Structural mobility and transformations in globular proteins

Although globular proteins are endowed with well defined three-dimensional structures, they exhibit substantial mobility within the framework of the given threedimensional structure. The different types of mobility found in proteins by and large correspond to the different levels of organisational hierarchy in protein architecture. They are of considerable structural and functional significance, and can be broadly classified into(a) thermal and conformational fluctuations, (b) segmental mobility, (c) interdomain mobility and (d) intersubunit mobility. Protein crystallographic studies has provided a wealth of information on all of them. The temperature factors derived from X-ray diffraction studies provide a measure of atomic displacements caused by thermal and conformational fluctuations. The variation of displacement along the polypeptide chain have provided functionally significant information on the flexibility of different regions of the molecule in proteins such as myoglobin, lysozyme and prealbumin. Segmental mobility often involves the movement of a region or a segment of a molecule with respect to the rest, as in the transition between the apo and the holo structures of lactate dehydrogenase. It may also involve rigidification of a disordered region of the molecule as in the activation of the zymogens of serine proteases. Transitions between the apo and the holo structures of alcohol dehydrogenase,and between the free and the sugar bound forms of hexokinase, are good examples of interdomain mobility caused by hinge-bending. The capability of different domains to move semi-independently contributes greatly to the versatility of immunoglobulin molecules. Interdomain mobility in citrate synthase appears to be more complex and its study has led to an alternative description of domain closure. The classical and the most thoroughly studied case of intersubunit mobility is that in haemoglobin. The stereochemical mechanism of the action of this allosteric protein clearly brings out the functional subtilities that could be achieved through intersubunit movements. In addition to ligand binding and activation,environmental changes also often cause structural transformations. The reversible transformation between 2 Zn insulin and 4 Zn insulin is caused by changes in the ionic strength of the medium. Adenylate Kinase provides a good example for functionally significant reversible conformational transitions induced by variation in pH. Available evidences indicate that reversible structural transformations in proteins could also be caused by changes in the aqueous environment, including those in the amount of water surrounding protein molecules.

A Dual Seven-Level Inverter Supply for an Open-End Winding Induction Motor Drive

This paper develops a seven-level inverter structure for open-end winding induction motor drives. The inverter supply is realized by cascading four two-level and two three-level neutral-point-clamped inverters. The inverter control is designed in such a way that the common-mode voltage (CMV) is eliminated. DC-link capacitor voltage balancing is also achieved by using only the switching-state redundancies. The proposed power circuit structure is modular and therefore suitable for fault-tolerant applications. By appropriately isolating some of the inverters, the drive can be operated during fault conditions in a five-level or a three-level inverter mode, with preserved CMV elimination and DC-link capacitor voltage balancing, within a reduced modulation range.

A Current Source Inverter Fed Induction Motor Drive with Power Factor Angle Control Using Microprocessor

This paper describes a method of adjusting the stator power factor angle for the control of an induction motor fed from a current source inverter (CSI) based on the concept of space vectors (or park vectors). It is shown that under steady state, if the torque angle is kept constant over the entire operating range, it has the advantage of keeping the slip frequency constant. This can be utilized to dispose of the speed feedback and simplify the control scheme for the drive, such that the stator voltage integral zero crossings alone can be used as a feedback for deciding the triggering instants of the CSI thyristors under stable operation of the system. A closed-loop control strategy is developed for the drive based on this principle, using a microprocessor-based control system and is implemented on a laboratory prototype CSI fed induction motor drive.

Chemical bond approach to determining conductivity band gaps in amorphous chalcogenides and pnictides

The minimum energy required for the formation of conjugate pair of charged defects is found to be approximately equal to the experimental activation energy for d.c. conductivity in a number of amorphous chalcoganides and pnictides. This observation implies that the defect pair formation energy represents an intrinsic gap for transport in amorphous chalcogenides.

Calorimetric, infrared and ESR studies of the plastically crystalline state of organic compounds

Enthalpy changes of the crystal-plastic and plastic-liquid transitions are related to the temperature range of stability of the plastic phase. Thermodynamics of the plastic state of binary mixtures have been examined. Infrared correlation times, τc, and activation energies have been measured for a few molecules in the plastic state. Molecular tumbling times, τt, have also been measured employing ESR spectra of a spin-probe. Plots of log τc(τt) 1/T are continuous through the plastic-liquid transition. Activation energies for molecular motion seem to vary in the same direction as the ΔH of the plastic-crystal transition. Infrared correlation times of solute molecules in binary solutions in the plastic and the liquid states show interesting variations with solute concentration.

A Multilevel Inverter with Hexagonal and 12-sided Polygonal Space Vector Structure for Induction Motor Drive

This paper proposes a multilevel inverter which produces hexagonal voltage space vector structure in lower modulation region and a 12-sided polygonal space vector structure in the over-modulation region. Normal conventional multilevel inverter produces 6n +/- 1 (n=odd) harmonics in the phase voltage during over-modulation and in the extreme square wave mode operation. However, this inverter produces a 12-sided polygonal space vector location leading to the elimination of 6n 1 (n=odd) harmonics in over-modulation region extending to a final 12-step mode operation. The inverter consists of three conventional cascaded two level inverters with asymmetric dc bus voltages. The switching frequency of individual inverters is kept low throughout the modulation index. In the low speed region, hexagonal space phasor based PWM scheme and in the higher modulation region, 12-sided polygonal voltage space vector structure is used. Experimental results presented in this paper shows that the proposed converter is suitable for high power applications because of low harmonic distortion and low switching losses.

