133 resultados para Bonding quality
Resumo:
We consider optimal power allocation policies for a single server, multiuser system. The power is consumed in transmission of data only. The transmission channel may experience multipath fading. We obtain very efficient, low computational complexity algorithms which minimize power and ensure stability of the data queues. We also obtain policies when the users may have mean delay constraints. If the power required is a linear function of rate then we exploit linearity and obtain linear programs with low complexity.
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The self-assembly of p-pyridyl-ended oligo-p-phenylenevinylenes (OPVs) in ethanol leads to the formation of either hollow or solid microrods. The corresponding protonated OPVs with n-butyl chains induce transparent gelation and also gel phase crystallization owing to various synergistic noncovalent interactions. The chloride ion-selective gelation, AIEE and stimuli responsiveness of the gel are also observed.
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Longitudinal relaxation due to cross-correlation between dipolar ((HN-1H alpha)-H-1) and amide-proton chemical shift anisotropy (H-1(N) CSA) has been measured in a model tripeptide Piv-(L)Pro-(L)Pro-(L)Phe-OMe. The peptide bond across diproline segment is known to undergo cis/trans isomerization and only in the cis form does the lone Phe amide-proton become involved in intramolecular hydrogen bonding. The strength of the cross correlated relaxation interference is found to be significantly different between cis and trans forms, and this difference is shown as an influence of intramolecular hydrogen bonding on the amide-proton CSA. (C) 2015 Elsevier B.V. All rights reserved.
Resumo:
The gas-phase infrared spectra of 1,2-ED and 1,4-BD have been, recorded at three different temperatures using a multipass gas cell of 6 m optical path length. DFT calculation has also been carried out using 6-311++G** and aug-cc-pVDZ basis sets to look for the existence of intramolecular hydrogen bonding, in them from the red shift and infrared absorption intensity enhancement of the bonded O-H band compared to that of the free O-H hand. Equilibrium population analysis With 10 conformers of 1,2-ED and 1,4-BD at experimental temperatures were-carried out for the reconstruction of the Observed vibrational spectra at that temperature,using standard statistical relationships. The most abundant conformer at experimental temperatures, was identified. In 1,2-ED a red shift of 45 cm(-1) in the intramolecularly interacting O-H stretching vibrational band position and no significant intensity enhancement compared to that of-the free O-H have been observed. On the contrary, in one of the hydrogen bonded conformers of 1,4-BD, a 124 cm(-1) red shift in the O-H stretching frequency and 8.5 times-intensity enhancement for the ``bonded'' O-H compared to that of the ``free'' O-H is seen. On the basis of this comparative study, we have concluded that strong intramolecular hydrogen bonding exists in 1,4-BD. But there appears, to be weak intramolecular hydrogen bonding in 1,2-ED at temperatures of 303, 313, and 323 Km the gas phase We have found that most stable hydrogen-bonded conformers of 1,4-BD are less populated than some of the non-hydrogen-bonded conformers. Even for the 1,4-BD, the relative population of the g'GG'Gt conformer, which has a strong intramolecular,hydrogen bond, is less than what is predicted. Perhaps the intramolecular hydrogen bond plays a less Significant role in the relative stability,of the various Conformers than what has been predicted from calculations and prevails in the literature.
Resumo:
Intramolecular S center dot center dot center dot O chalcogen bonding and its potential to lock molecular conformation have been examined in the crystal forms of sulfamethizole, a sulfonamide antibiotic. Molecular complexes of sulfamethizole, including salts and cocrystal, have been synthesized, and their crystal structures were analyzed in order to examine the possible conformational preferences of the molecule in various ionic states and supramolecular environments (neutral/cocrystal, anionic salt, and cationic salt forms). The electrostatic potential mapped on Hirshfeld surfaces generated for these crystal forms provides insights into the possible binding modes of the drug in different environments. Further, the observed conformation locking feature has been rationalized in terms of the experimental charge density features of the intramolecular S center dot center dot O chalcogen bonding in sulfamethizole. The study quantitatively illustrates and rationalizes an intriguing case of a local minimum of molecular conformation being exclusively preferred over the global minimum, as it facilitates more efficient intermolecular interactions in a supramolecular environment.
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We demonstrate in here a powerful scalable technology to synthesize continuously high quality CdSe quantum dots (QDs) in supercritical hexane. Using a low cost, highly thermally stable Cd-precursor, cadmium deoxycholate, the continuous synthesis is performed in 400 mu m ID stainless steel capillaries resulting in CdSe QDs having sharp full-width-at-half-maxima (23 nm) and high photoluminescence quantum yields (45-55%). Transmission electron microscopy images show narrow particles sizes distribution (sigma <= 5%) with well-defined crystal lattices. Using two different synthesis temperatures (250 degrees C and 310 degrees C), it was possible to obtain zinc blende and wurtzite crystal structures of CdSe QDs, respectively. This synthetic approach allows achieving substantial production rates up to 200 mg of QDs per hour depending on the targeted size, and could be easily scaled to gram per hour.
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An organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole, has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystallizing in a non-centrosymmetric space group (Z' = 1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (Z' = 2). Topological analysis based on QTAIM clearly brings out the dominance of the chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms.
