Discrimination of alpha-Amino Acids Using Green Tea Flavonoid (-)-Epigallocatechin Gallate as a Chiral Solvating Agent

We report a special, hitherto-unexplored property of (-)-epigallocatechin gallate (EGCG) as a chiral solvating agent for enantiodiscrimination of alpha-amino acids in the polar solvent DMSO. This phenomenon has been investigated by H-1 NMR spectroscopy. The mechanism of the interaction property of EGCG with alpha-amino acids has been understood as arising out of hydrogen-bonded noncovalent interactions, where the -OH groups of two phenyl rings of EGCG play dominant roles. The conversion of the enantiomeric mixture into diastereomers yielded well-resolved peaks for D and L amino acids permitting the precise measurement of enantiomeric composition. Often one encounters complex situations when the spectra are severely overlapped or partially resolved hampering the testing of enantiopurity and the precise measurement of enantiomeric excess (ee). Though higher concentration of EGCG yielded better discrimination, the use of lower concentration being economical, we have exploited an appropriate 2D NMR experiment in overcoming such problems. Thus, in the present study we have successfully demonstrated the utility of the bioflavonoid (-)-EGCG, a natural product as a chiral solvating agent for the discrimination of large number of alpha-amino acids in a polar solvent DMSO. Another significant advantage of this new chiral sensing agent is that it is a natural product and does not require tedious multistep synthesis unlike many other chiral auxiliaries.

Nucleation dynamics and pool boiling characteristics of high pressure refrigerant using thermochromic liquid crystals

This paper reports an experimental investigation of oscillating temperature field beneath a single isolated nucleation site using a non-invasive TLC (thermochromic liquid crystal) based thermography technique. Empirical correlations are presented to demonstrate the influence of system pressure and wall heat flux on different ebullition characteristics in the nucleate pool boiling regime of refrigerant R-134a. TLC transient response and two-phase flow structure are captured using synchronized, high resolution imaging. It is observed that the area of influence of nucleation site exhibits a two-part distinct transient behavior during the bubble growth period and broadens to a maximum of 1.57 times the bubble diameter at the instant of bubble departure. This is accompanied by a sharp fall of 2.5 degrees C in the local excess temperature at the nucleation site, which results in momentary augmentation (similar to 40%) in the local heat transfer coefficient at the nucleation origin. The enhanced heat transfer rate observed during the bubble peel-off event is primarily due to transient micro-convection in the wake of the retreating bubble. Further, the results indicate that a slight increase in system pressure from 813.6 to 882.5 kPa has no considerable effect on either the wall superheat or the overall heat transfer coefficient and ebullition frequency. In addition, correlations have been obtained for bubble Reynolds number, Jackob number and the dimensionless bubble generation frequency in terms of modified boiling number.

Predicting the extremes of Indian summer monsoon rainfall with coupled ocean-atmosphere models

An analysis of the retrospective predictions by seven coupled ocean atmosphere models from major forecasting centres of Europe and USA, aimed at assessing their ability in predicting the interannual variation of the Indian summer monsoon rainfall (ISMR), particularly the extremes (i.e. droughts and excess rainfall seasons) is presented in this article. On the whole, the skill in prediction of extremes is not bad since most of the models are able to predict the sign of the ISMR anomaly for a majority of the extremes. There is a remarkable coherence between the models in successes and failures of the predictions, with all the models generating loud false alarms for the normal monsoon season of 1997 and the excess monsoon season of 1983. It is well known that the El Nino and Southern Oscillation (ENSO) and the Equatorial Indian Ocean Oscillation (EQUINOO) play an important role in the interannual variation of ISMR and particularly the extremes. The prediction of the phases of these modes and their link with the monsoon has also been assessed. It is found that models are able to simulate ENSO-monsoon link realistically, whereas the EQUINOO-ISMR link is simulated realistically by only one model the ECMWF model. Furthermore, it is found that in most models this link is opposite to the observed, with the predicted ISMR being negatively (instead of positively) correlated with the rainfall over the western equatorial Indian Ocean and positively (instead of negatively) correlated with the rainfall over the eastern equatorial Indian Ocean. Analysis of the seasons for which the predictions of almost all the models have large errors has suggested the facets of ENSO and EQUINOO and the links with the monsoon that need to be improved for improving monsoon predictions by these models.

