Typical aromatic noncovalent interactions in proteins: A theoretical study using phenylalanine

A systematic study of CH ··· π, OH ··· π, NH ··· π, and cation ··· π interactions has been done using complexes of phenylalanine in its cationic, anionic, neutral, and zwitterionic forms with CH₄, H₂O, NH₃, and NH at B3LYP, MP2, MPWB1K, and M06‐2X levels of theory. All noncovalent interactions are identified by the presence of bond critical points (bcps) of electron density (ρ( r )) and the values of ρ( r ) showed linear relationship to the binding energies (E_total). The estimated E_total from supermolecule, fragmentation, and ρ( r ) approaches suggest that cation ··· π interactions are in the range of 36 to 46 kcal/mol, whereas OH ··· π, and NH ··· π interactions have comparable strengths of 6 to 27 kcal/mol and CH ··· π interactions are the weakest (0.62–2.55 kcal/mol). Among different forms of phenylalanine, cationic form generally showed the highest noncovalent interactions at all levels of theory. Cooperativity of multiple interactions is analyzed on the basis of ρ( r ) at bcps which suggests that OH ··· π and NH ··· π interactions show positive, whereas CH ··· π and cation ··· π interactions exhibit negative cooperativity with respect to the side chain hydrogen bond interactions. In general, side chain interactions are strengthened as a result of aromatic interaction. Solvation has no significant effect on the overall geometry of the complex though slight weakening of noncovalent interactions by 1–2 kcal/mol is observed. An assessment of the four levels of theory studied herein suggests that both MPWB1K and M06‐2X give better performance for noncovalent interactions. The results also support the fact that B3LYP is inadequate for the study of weak interactions. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009     

Reevaluation of the mechanism of the amination of aryl halides catalyzed by BINAP-ligated palladium complexes

Two previous mechanistic studies of the amination of aryl halides catalyzed by palladium complexes of 1,1'-binaphthalene-2,2'-diylbis(diphenylphosphine) (BINAP) are reexamined by the authors of both studies. This current work includes a detailed study of the identity of the BINAP-ligated palladium complexes present in reactions of amines with aryl halides and rate measurements of these catalytic reactions initiated with pure precatalysts and precatalysts generated in situ from [Pd2(dba)3] and BINAP. This work reveals errors in both previous studies, and we describe our current state of understanding of the mechanism of this synthetically important transformation. 31P NMR spectroscopy shows that several palladium(0) species are present in the catalytic system when the catalyst is generated in situ from [Pd2(dba)3] and BINAP, and that at least two of these complexes generate catalytic intermediates. Further, these spectroscopic studies and accompanying kinetic data demonstrate that an apparent positive order in the concentration of amine during reactions of secondary amines is best attributed to catalyst decomposition. Kinetic studies with isolated precatalysts show that the rates of the catalytic reactions are independent of the identity and the concentration of amine, and studies with catalysts generated in situ show that the rates of these reactions are independent of the concentration of amine. Further, reactions catalyzed by [Pd(BINAP)2] with added BINAP are found to be first-order in bromoarene and inverse first-order in ligand, in contrast to previous work indicating zero-order kinetics in both. These data, as well as a correlation between the decay of bromobenzene in the catalytic reaction and the predicted decay of bromobenzene from rate constants of studies on stoichiometric oxidative addition, are consistent with a catalytic process in which oxidative addition of the bromoarene occurs to [Pd(BINAP)] prior to coordination of amine and in which [Pd(BINAP)2], which generates [Pd(BINAP)] by dissociation of BINAP, lies off the cycle. By this mechanism, the amine and base react with [Pd(BINAP)(Ar)(Br)] to form an arylpalladium amido complex, and reductive elimination from this amido complex forms the arylamine.     

Nonlocalized modulation of periodic reaction diffusion waves: The Whitham equation

In a companion paper, we established nonlinear stability with detailed diffusive rates of decay of spectrally stable periodic traveling-wave solutions of reaction diffusion systems under small perturbations consisting of a nonlocalized modulation plus a localized (L ¹) perturbation. Here, we determine time-asymptotic behavior under such perturbations, showing that solutions consist of a leading order of a modulation whose parameter evolution is governed by an associated Whitham averaged equation.     

Shock-Wave Consolidation of Nanostructured Bismuth Telluride Powders

Nanostructured thermoelectric powders can be produced using a variety of techniques. However, it is very challenging to build a bulk material from these nanopowders without losing the nanostructure. In the present work, nanostructured powders of the bismuth telluride alloy system are obtained in kilogram quantities via a gas atomization process. These powders are characterized using a variety of methods including scanning electron microscopy, transition electron microscopy, and x-ray diffraction analysis. Then the powders are consolidated into a dense bulk material using a shock-wave consolidation technique whereby a nanopowder-containing tube is surrounded by explosives and then detonated. The resulting shock wave causes rapid fusing of the powders without the melt and subsequent grain growth of other techniques. We describe the test setup and consolidation results.     

