Biochemical and structural characterization of residue 96 mutants of Plasmodium falciparum triosephosphate isomerase: active-site loop conformation, hydration and identification of a dimer-interface ligand-binding site

Plasmodium falciparum TIM (PfTIM) is unique in possessing a Phe residue at position 96 in place of the conserved Ser that is found in TIMs from the majority of other organisms. In order to probe the role of residue 96, three PfTIM mutants, F96S, F96H and F96W, have been biochemically and structurally characterized. The three mutants exhibited reduced catalytic efficiency and a decrease in substrate-binding affinity, with the most pronounced effects being observed for F96S and F96H. The k(cat) values and K-m values are (2.54 +/- 0.19) x 10(5) min(-1) and 0.39 +/- 0.049 mM, respectively, for the wild type; (3.72 +/- 0.28) x 10(3) min(-1) and 2.18 +/- 0.028 mM, respectively, for the F96S mutant;(1.11 +/- 0.03) x 10(4) min(-1) and 2.62 +/- 0.042 mM, respectively, for the F96H mutant; and (1.48 +/- 0.05) x 10(5) min(-1) and 1.20 +/- 0.056 mM, respectively, for the F96W mutant. Unliganded and 3-phosphoglycerate (3PG) complexed structures are reported for the wild-type enzyme and the mutants. The ligand binds to the active sites of the wild-type enzyme (wtPfTIM) and the F96W mutant, with a loop-open state in the former and both open and closed states in the latter. In contrast, no density for the ligand could be detected at the active sites of the F96S and F96H mutants under identical conditions. The decrease in ligand affinity could be a consequence of differences in the water network connecting residue 96 to Ser73 in the vicinity of the active site. Soaking of crystals of wtPfTIM and the F96S and F96H mutants resulted in the binding of 3PG at a dimer-interface site. In addition, loop closure at the liganded active site was observed for wtPfTIM. The dimer-interface site in PfTIM shows strong electrostatic anchoring of the phosphate group involving the Arg98 and Lys112 residues of PfTIM.

Surface waves in the presence of external high frequency fields

The system equations of a collisionless, unmagnetized plasma, contained in a box where a high frequency (h.f.1 electric field is incident, are solved in the electrostatic approximation. The surface modes of the plasma in the semi-infinite and box geometry are investigated. In the high frequency limit, the mode frequencies are not significantly changed by the h.f. field but their group velocities can be quite different. Two long wavelength low frequency modes, which are not excited in the absence of h.f. field, are found. These modes are true surface modes (decaying on one wavelength from the surface) unlike the only low frequency ion acoustic mode in the zero field case. In the short wavelength limit the low frequency mode occurs at &/2, oi being the ion plasma frequency, a result similar to the case of no h.f. field.

Prediction of Breakdown Voltages of Binary Gas Mixtures in Uniform Electric Fields

A simple equation to predict the breakdown voltages for binary mixtures (Vmix) of electronegative gases (SF6, CCl2F2) and buffer gases (N2, N2O, CO2, air) under uniform electric field has been proposed. Values of Vmix evaluated using this equation for mixtures of SF6-N2, SF6-air, SF6-N2O, SF6-CO2 and CCl2F2-N2 over a wide range of pd show an excellent agreement with the experimentally measured data available in the literature.

A Huge Effect of Weak dc Electrical Fields on Grain Growth in Zirconia

We show that the application of a modest dc electrical field, about 4 V/cm, can significantly reduce grain growth in yttria-stabilized polycrystalline zirconia. These measurements were made by annealing samples, for 10 h at 1300°C, with and without an electrical field. The finding adds a new dimension to the role of applied electrical fields in sintering and superplasticity, phenomena that are critical to the net-shape processing of ceramics. Grain-growth retardation will considerably enhance the rates of sintering and superplasticity, leading to significant energy efficiencies in the processing of ceramics.

Mixed ligand complexes in vinyl polymerization-II: [NN-ethylenebis(salicylideneiminato)] (benzoylacetonato)cobalt(III) as an initiator

The polymerization of methyl methacrylate initiated by a mixed ligand complex. [NN-ethylenebis(salicylideneiminato)](benzoylacetonato)cobalt(III) has been studied in bulk and in benzene at 70° and 80°. The rate of polymerization is proportional to (concentration of the chelate)Image and the monomer exponent is close to 1.5. The activation energy and the kinetic and transfer constants are evaluated. A free radical mechanism has been proposed.

Calculation of Sparking Potentials of SF6 and SF6-GAS Mixtures in Uniform and Non-Uniform Electric Fields

A simple formula is developed to predict the sparking potentials of SF6 and SF6-gas mixture in uniform and non-uniform fields. The formula has been shown to be valid over a very wide range from 1 to 1800 kPa·cm of pressure and electrode gap separation for mixtures containing 5 to 100% SF6. The calculated values are found to be in good agreement with the previously reported measurements in the literature. The formula should aid design engineers in estimating electrode-spacings and clearances in power apparatus and systems.

Surface instability in a semi-infinite plasma in the presence of high frequency fields

The surface instability of a semi-infinite plasma immersed in a high frequency field is investigated. When the natural Langmuir frequency of the surface is nearly equal to the frequency of the high frequency field, the dispersion relation predicts build-up of oscillations with a growth rate comparable with the real part of the frequency. Threshold values above which the instability is possible are derived.