A summer monsoon pump to keep the Bay of Bengal salty

The Bay of Bengal receives a large influx of freshwater from precipitation and river discharge. Outflow of excess freshwater and inflow of saltier water is required to prevent the bay from freshening. Relatively fresh water flows out of the bay along its boundaries and inflow of saltier water occurs via the Summer Monsoon Current (SMC), which flows eastward from the Arabian Sea into the bay. This saltier water, however, slides under the lighter surface water of the bay. Maintaining the salt balance of the bay therefore demands upward mixing of this saltier, subsurface water. Here, we show that an efficient mechanism for this mixing is provided by upward pumping of saltier water in several bursts during the summer monsoon along the meandering path of the SMC. Advection by currents can then take this saltier water into the rest of the basin, allowing the bay to stay salty despite a large net freshwater input.

Role of Fly Ash Pozzolanic Reactions in Controlling Fluoride Release from Phosphogypsum

Phosphogypsum is added to building materials to accelerate fly ash pozzolanic reaction and contributes to early strength development of concrete. The release of unacceptable fluoride levels by phoshogypsum on contact with water is a major impediment in its usage to manufacture building products because excess fluoride consumption causes dental and skeletal fluorosis. This paper examines the efficacy of fly ash pozzolanic reactions in controlling fluoride release by phosphogypsum. Fly ash (FA), sand (S), lime (L), and phosphogypsum (G) (FA-S-L-G) slurries are cured for various periods, and the fluoride released by the mix is monitored as a function of time. A substantial reduction in fluoride release was observed and is attributed to entrapment of phosphogypsum particles in a cementious matrix formed by fly ash-lime pozzolanic reactions coupled with consumption of fluoride in formation of insoluble compounds. The compressive strength developed by compacted FA-S-L-G specimens with time was observed to be a three-stage process; maximum strength mobilization occurred during 14 and 28days of curing at room temperature. Exposure of the compacted FA-S-L-G specimens to acidic and alkaline environments for 9 days did not impact their compressive strengths. (C) 2013 American Society of Civil Engineers.

The effect of cell size and channel density on neuronal information encoding and energy efficiency

Identifying the determinants of neuronal energy consumption and their relationship to information coding is critical to understanding neuronal function and evolution. Three of the main determinants are cell size, ion channel density, and stimulus statistics. Here we investigate their impact on neuronal energy consumption and information coding by comparing single-compartment spiking neuron models of different sizes with different densities of stochastic voltage-gated Na+ and K+ channels and different statistics of synaptic inputs. The largest compartments have the highest information rates but the lowest energy efficiency for a given voltage-gated ion channel density, and the highest signaling efficiency (bits spike(-1)) for a given firing rate. For a given cell size, our models revealed that the ion channel density that maximizes energy efficiency is lower than that maximizing information rate. Low rates of small synaptic inputs improve energy efficiency but the highest information rates occur with higher rates and larger inputs. These relationships produce a Law of Diminishing Returns that penalizes costly excess information coding capacity, promoting the reduction of cell size, channel density, and input stimuli to the minimum possible, suggesting that the trade-off between energy and information has influenced all aspects of neuronal anatomy and physiology.

Effect of hinged leaflets on vortex pair generation

We experimentally study the effect of having hinged leaflets at the jet exit on the formation of a two-dimensional counter-rotating vortex pair. A piston-cylinder mechanism is used to generate a starting jet from a high-aspect-ratio channel into a quiescent medium. For a rigid exit, with no leaflets at the channel exit, the measurements at a central plane show that the trailing jet in the present case is never detached from the vortex pair, and keeps feeding into the latter, unlike in the axisymmetric case. Passive flexibility is introduced in the form of rigid leaflets or flaps that are hinged at the exit of the channel, with the flaps initially parallel to the channel walls. The experimental arrangement closely approximates the limiting case of a free-to-rotate rigid flap with negligible structural stiffness, damping and flap inertia, as these limiting structural properties permit the largest flap openings. Using this arrangement, we start the flow and measure the flap kinematics and the vorticity fields for different flap lengths and piston velocity programs. The typical motion of the flaps involves a rapid opening and a subsequent more gradual return to its initial position, both of which occur when the piston is still moving. The initial opening of the flaps can be attributed to an excess pressure that develops in the channel when the flow starts, due to the acceleration that has to be imparted to the fluid slug between the flaps. In the case with flaps, two additional pairs of vortices are formed because of the motion of the flaps, leading to the ejection of a total of up to three vortex pairs from the hinged exit. The flaps' length (L-f) is found to significantly affect flap motions when plotted using the conventional time scale L/d, where L is the piston stroke and d is the channel width. However, with a newly defined time scale based on the flap length (L/L-f), we find a good collapse of all the measured flap motions irrespective of flap length and piston velocity for an impulsively started piston motion. The maximum opening angle in all these impulsive velocity program cases, irrespective of the flap length, is found to be close to 15 degrees. Even though the flap kinematics collapses well with L/L-f, there are differences in the distribution of the ejected vorticity even for the same L/L-f. Such a redistribution of vorticity can lead to important changes in the overall properties of the flow, and it gives us a better understanding of the importance of exit flexibility in such flows.

