Catalysis of tRNA Aminoacylation: Single Turnover to Steady-State Kinetics of tRNA Synthetases

Aminoacyl-tRNA synthetases (aaRS) catalyze the bimolecular association reaction between amino acid and tRNA by specifically and unerringly choosing the cognate amino acid and tRNA. There are two classes of such synthetases that perform tRNA-aminoacylation reaction. Interestingly, these two classes of aminoacyl-tRNA synthetases differ not only in their structures but they also exhibit remarkably distinct kinetics under pre-steady-state condition. The class I synthetases show initial burst of product formation followed by a slower steady-state rate. This has been argued to represent the influence of slow product release. In contrast, there is no burst in the case of class H enzymes. The tight binding of product with enzyme for class I enzymes is correlated with the enhancement of rate in presence of elongation factor. EF-TU. In spite of extensive experimental studies, there is no detailed theoretical analysis that can provide a quantitative understanding of this important problem. In this article, we present a theoretical investigation of enzyme kinetics for both classes of aminoacyl-tRNA synthetases. We present an augmented kinetic scheme and then employ the methods of time-dependent probability statistics to obtain expressions for the first passage time distribution that gives both the time-dependent and the steady-state rates. The present study quantitatively explains all the above experimental observations. We propose an alternative path way in the case of class II enzymes showing the tRNA-dependent amino acid activation and the discrepancy between the single-turnover and steady-state rate.

125 GeV Higgs state in the context of four generations with two Higgs doublets

We interpret the recent discovery of a 125 GeV Higgs-like state in the context of a two-Higgs-doublet model with a heavy fourth sequential generation of fermions, in which one Higgs doublet couples only to the fourth-generation fermions, while the second doublet couples to the lighter fermions of the first three families. This model is designed to accommodate the apparent heaviness of the fourth-generation fermions and to effectively address the low-energy phenomenology of a dynamical electroweak-symmetry-breaking scenario. The physical Higgs states of the model are, therefore, viewed as composites primarily of the fourth-generation fermions. We find that the lightest Higgs, h, is a good candidate for the recently discovered 125 GeV spin-zero particle, when tan beta similar to O(1), for typical fourth-generation fermion masses of M-4G = 400-600 GeV, and with a large t-t' mixing in the right-handed quark sector. This, in turn, leads to BR(t' -> th) similar to O(1), which drastically changes the t' decay pattern. We also find that, based on the current Higgs data, this two-Higgs-doublet model generically predicts an enhanced production rate (compared to the Standard Model) in the pp -> h -> tau tau channel, and reduced rates in the VV -> h -> gamma gamma and p (p) over bar /pp -> V -> hV -> Vbb channels. Finally, the heavier CP-even Higgs is excluded by the current data up to m(H) similar to 500 GeV, while the pseudoscalar state, A, can be as light as 130 GeV. These heavier Higgs states and the expected deviations from the Standard Model din some of the Higgs production channels can be further excluded or discovered with more data.

Arithmetic coding based lossless compression schemes for power system steady state operational data

Introduction of processor based instruments in power systems is resulting in the rapid growth of the measured data volume. The present practice in most of the utilities is to store only some of the important data in a retrievable fashion for a limited period. Subsequently even this data is either deleted or stored in some back up devices. The investigations presented here explore the application of lossless data compression techniques for the purpose of archiving all the operational data - so that they can be put to more effective use. Four arithmetic coding methods suitably modified for handling power system steady state operational data are proposed here. The performance of the proposed methods are evaluated using actual data pertaining to the Southern Regional Grid of India. (C) 2012 Elsevier Ltd. All rights reserved.

PEO|Sncl(2)|PANI composites: as an electrolyte in solid-state battery

Solid-state polymer electrolytes possess high conductivity and have advantages compared with their liquid counterparts. The polyethylene oxide (PEO)-based polymer is a good candidate for this purpose. The PEO/SnCl2/polyaniline composite (PSP composites) at different weight percentages were prepared in anhydrous acetonitrile media. Structural studies were carried out of the prepared composites by X-ray diffraction, Fourier transmission infrared spectroscopy, and surface morphology by scanning electron microscopy. The sigma (dc) was carried out by a two-probe method, and it is found that the conductivity increases with an increase in temperature. The temperature-dependent conductivity of the composites exhibits a typical semi-conducting behavior and hence can be explained by the 1D variable range hopping model proposed by Mott. The electrochemical cell parameters for battery applications at room temperature have also been determined. The samples are fabricated for battery application in the configuration of Na: (PSP): (I-2 + C + sample), and their experimental data are measured using Wagner's polarization technique. The cell parameters result in an open-circuit voltage of 0.83 V and a short-circuit current of 912 mu A for PSP (70:30:10) composite. Hence, these composites can be used in polymer electrolyte studies.