Pseudo-Parallel Datapath Structure for Power Optimal Implementation of 128-pt FFT/IFFT for WPAN

An optimal implementation of 128-Pt FFT/IFFT for low power IEEE 802.15.3a WPAN using pseudo-parallel datapath structure is presented, where the 128-Pt FFT is devolved into 8-Pt and 16-Pt FFTs and then once again by devolving the 16-Pt FFT into 4×4 and 2×8. We analyze 128-Pt FFT/IFFT architecture for various pseudo-parallel 8-Pt and 16-Pt FFTs and an optimum datapath architecture is explored. It is suggested that there exists an optimum degree of parallelism for the given algorithm. The analysis demonstrated that with a modest increase in area one can achieve significant reduction in power. The proposed architectures complete one parallel-to-parallel (i.e., when all input data are available in parallel and all output data are generated in parallel) 128-point FFT computation in less than 312.5 ns and thereby meet the standard specification. The relative merits and demerits of these architectures have been analyzed from the algorithm as well as implementation point of view. Detailed power analysis of each of the architectures with a different number of data paths at block level is described. We found that from power perspective the architecture with eight datapaths is optimum. The core power consumption with optimum case is 60.6 MW which is only less than half of the latest reported 128-point FFT design in 0.18u technology. Furthermore, a Single Event Upset (SEU) tolerant scheme for registers is also explored. The SEU tolerant scheme will not affect the performance, however, there is an increase power consumption of about 42 percent. Apart from the low power consumption, the advantages of the proposed architectures include reduced hardware complexity, regular data flow and simple counter based control.     

Studies of nonlinear optical properties of PicoGreen dye using Z-scan technique

In this paper we study the nonlinear optical properties of PicoGreen dye. The investigations involve the single-beam Z-scan technique and measurements were carried out at different incident intensities. Both open and closed aperture Z-scan techniques were performed at 532 nm and it was found that the dye exhibited a reverse saturable absorption with significant nonlinear absorption coefficient and intensity-dependent negative nonlinear refraction coefficient, indicating self-defocusing phenomena. The third-order nonlinear susceptibility and optical limiting threshold were also measured.     

A Review on Characterization Techniques for Carbon Quantum Dots and Their Applications in Agrochemical Residue Detection

Journal of Fluorescence - Carbon quantum dots (CQDs) have emerged as one of the most promising nanomaterials in the carbon nanostructures family in recent years due to their low toxicity, simple...     

A triple-mode hexa-standard reconfigurable TI cross-coupled ΣΔ modulator

Hardware reconfigurability is an attractive solution for modern multi-standard wireless systems. This paper analyses the performance and implementation of an efficient triple-mode hexa-standard reconfigurable sigma-delta (∑?) modulator designed for six different wireless communication standards. Enhanced noise-shaping characteristics and increased digitisation rate, obtained by time-interleaved cross-coupling of ∑? paths, have been utilised for the modulator design. Power/hardware efficiency and the capability to acclimate the requirements of wide hexa-standard specifications are achieved by introducing an advanced noise-shaping structure, the dual-extended architecture. Simulation results of the proposed architecture using Hspice shows that the proposed modulator obtains a peak signal-to-noise ratio of 83.4/80.2/67.8/61.5/60.8/51.03 dB for hexa-standards, i.e. GSM????????/Bluetooth/GPS/WCDMA/WLAN/WiMAX standards with significantly less hardware and low operating frequency. The proposed architecture is implemented in 45 nm CMOS process using a 1 V supply and 0.7 V input range with a power consumption of 1.93 mW. Both architectural- and transistor-level simulation results prove the effectiveness and feasibility of this architecture to accomplish multi-standard cellular communication characteristics.     

Impact of glucose on the electrochemical performance of nano-LiCoPO4 cathode for Li-ion batteries

LiCoPO₄ nanoparticles were synthesized by standard and glucose-assisted sol–gel methods for use as cathodes in lithium-ion batteries. The effect of glucose on the characteristics of the formed LiCoPO₄ nanoparticles was investigated by TGA, XRD, and FESEM. The TGA results indicated gradual decomposition of glucose in the temperature range 400–700 °C. The XRD results showed olivine phases in addition to small traces of Co₃O₄ for samples calcined at 400 °C while pure olivine phases were confirmed for the 700 °C calcined samples. The addition of glucose strongly suggests promotion of LiCoPO₄ crystallization, as revealed by FESEM studies. The electrochemical measurements pertaining to LiCoPO₄ samples calcined at 400 °C suggested an enhancement of initial discharge capacity from 103.3 to 144.6 mAh/g for the standard and glucose-based electrodes, respectively. Further, the effects of conductive additive and excess lithium on the electrochemical performance of LiCoPO₄ have also been investigated.     

Chemoselective Staudinger-phosphite reaction of symmetrical glycosyl-phosphites with azido-peptides and polygycerols

In this paper we present the synthesis of glyco-phosphoramidate conjugates as easily accessible analogs of glyco-phosphorous esters via the Staudinger-phosphite reaction. This protocol takes advantage of synthetically accessible symmetrical carbohydrate phosphites in good overall yields, in which ethylene or propylene linkers can be introduced between phosphorous and galactose or lactose moieties. The phosphites were finally applied for the chemoselective reaction with azido-peptides and polyazido(poly)glycerols.