Does lean imply green?: a study of the power performance implications of Java runtime bloat

The presence of software bloat in large flexible software systems can hurt energy efficiency. However, identifying and mitigating bloat is fairly effort intensive. To enable such efforts to be directed where there is a substantial potential for energy savings, we investigate the impact of bloat on power consumption under different situations. We conduct the first systematic experimental study of the joint power-performance implications of bloat across a range of hardware and software configurations on modern server platforms. The study employs controlled experiments to expose different effects of a common type of Java runtime bloat, excess temporary objects, in the context of the SPECPower_ssj2008 workload. We introduce the notion of equi-performance power reduction to characterize the impact, in addition to peak power comparisons. The results show a wide variation in energy savings from bloat reduction across these configurations. Energy efficiency benefits at peak performance tend to be most pronounced when bloat affects a performance bottleneck and non-bloated resources have low energy-proportionality. Equi-performance power savings are highest when bloated resources have a high degree of energy proportionality. We develop an analytical model that establishes a general relation between resource pressure caused by bloat and its energy efficiency impact under different conditions of resource bottlenecks and energy proportionality. Applying the model to different "what-if" scenarios, we predict the impact of bloat reduction and corroborate these predictions with empirical observations. Our work shows that the prevalent software-only view of bloat is inadequate for assessing its power-performance impact and instead provides a full systems approach for reasoning about its implications.

Dynamics of edge dislocations in a sheared lamellar mesophase

The dynamics and interactions of edge dislocations in a nearly aligned sheared lamellar mesophase is analysed to provide insights into the relationship between disorder and rheology. First, the mesoscale permeation and momentum equations for the displacement field in the presence of external forces are derived from the model H equations for the concentration and momentum field. The secondary flow generated due to the mean shear around an isolated defect is calculated, and the excess viscosity due to the presence of the defect is determined from the excess energy dissipation due to the secondary flow. The excess viscosity for an isolated defect is found to increase with system size in the cross-stream direction as L-3/2 for an isolated defect, though this divergence is cut-off due to interactions in a defect suspension. As the defects are sheared past each other due to the mean flow, the Peach-Koehler force due to elastic interaction between pairs of defects is found to cause no net displacement relative to each other as they approach from large separation to the distance of closest approach. The equivalent force due to viscous interactions is found to increase the separation for defects of opposite sign, and decrease the separation for defects of same sign. During defect interactions, we find that there is no buckling instability due to dilation of layers for systems of realistic size. However, there is another mechanism, which is the velocity difference generated across a slightly deformed bilayer due to the mean shear, which could result in the creation of new defects. (C) 2013 AIP Publishing LLC.

A two-axis in-plane motion measurement system based on optical beam deflection

Measurement of in-plane motion with high resolution and large bandwidth enables model-identification and real-time control of motion-stages. This paper presents an optical beam deflection based system for measurement of in-plane motion of both macro- and micro-scale motion stages. A curved reflector is integrated with the motion stage to achieve sensitivity to in-plane translational motion along two axes. Under optimal settings, the measurement system is shown to theoretically achieve sub-angstrom measurement resolution over a bandwidth in excess of 1 kHz and negligible cross-sensitivity to linear motion. Subsequently, the proposed technique is experimentally demonstrated by measuring the in-plane motion of a piezo flexure stage and a scanning probe microcantilever. For the former case, reflective spherical balls of different radii are employed to measure the in-plane motion and the measured sensitivities are shown to agree with theoretical values, on average, to within 8.3%. For the latter case, a prototype polydimethylsiloxane micro-reflector is integrated with the microcantilever. The measured in-plane motion of the microcantilever probe is used to identify nonlinearities and the transient dynamics of the piezo-stage upon which the probe is mounted. These are subsequently compensated by means of feedback control. (C) 2013 AIP Publishing LLC.