Resumo:
Experimental charge density analysis combined with the quantum crystallographic technique of X-ray wavefunction refinement (XWR) provides quantitative insights into the intra-and intermolecular interactions formed by acetazolamide, a diuretic drug. Firstly, the analysis of charge density topology at the intermolecular level shows the presence of exceptionally strong interaction motifs such as a DDAA-AADD (D-donor, A-acceptor) type quadruple hydrogen bond motif and a sulfonamide dimer synthon. The nature and strength of intra-molecular S center dot center dot center dot O chalcogen bonding have been characterized using descriptors from the multipole model (MM) and XWR. Although pure geometrical criteria suggest the possibility of two intra-molecular S center dot center dot center dot O chalcogen bonded ring motifs, only one of them satisfies the ``orbital geometry'' so as to exhibit an interaction in terms of an electron density bond path and a bond critical point. The presence of `s-holes' on the sulfur atom leading to the S center dot center dot center dot O chalcogen bond has been visualized on the electrostatic potential surface and Laplacian isosurfaces close to the `reactive surface'. The electron localizability indicator (ELI) and Roby bond orders derived from the `experimental wave function' provide insights into the nature of S center dot center dot center dot O chalcogen bonding.
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In this paper we present a depth-guided photometric 3D reconstruction method that works solely with a depth camera like the Kinect. Existing methods that fuse depth with normal estimates use an external RGB camera to obtain photometric information and treat the depth camera as a black box that provides a low quality depth estimate. Our contribution to such methods are two fold. Firstly, instead of using an extra RGB camera, we use the infra-red (IR) camera of the depth camera system itself to directly obtain high resolution photometric information. We believe that ours is the first method to use an IR depth camera system in this manner. Secondly, photometric methods applied to complex objects result in numerous holes in the reconstructed surface due to shadows and self-occlusions. To mitigate this problem, we develop a simple and effective multiview reconstruction approach that fuses depth and normal information from multiple viewpoints to build a complete, consistent and accurate 3D surface representation. We demonstrate the efficacy of our method to generate high quality 3D surface reconstructions for some complex 3D figurines.
Resumo:
Thermal interface materials (TIMs) form a mechanical and thermal link between a heat source and a heat sink. Thus, they should have high thermal conductivity and high compliance to efficiently transfer heat and accommodate any differential strain between the heat source and the sink, respectively. This paper reports on the processing and the characterization of potential metallic TIM composite solders comprising of Cu, a high conductivity phase, uniformly embedded in In matrix, a highly compliant phase. We propose the fabrication of such a material by a two-step fabrication technique comprising of liquid phase sintering (LPS) followed by accumulative roll bonding (ARB). To demonstrate the efficacy of the employed two-step processing technique, an In-40 vol. % Cu composite solder was produced first using LPS with short sintering periods (30 or 60 s at 160 degrees C) followed by ARB up to five passes, each pass imposing a strain of 50%. Mechanical response and electrical and thermal conductivities of the fabricated samples were evaluated. It was observed that processing through ARB homogenizes the distribution of Cu in an In matrix, disintegrates the agglomerates of Cu powders, and also significantly increases thermal and electrical conductivities, almost attaining theoretically predicted values, without significantly increasing the flow stress. Furthermore, the processing technique also allows the insertion of desired foreign species, such as reduced graphene oxide, in In-Cu for further enhancing a target property, such as electrical conductivity.
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Background: Animals that hoard food to mediate seasonal deficits in resource availability might be particularly vulnerable to climate-mediated reductions in the quality and accessibility of food during the caching season. Central-place foragers might be additionally impacted by climatic constraints on their already restricted foraging range. Aims: We sought evidence for these patterns in a study of the American pika (Ochotona princeps), a territorial, central-place forager sensitive to climate. Methods: Pika food caches and available forage were re-sampled using historical methods at two long-term study sites, to quantify changes over two decades. Taxa that changed in availability or use were analysed for primary and secondary metabolites. Results: Both sites trended towards warmer summers, and snowmelt trended earlier at the lower latitude site. Graminoid cover increased at each site, and caching trends appeared to reflect available forage rather than primary metabolites. Pikas at the lower latitude site preferred species higher in secondary metabolites, known to provide higher-nutrient winter forage. However, caching of lower-nutrient graminoids increased in proportion with graminoid availability at that site. Conclusions: If our results represent trends in climate, cache quality and available forage, we predict that pikas at the lower latitude site will soon face nutritional deficiencies.
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An efficient buffer layer scheme has been designed to address the issue of curvature management during metalorganic chemical vapour deposition growth of GaN on Si (111) substrate. This is necessary to prevent cracking of the grown layer during post-growth cooling down from growth temperature to room temperature and to achieve an allowable bow (<40 m) in the wafer for carrying out lithographic processes. To meet both these ends simultaneously, the stress evolution in the buffer layers was observed carefully. The reduction in precursor flow during the buffer layer growth provided better control over curvature evolution in the growing buffer layers. This has enabled the growth of a suitable high electron mobility transistor (HEMT) stack on 2'' Si (111) substrate of 300 m thickness with a bow as low as 11.4 m, having a two-dimensional electron gas (2DEG) of mobility, carrier concentration, and sheet resistance values 1510 cm(2)/V-s, 0.96 x 10(13)/cm(2), and 444 /, respectively. Another variation of similar technique resulted in a bow of 23.4 m with 2DEG mobility, carrier concentration, and sheet resistance values 1960 cm(2)/V-s, 0.98 x 10(13)/cm(2), and 325 /, respectively.
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The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.