Solid State and Solution Mediated Multistep Sequential Transformations in Metal-Organic Coordination Networks

Sequential transformation in a family of metal-organic framework compounds has been investigated employing both a solid-state as well as a solution mediated route. The compounds, cobalt oxy-bis(benzoate) and manganese oxybis(benzoate) having a two-dimensional structure, were reacted with bipyridine forming cobalt oxy-bis(benzoate)-4,4'-bipyridine and manganese oxy-bis(benzoate)-4,4'-bipyridine, respectively. The bipyridine containing compounds appear to form sequentially through stable intermediates. For the cobalt system, the transformation from a two-dimensional compound, Co(H2O)(2)(OBA)] (OBA = 4,4'-oxy-bis(benzoate)), I, to two different three-dimensional compounds, Co(bpy)(OBA)]center dot bpy, II, (bpy = 4,4'-bipyridine) and Co(bpy)(0.5)(OBA)], III, and reversibility between II and III have been investigated. In the manganese system, transformation from a two-dimensional compound, Mn(H2O)(2)(OBA)], Ia, to two different three-dimensional compounds, Mn (bpy)(OBA)]center dot bpy, Ha and Ha to Mn(bpy)(0.5)(OBA)], Ilia, has been investigated. It has also been possible to identify intermediate products during these transformation reactions. The possible pathways for the formation of the compounds were postulated.

Effect of chlorine substitution on triplet state structure of thioxanthone: A time-resolved resonance Raman study

Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time-resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2-chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of 3n-pi* to 3 pi-pi* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright (C) 2013 John Wiley & Sons, Ltd.

Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

Observation of the nuclear magnetic octupole moment of Yb-173 from precise measurements of the hyperfine structure in the P-3(2) state

We measure hyperfine structure in the metastable P-3(2) state of Yb-173 and extract the nuclear magnetic octupole moment. We populate the state using dipole-allowed transitions through the P-3(1) and S-3(1) states. We measure frequencies of hyperfine transitions of the P-3(2) -> S-3(1) line at 770 nm using a Rb-stabilized ring cavity resonator with a precision of 200 kHz. Second-order corrections due to perturbations from the nearby P-3(1) and P-1(1) states are below 30 kHz. We obtain the hyperfine coefficients as A = -742.11(2) MHz and B = 1339.2(2) MHz, which represent a two orders-of-magnitude improvement in precision, and C = 0.54(2) MHz. From atomic structure calculations, we obtain the nuclear moments quadrupole Q = 2.46(12) b and octupole Omega = -34.4(21) b x mu(N). DOI: 10.1103/PhysRevA.87.012512

Linear programming approach for state estimation incorporating phasor measurements

This paper presents methodologies for incorporating phasor measurements into conventional state estimator. The angle measurements obtained from Phasor Measurement Units are handled as angle difference measurements rather than incorporating the angle measurements directly. Handling in such a manner overcomes the problems arising due to the choice of reference bus. Current measurements obtained from Phasor Measurement Units are treated as equivalent pseudo-voltage measurements at the neighboring buses. Two solution approaches namely normal equations approach and linear programming approach are presented to show how the Phasor Measurement Unit measurements can be handled. Comparative evaluation of both the approaches is also presented. Test results on IEEE 14 bus system are presented to validate both the approaches.

Optical Properties of 1P State Electron Bubbles in Liquid Helium-4

When an electron is injected into liquid helium, it forces open a cavity that is free of helium atoms (an electron bubble). If the electron is in the ground 1S state, this bubble is spherical. By optical pumping it is possible to excite a significant fraction of the electron bubbles to the 1P state; the bubbles then lose spherical symmetry. We present calculations of the energies of photons that are needed to excite these 1P bubbles to higher energy states (1D and 2S) and the matrix elements for these transitions. Measurement of these transition energies would provide detailed information about the shape of the 1P bubbles.

