Connecting Active-Site Loop Conformations and Catalysis in Triosephosphate Isomerase: Insights from a Rare Variation at Residue96 in the Plasmodial Enzyme

Despite extensive research into triosephosphate isomerases (TIMs), there exists a gap in understanding of the remarkable conjunction between catalytic loop-6 (residues 166-176) movement and the conformational flip of Glu165 (catalytic base) upon substrate binding that primes the active site for efficient catalysis. The overwhelming occurrence of serine at position96 (98% of the 6277 unique TIM sequences), spatially proximal to E165 and the loop-6 residues, raises questions about its role in catalysis. Notably, Plasmodium falciparum TIM has an extremely rare residuephenylalanineat this position whereas, curiously, the mutant F96S was catalytically defective. We have obtained insights into the influence of residue96 on the loop-6 conformational flip and E165 positioning by combining kinetic and structural studies on the PfTIM F96 mutants F96Y, F96A, F96S/S73A, and F96S/L167V with sequence conservation analysis and comparative analysis of the available apo and holo structures of the enzyme from diverse organisms.

Low temperature solution processed high-kappa ZrO2 gate dielectrics for nanoelectonics

The high-kappa gate dielectrics, specifically amorphous films offer salient features such as exceptional mechanical flexibility, smooth surfaces and better uniformity associated with low leakage current density. In this work, similar to 35 nm thick amorphous ZrO2 films were deposited on silicon substrate at low temperature (300 degrees C, 1 h) from facile spin-coating method and characterized by various analytical techniques. The X-ray diffraction and X-ray photoelectron spectroscopy reveal the formation of amorphous phase ZrO2, while ellipsometry analysis together with the Atomic Force Microscope suggest the formation of dense film with surface roughness of 1.5 angstrom, respectively. The fabricated films were integrated in metal-oxide-semiconductor (MOS) structures to check the electrical capabilities. The oxide capacitance (C-ox), flat band capacitance (C-FB), flat band voltage (V-FB), dielectric constant (kappa) and oxide trapped charges (Q(ot)) extracted from high frequency (1 MHz) C-V curve are 186 pF, 104 pF, 0.37V, 15 and 2 x 10(-11) C, respectively. The small flat band voltage 0.37V, narrow hysteresis and very little frequency dispersion between 10 kHz-1 MHz suggest an excellent a-ZrO2/Si interface with very less trapped charges in the oxide. The films exhibit a low leakage current density 4.7 x 10(-9)A/cm(2) at 1V. In addition, the charge transport mechanism across the MOSC is analyzed and found to have a strong bias dependence. The space charge limited conduction mechanism is dominant in the high electric field region (1.3-5 V) due to the presence of traps, while the trap-supported tunneling is prevailed in the intermediate region (0.35-1.3 V). Low temperature solution processed ZrO2 thin films obtained are of high quality and find their importance as a potential dielectric layer on Si and polymer based flexible electronics. (C) 2016 Published by Elsevier B.V.