Ternary ion-pair complexation: a protocol for chiral discrimination and the assignment of absolute configuration of chiral hydroxy acids

The study demonstrates the utility of ternary ion-pair complex formed among BINOL (1,1'-Bi-2-naphthol), a carboxylic acid and an organic base, such as, dimethylpyridine (DMAP), 1,4-diazabicyclo2.2.2]octane (DABCO), as a versatile chiral solvating agent (CSA) for the enantiodiscrimination of carboxylic acids, measurement of enantiomeric excess (ee) and the assignment of absolute configuration of hydroxy acids. The proposed mechanism of ternary complex has wider application for testing the enantiopurity owing to the fact that the binary mixture using BINOL alone does not serve as a solvating agent for their discrimination. In addition, the developed protocol has an excellent utility for the assignment of the absolute configurations of hydroxy acids.

FLOTATION OF QUARTZ WITH SOAPS OF BOMBAX MALABARICA OIL AND SHARK LIVER OIL AS COLLECTORS

An attempt has been made to use the indigeneous oils-Bombax Malabarica oil and Shark liver oil in the form of sodium soaps as collectors in the flotation of quartz using barium chloride as activator. The effect of pH, collector concentration and activator concentration on the flotation of quartz is studied in a Leaf and knoll flotation cell. The experiments show that it is possible to obtain 98.0 per cent of quartz as float using 10 mg. of Bombax. Malabarica oil and Shark liver oil soaps at pH values of more than 7.0 and when barium ion concentration is in excess of that required to form barium soaps. Bombax Malabarica oil is found to be superior to Shark liver oil as collector in the flotation of quartz.

Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

In situ approach for testing the enantiopurity of chiral amines and amino alcohols by H-1 NMR

An in situ approach involving a simple mix and shake method for testing the enantiopurity of primary, secondary and tertiary chiral amines and their derivatives, chiral amino alcohols, by H-1-NMR spectroscopy is developed. The protocol involves the in situ formation of chiral ammonium borate salt from a mixture of C-2 symmetric chiral BINOL, trialkoxyborane and chiral amines. The proposed concept was demonstrated convincingly on a large number of chiral and pro-chiral amines and amino alcohols, and also aids the precise measurement of enantiomeric excess. The protocol can be completed in a couple of minutes directly in the NMR sample tube, without the need for any physical separation.

The upper Bay of Bengal salinity structure in a high-resolution model

Salinity in the Bay of Bengal is highly heterogeneous, with extremely fresh waters found at the surface in the Northern part of the basin, and saltier waters at subsurface as well as to the south. This paper investigates the seasonal structure of sea surface salinity of the Bay in a regional high-resolution model forced by ERA-Interim reanalysis and various precipitation products. Surface circulation is believed to drive the spreading of northern Bay of Bengal fresh waters to the rest of the Indian Ocean. We first present a series of experiments to infer the sensitivity of modeled circulation to various numerical choices. Surface circulation is found to be sensitive to the horizontal resolution of the model, with the 1/12 degrees version appearing much more realistic than the 1/4 degrees version. The sidewall boundary condition is also drastically influencing the characteristics of the western boundary current simulated. We then investigate the sensitivity of the salinity response to the various precipitation products. We observe that ERA-Interim excess precipitation induces a fresh bias in the surface salinity response. Spaceborne precipitation products are more satisfactory. We then identify the pathways of the northern Bay freshwater mass, based on passive tracers experiments. Our model suggests that over timescales of a few months, vertical exchanges between the upper fresh layer and the underlying saltier layer appear to be the main export pathway for the freshwater. The horizontal circulation within the mixed layer also acts to convey fresh waters out of the Bay at these timescales, but in a lesser quantity compared to the vertical export. Beyond its intrinsic interest for the understanding of Bay of Bengal physics, this study highlights the need for a careful design of any realistic numerical model, in three key aspects: the choice of the resolution of the model, the choice of the sub-grid scale parameterizations, and the choice of the forcing fluxes. (C) 2013 Elsevier Ltd. All rights reserved.