectra based on the C-type Y2O3 structure. (c) 2006 Elsevier B.V. All rights reserved.

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A numerical continuation method has been carried out seeking solutions for two distinct flow configurations, planar Couette flow (PCF) and laterally heated flow in a vertical slot (LHF). We found that the spanwise vortex solution in LHF identifies a new solution in PCF. The vortical structure of our new solution has the shape of a hairpin observed ubiquitously in high-Reynolds-number turbulent flow, and we believe this discovery may provide the paradigm for a hierarchical organization of coherent structures in turbulent shear layers.

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We present a simple optical chemsensor device based on tilted Bragg grating structures ultraviolet-inscribed in conventional multimode fiber and sensitized by a hydrofluoric (HF)-etching treatment. The transition behaviors of fiber Bragg gratings (FBGs) from normal to tilted structures and their spectral evolution under HF-etching have been studied. The etched devices have been used to measure the concentrations of sugar solution, showing a potential capability of detecting concentration changes as small as 0.5%, which is an order of magnitude lower than that of previously reported FBG sensors in single-mode fiber.

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This thesis demonstrates that the use of finite elements need not be confined to space alone, but that they may also be used in the time domain, It is shown that finite element methods may be used successfully to obtain the response of systems to applied forces, including, for example, the accelerations in a tall structure subjected to an earthquake shock. It is further demonstrated that at least one of these methods may be considered to be a practical alternative to more usual methods of solution. A detailed investigation of the accuracy and stability of finite element solutions is included, and methods of applications to both single- and multi-degree of freedom systems are described. Solutions using two different temporal finite elements are compared with those obtained by conventional methods, and a comparison of computation times for the different methods is given. The application of finite element methods to distributed systems is described, using both separate discretizations in space and time, and a combined space-time discretization. The inclusion of both viscous and hysteretic damping is shown to add little to the difficulty of the solution. Temporal finite elements are also seen to be of considerable interest when applied to non-linear systems, both when the system parameters are time-dependent and also when they are functions of displacement. Solutions are given for many different examples, and the computer programs used for the finite element methods are included in an Appendix.

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In this second talk on dissipative structures in fiber applications, we overview theoretical aspects of the generation, evolution and characterization of self-similar parabolic-shaped pulses in fiber amplifier media. In particular, we present a perturbation analysis that describes the structural changes induced by third-order fiber dispersion on the parabolic pulse solution of the nonlinear Schrödinger equation with gain. Promising applications of parabolic pulses in optical signal post-processing and regeneration in communication systems are also discussed.

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In this second talk on dissipative structures in fiber applications, we overview theoretical aspects of the generation, evolution and characterization of self-similar parabolic-shaped pulses in fiber amplifier media. In particular, we present a perturbation analysis that describes the structural changes induced by third-order fiber dispersion on the parabolic pulse solution of the nonlinear Schrödinger equation with gain. Promising applications of parabolic pulses in optical signal post-processing and regeneration in communication systems are also discussed.