Studies on the conformation of amino acids XII. Energy calculations on prolyl residue

The favoured conformations of the prolyl residue have been obtained by calculating their potential energies arising from bond-angle strain, torsion-angle strain, non-bonded and electrostatic interatomic energies. In addition to the five membered ring, the peptide unit at the amino end (with ω = 180°) and the C′ atom at the carboxyl end have been taken into account. It is found that there are two local minima in the configurational space of the parameters defining the conformation, as is actually observed-one (denoted by B) with Cγ displaced on the same side as C′, which is lower in energy than the other (denoted by A) with Cγ displaced on the opposite side of C′. The other four atoms Cδ, N, Cα, Cβ are nearly in a plane. The conformations of minimum energy (for both A and B) have bond angles very close to the mean observed values while the torsion angles are well within the range observed in various structures for each type. Taking into account the fact that the influence of neighbouring molecules in a crystal structure may make the conformation of a molecule different from the minimal one, the ranges of the conformational parameters for which the energy is within 0.6 kcal/mole above the minimum value (called the "most probable range") and within 1.2 kcal/mole (called the "probable range") have been determined. The ranges thus obtained, agree well with observation, and most of the observed data lie within the most probable ranges, although differing appreciably from the conformation of minimum energy. The study has been extended, in a limited way, to the conformation of the ring in the amino acid proline. Since the nitrogen is tetrahedral in this (as contrasted with being planar in the prolyl residue), it is found that any one of the five atoms can be out of plane (either way), with the other four lying nearly in a plane. These correspond to low energy conformations (up to 1.2 kcal/mole above the minimum). One such example, in which the Cα atom is out of plane is known for dl-proline · HCl. It is also shown that in these calculations energies due to bond length distortions can be neglected to a good degree of approximation, provided the 'best' values of the bond lengths for the particular compound are used in the theoretical calculations.

Free energy of mixing of divalent basic oxides with silica

An expression derived for the free energy of mixing of a divalent basic oxide (MO) with SiO2 based on a model of silicate structure, takes into account the distribution of O2- (from MO) into the silica network, the mixing of silicate ions with O2- and the enthalpy of mixing. The resulting expression is ΔGmix=RT{N11n (2N1-N)2/4N1(1-N)+N21n N 2-N/1-N}, where N={(β+N1)-√(β+N 1)2-8βN1N2}/2β β=characteristic constant for the system N1=mol fraction of silica N2=mol fraction of MO. For the proper choice of β, calculated values of the activity of MO for the system PbO-SiO2, MnO-SiO2, FeO-SiO2 and CaO-SiO2 are in good agreement with experiment. The model predicts that the activity of the basic oxide decreases with increase in temperature.

Potential functions for hydrogen bond interactions - IV. Minimum Energy Conformation of the α-Helical Structure of PoIy-L-Alanine

Making use of the empirical potential functions for peptide NH .. O bonds, developed in this laboratory, the relative stabilities of the rightand left-handed α-helical structures of poly-L-alanine have been investigated, by calculating their conformational energies (V). The value of Vmin of the right-handed helix (αP) is about - 10.4 kcal/mole, and that of the left-handed helix (αM) is about - 9.6 kcal/mole, showing that the former is lower in energy by 0.8 kcal/mole. The helical parameters of the stable conformation of αP are n ∼ 3.6 and h ∼ 1.5 Å. The hydrogen bond of length 2.85 Å and nonlinearity of about 10° adds about 4.0 kcal/ mole to the stabilising energy of the helix in the minimum enregy region. The energy minimum is not sharply defined, but occurs over a long valley, suggesting that a distribution of conformations (φ{symbol}, ψ) of nearly the same energy may occur for the individual residues in a helix. The experimental data of a-helical fibres of poly-L-alanine are in good agreement with the theoretical results for αP. In the case of proteins, the mean values of (φ{symbol}, ψ) for different helices are distributed, but they invariably occur within the contour for V = Vmin + 2 kcal/mole for αP.

Electron energy equation for an atomic radiating plasma

The electron-energy equation for an atomic radiating plasma is considered in this work. Using the atomic model of Bates, Kingston and McWhirter, the radiation loss-term valid for all optical thicknesses is obtained. A study of the energy gained by electrons in inelastic collisions shows that the radiation loss term can be neglected only for rapidly-decaying or fast-growing plasmas. Emission from optically thin plasmas is considered next and an exact expression is given for the total radiation loss in a recombination continuum. A derivation of the Kramers-Unsöld approximation is presented and the error involved in estimating the total emitted recombination radiation by this approximation is shown to be small.

Energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals

Thermotropic liquid crystals are known to display rich phase behavior on temperature variation. Although the nematic phase is orientationally ordered but translationally disordered, a smectic phase is characterized by the appearance of a partial translational order in addition to a further increase in orientational order. In an attempt to understand the interplay between orientational and translational order in the mesophases that thermotropic liquid crystals typically exhibit upon cooling from the high-temperature isotropic phase, we investigate the potential energy landscapes of a family of model liquid crystalline systems. The configurations of the system corresponding to the local potential energy minima, known as the inherent structures, are determined from computer simulations across the mesophases. We find that the depth of the potential energy minima explored by the system along an isochor grows through the nematic phase as temperature drops in contrast to its insensitivity to temperature in the isotropic and smectic phases. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures; the inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the isotropic-nematic transition. We find that this breakdown occurs at a temperature below which the system explores increasingly deeper potential energy minima.

Commercialization of sustainable energy technologies

Commercialization efforts to diffuse sustainable energy technologies (SETs1) have so far remained as the biggest challenge in the field of renewable energy and energy efficiency. Limited success of diffusion through government driven pathways urges the need for market based approaches. This paper reviews the existing state of commercialization of SETs in the backdrop of the basic theory of technology diffusion. The different SETs in India are positioned in the technology diffusion map to reflect their slow state of commercialization. The dynamics of SET market is analysed to identify the issues, barriers and stakeholders in the process of SET commercialization. By upgrading the ‘potential adopters’ to ‘techno-entrepreneurs’, the study presents the mechanisms for adopting a private sector driven ‘business model’ approach for successful diffusion of SETs. This is expected to integrate the processes of market transformation and entrepreneurship development with innovative regulatory, marketing, financing, incentive and delivery mechanisms leading to SET commercialization.

Stringent constraints on the scalar K pi form factor from analyticity, unitarity and low-energy theorems

We investigate the scalar K pi form factor at low energies by the method of unitarity bounds adapted so as to include information on the phase and modulus along the elastic region of the unitarity cut. Using at input the values of the form factor at t = 0 and the Callan-Treiman point, we obtain stringent constraints on the slope and curvature parameters of the Taylor expansion at the origin. Also, we predict a quite narrow range for the higher-order ChPT corrections at the second Callan-Treiman point.

Exact energy eigenvalues for an attractive Coulomb potential with zero-radius hard core

Following a peratization procedure, the exact energy eigenvalues for an attractive Coulomb potential, with a zero-radius hard core, are obtained as roots of a certain combination of di-gamma functions. The physical significance of this entirely new energy spectrum is discussed.

Consideration on thermal decomposition of calcium hydroxide pellets for energy storage

The reversible chemical reaction of Ca(OH)2/CaO appears to be attractive for storage of solar thermal energy, in view of the nonpolluting and nontoxic nature of the reactants. This paper presents some data on thermal decomposition of calcium hydroxide pellets along with its additives of aluminum, aluminum hydroxide, zinc, and copper. The addition of aluminum and zinc powder enhanced the rate of decomposition considerably at 450°C, but copper had no effect. Considerations on the effect of additives are also discussed in some detail, though their effects are not established with certainty. There is some evidence that heat transfer into the pellet, and the number of potential nucleation sites due to thermal stresses, influence the kinetics and mechanism of decomposition.

Penetration of hydromagnetic energy deep into the magnetosphere

Magnetometer data, acquired on spacecraft and simultaneously at high and low latitudes on the ground, are compared in order to study the propagation characteristics of hydromagnetic energy deep into the magnetosphere. Single events provide evidence that wave energy at L ∼ 3 can at times be only one order of magnitude lower than at L ∼ 13. In addition, statistical analyses of the H-component groundbased data obtained during local daytime hours of 17 July-3 August 1985 show that wave amplitudes at L ∼ 3 are generally 10-30 times lower than at L ∼ 13. The L-dependence of near-equator magnetic field fluctuations measured on ISEE-2 show a sharp drop in energy near the magnetopause and a more gradual fall-off of energy deeper inside the magnetosphere. Such high levels of wave power deep in the magnetosphere have not been quantitatively understood previously. Our initial attempt is to calculate the decay length of an evanescent wave generated at a thick magnetopause boundary. Numerical calculations show that fast magnetosonic modes (called magnetopause and inner mode) can be generated under very restrictive conditions for the field and plasma parameters. These fast compressional modes may have their energy reduced by only one order of magnitude over a penetration depth of about 8RE. More realistic numerical simulations need to be carried out to see whether better agreement with the data can be attained.