Computational representations for multi state design tasks and enumeration of mechanical device behaviour

The role of a computer emerged from modeling and analyzing concepts (ideas) to generate concepts. Research into methods for supporting conceptual design using automated synthesis had attracted much attention in the past decades. To find out how designers synthesize solution concepts for multi-state mechanical devices, ten experimental studies were conducted. Observations from these empirical studies would be used as the basis to develop knowledge involved in the multi-state design synthesis process. In this paper, we propose a computational representation for expressing the multi-state design task and for enumerating multi-state behaviors of kinematic pairs and mechanisms. This computational representation would be used to formulate computational methods for the synthesis process to develop a system for supporting design synthesis of multiple state mechanical devices by generating a comprehensive variety of solution alternatives.

Analysing modifica-tions in the synthesis of multiple state mechanical devices using configuration space and topology graphs

Automated synthesis of mechanical designs is an important step towards the development of an intelligent CAD system. Research into methods for supporting conceptual design using automated synthesis has attracted much attention in the past decades. In our research, ten experimental studies are conducted to find out how designers synthesize solution concepts for multi-state mechanical devices. The designers are asked to think aloud, while carrying out the synthesis. These design synthesis processes are video recorded. It has been found that modification of kinematic pairs and mechanisms is the major activity carried out by all the designers. This paper presents an analysis of these synthesis processes using configuration space and topology graph to identify and classify the types of modifications that take place. Understanding of these modification processes and the context in which they happened is crucial to develop a system for supporting design synthesis of multiple state mechanical devices that is capable of creating a comprehensive variety of solution alternatives.

The Relationship of Solid-State Plasticity to Mechanochromic Luminescence in Difluoroboron Avobenzone Polymorphs

In solid-state mechanochromic luminescence (ML) materials, it remains a challenge to establish the origin of fluorescence color changes upon mechanical action and to determine why only some fluorophores exhibit ML behavior. The study of mechanical properties by nanoindentation, followed by ML experiments on green- and cyan-emitting polymorphs of difluoroboron avobenzone reveals that upon smearing, the plastically deformable cyan form shows a prominent color change to yellow, while in the harder green form the redshifted emission is barely detectable. Crystal structure analysis reveals the presence of slip planes in the softer cyan form that can facilitate the formation of recoverable and low energy defects in the structure. Hence, the cyan form exhibits prominent and reversible ML behavior. This suggests a potential design strategy for efficient ML materials.

Adaptive constellation rotation scheme for two-user fading MAC with quantized fade state feedback

With no Channel State Information (CSI) at the users, transmission over the two-user Gaussian Multiple Access Channel with fading and finite constellation at the input, will have high error rates due to multiple access interference (MAI). However, perfect CSI at the users is an unrealistic assumption in the wireless scenario, as it would involve extremely large feedback overheads. In this paper we propose a scheme which removes the adverse effect of MAI using only quantized knowledge of fade state at the transmitters such that the associated overhead is nominal. One of the users rotates its constellation relative to the other without varying the transmit power to adapt to the existing channel conditions, in order to meet certain predetermined minimum Euclidean distance requirement in the equivalent constellation at the destination. The optimal rotation scheme is described for the case when both the users use symmetric M-PSK constellations at the input, where M = 2(gimel), gimel being a positive integer. The strategy is illustrated by considering the example where both the users use QPSK signal sets at the input. The case when the users use PSK constellations of different sizes is also considered. It is shown that the proposed scheme has considerable better error performance compared to the conventional non-adaptive scheme, at the cost of a feedback overhead of just log log(2) (M-2/8 - M/4 + 2)] + 1 bits, for the M-PSK case.

Sex and physiological state influence the rate of resource acquisition and monopolisation in urban free-ranging dogs, Canis familiaris

In animal populations, the constraints of energy and time can cause intraspecific variation in foraging behaviour. The proximate developmental mediators of such variation are often the mechanisms underlying perception and associative learning. Here, experience-dependent changes in foraging behaviour and their consequences were investigated in an urban population of free-ranging dogs, Canis familiaris by continually challenging them with the task of food extraction from specially crafted packets. Typically, males and pregnant/lactating (PL) females extracted food using the sophisticated `gap widening' technique, whereas non-pregnant/non-lactating (NPNL) females, the relatively underdeveloped `rip opening' technique. In contrast to most males and PL females (and a few NPNL females) that repeatedly used the gap widening technique and improved their performance in food extraction with experience, most NPNL females (and a few males and PL females) non-preferentially used the two extraction techniques and did not improve over successive trials. Furthermore, the ability of dogs to sophisticatedly extract food was positively related to their ability to improve their performance with experience. Collectively, these findings demonstrate that factors such as sex and physiological state can cause differences among individuals in the likelihood of learning new information and hence, in the rate of resource acquisition and monopolization.