New temperature fluctuation method for direct determination of thermal activation energy of deep levels in semiconductors

A new method is suggested where the thermal activation energy is measured directly and not as a slope of an Arrhenius plot. The sample temperature T is allowed to fluctuate about a temperature T0. The reverse-biased sample diode is repeatedly pulsed towards zero bias and the transient capacitance C1 at time t1 is measured The activation energy is obtained by monitoring the fluctuations in C1 and T. The method has been used to measure the activation energy of the gold acceptor level in silicon.

Graphical method to include temperature variation of activation energy in Hall data analysis

A graphical method is presented for Hall data analysis, including the temperature variation of activation energy due to screening. This method removes the discrepancies noted in the analysis of recently reported Hall data on Si(In).

Noble Metal Ionic Catalysts

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

A Pulsewidth Modulated Control of Induction Motor Drive Using Multilevel 12-Sided Polygonal Voltage Space Vectors

In this paper, a novel 12-sided polygonal space vector structure is proposed for an induction motor drive. The space vector pattern presented in this paper consists of two 12-sided concentric polygons with the outer polygon having a radius double the inner one. As compared to previously reported 12-sided polygonal space vector structures, this paper subdivides the space vector plane into smaller sized triangles. This helps in reducing the switching frequency of the inverters without deteriorating the output voltage quality. It also reduces the device ratings and dv/dt stress on the devices to half. At the same time, other benefits obtained from the existing 12-sided space vector structure, such as increased linear modulation range and complete elimination of 5th and 7th order harmonics in the phase voltage, are also retained in this paper. The space vector structure is realized by feeding an open-end induction motor with two conventional three-level neutral point clamped (NPC) inverters with asymmetric isolated dc link voltage sources. The neutral point voltage fluctuations in the three-level NPC inverters are eliminated by utilizing the switching state multiplicities for a space vector point. The pulsewidth modulation timings are calculated using sampled reference waveform amplitudes and are explained in detail in this paper. Experimental verification on a laboratory prototype shows that this configuration may be considered suitable for high power drives.

Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.

Oxygen desorption from high Tc YBa2Cu3O7−δ (δ = 0.05, 0.5)

From a temperature programmed desorption study employing a quadrupole mass spectrometer, the superconducting oxide YBa2Cu3O7−δ (δ = 0.05) showed two distinct oxygen desorption peaks, one below and one above 470°C. The activation energy of oxygen desorption of the superconducting oxide was 28 Kcals/mole and that of non-superconducting oxide (YBa2Cu3O6.5) was 54 Kcals/mole. No impurity peaks due to H2O, CO and CO2 from the bulk or adsorbed on surfaces could be observed when a well prepared superconducting oxide was heated up to 650°C.

Influence of electroslag refining on the hot ductility of AISI 4340 steel in torsion

Electroslag refining is a useful remelting process by which clean steels can be produced for sophisticated applications. In this investigation, AISI 4340 steel has been electroslag refined and the improvement in its hot ductility has been assessed using hot torsion tests; electroslag refining has improved the hot ductility considerably. The temperature at which peak ductility is obtained has also increased — from 1473 K in the unrefined steel to 1573 K in ESR steel. Results indicate that it should be possible to subject the ESR ingot to much higher strains per unit operation during industrial hot working processes such as forging, which would result in a considerable saving of power. The improvement in hot ductility in ESR steel has been attributed primarily to the removal of non-metallic inclusions and the reduction in sulphur content. From the apparent activation energy estimated from the hot torsion data, the dynamic recrystallization process is identified as the mechanism controlling the rate of hot deformation.

XPS and XAES studies of surface segregation and oxidation of Cu-Ge alloy

Surface segregation of Ge is seen in the Cu-5at%Ge alloy with an activation enthalpy equal to 17 kJ/mol. Oxidation of the alloy in the temperature range 400 to 600 K shows the formation of Cu2O and GeO which on further heating in vacuum at 650 K converts to GeO2 with the reduction of Cu2O to Cu.

Thermodynamic and kinetic studies on saccharide binding to soya-bean agglutinin.

The fluorescence of N-dansylgalactosamine [N-(5-dimethylaminonaphthalene-1-sulphonyl)galactosamine] was enhanced 11-fold with a 25 nm blue-shift in the emission maximum upon binding to soya-bean agglutinin (SBA). This change was used to determine the association constants and thermodynamic parameters for this interaction. The association constant of 1.51 X 10(6) M-1 at 20 degrees C indicated a very strong binding, which is mainly due to a relatively small entropy value, as revealed by the thermodynamic parameters: delta G = -34.7 kJ X mol-1, delta H = -37.9 kJ X mol-1 and delta S = -10.9 J X mol-1 X K-1. The specific binding of this sugar to SBA shows that the lectin can accommodate a large hydrophobic substituent on the C-2 of galactose. Binding of non-fluorescent ligands, studied by monitoring the fluorescence changes when they are added to a mixture of SBA and N-dansylgalactosamine, indicates that a hydrophobic substituent at the anomeric position increases the affinity of the interaction. The C-6 hydroxy group also stabilizes the binding considerably. Kinetics of binding of N-dansylgalactosamine to SBA studied by stopped-flow spectrofluorimetry are consistent with a single-step mechanism and yielded k+1 = 2.4 X 10(5) M-1 X s-1 and k-1 = 0.2 s-1 at 20 degrees C. The activation parameters indicate an enthalpicly controlled association process.