Note on the stability of parallel magnetic fields

The stability characteristics of parallel magnetic fields when fluid motions are present along the lines of force is studied. The stability criterion for both symmetric (m=0) and asymmetric (m=1) modes are discussed and the results obtained by Trehan and Singh (1978) are amended in the present study. The results obtained for the cylindrical geometry are shown to play an important role forka<4, wherek is the wave number,a is the radius of the cylinder, compared to the results obtained by Geronicolas (1977) for the slab geometry.

Effect of magnetic and electrical fields on dendritic freezing of aqueous solutions of sodium chloride

Aqueous solutions of sodium chloride were solidified under the influence of magnetic and electrical fields using two different freezing systems. In the droplet system, small droplets of the solution are introduced in an organic liquid column at −20°C which acts as the heat sink. In the unidirectional freezing system the solutions are poured into a tygon tube mounted on a copper chill, maintained at −70°C, from which the freezing initiates. Application of magnetic fields caused an increase in the spacing and promoted side branching of primary ice dendrites in the droplet freezing system, but had no measurable effect on the dendrites formed in the unidirectional freezing system. The range of electric fields applied in this investigation had no measurable effect on the dendritic structure. Possible interactions between external magnetic and electrical fields have been reviewed and it is suggested that the selective effect of magnetic fields on dendrite spacings in a droplet system could be due to a change in the nucleation behaviour of the solution in the presence of a magnetic field.

Generation of High Magnetic Fields Using Thyristors

This paper describes the use of high-power thyristors in conjunction with a low-voltage supply for generating pulsed magnetic fields. A modular bank of electrolytic capacitors is charged through a programmable solid-state power supply and then rapidly discharged through a bank of thyristors into a magnetizing coil. The modular construction of capacitor banks enables the discrete control of pulse energy and time. Peak fields up to 15 telsa (150 KOe) and a half period of about 200 microseconds are generated through the discharges. Still higher fields are produced by discharging into a precooled coil ( 77°K). Measurement method for a pulsed field is described.

Mixed ligand complexes in vinyl polymerization-II: [NN′-ethylenebis(salicylideneiminato)] (benzoylacetonato)cobalt(III) as an initiator

The polymerization of methyl methacrylate initiated by a mixed ligand complex. [NN′-ethylenebis(salicylideneiminato)](benzoylacetonato)cobalt(III) has been studied in bulk and in benzene at 70° and 80°. The rate of polymerization is proportional to (concentration of the chelate)1/2 and the monomer exponent is close to 1.5. The activation energy and the kinetic and transfer constants are evaluated. A free radical mechanism has been proposed.

Mixed ligand complexes in vinyl polymerization. I. [N,N-ethylenebis (salicylideneiminato)](acetylacetonato)cobalt(III) as an initiator

Polymerization of methyl methacrylate in the presence of a mixed ligand complex, [N,N-ethylenebis(salicylideneiminato)](acetylacetonato)cobalt(III) in benzene was studied. The rate of polymerization was proportional to the square root of the concentration of the chelate and the monomer exponent was 1.67 and 1.69 at 60 and 70°C, respectively. The activation energy and the kinetic and transfer constants were evaluated. A free-radical mechanism has been proposed.

Mössbauer Lineshape in the Presence of Radio-Frequency Fields

A general expression for the Mössbauer lineshape in the presence of a radio frequency field is derived. As an example the effect of the rf field on Fe57 nuclei is discussed for a situation where the 3/2 sublevel of 14.4 keV state of Fe57 is selectively populated. At resonance, both the diagonal and non-diagonal matrix elements contribute to the correlation function. As a result, in addition to a slight rf induced distortion of the main Mössbauer line. additional transition lines are obtained. Thus the present calculation supports the experimental observations of Heiman et al.

2-Thioacetamido thiazole as an ambidentate ligand. Complexes of Zn(II), Cd(II), Hg(II) and Cu(I)

Metal complexes of thiazoles have been studied in recent years[I-3] because of their biochemical importance[4,5]. However, data on metal complexes of thiazole derivatives containing another coordinating function are limited[2]. We have synthesized and examined the donor characteristics of a new ligand, 2-thioacetamide thiazole (TATZ)(I) towards chlorides and bromides of Zn(II), Cd(II), Hg(II) and Cu(I). The presence of four potential donor atoms and extensive charge delocalization should render TATZ a versatile ligand.

Townsend's First Ionization Coefficients and Sparking Potentials in Crossed Electric and Magnetic Fields

Townsend's first ionization coefficients have been measured in corssed electric and magnetic fields for values of B/p ranging from 0.013 TESLA. TORR-1 to 0.064 TESLA.TORR-1 and for 103 x 102¿ E/p 331 x 102 V.M-1. TORR-1 in oxygen and for 122 x 102¿ E/pÂ488 x 102 V.M-1.TORR-1 for dry air. The values of effective collision frequencies determined from the equivalent pressure (pe) concept generally increase with E/p at constant B/p and decrease with increasing B/p at constant E/p. Effective collision frequencies determined from measured sparking potentials at high values of E/p increase with decreasing E/pe. The drift velocity and mean energy of electrons in oxygen in crossed electric and magnetic fields have been derived.