Cover Feature: Superior Proton-Transfer Catalytic Promiscuity of Cytochrome c in Self-Organized Media (7/2021)

Evolutionarily elderly proteins commonly feature greater catalytic promiscuity. Cytochrome c is among the first set of proteins in evolution to have known prospects in electron transport and peroxidative properties. Here, we report that cyt c is also a proficient proton-transfer catalyst and enhances the Kemp elimination (KE; model reaction to show proton transfer catalytic property) by ∼750-fold on self-organized systems like micelles and vesicles. The self-organized systems mimic the mitochondrial environment in vitro for cyt c. Using an array of biophysical and biochemical mutational assays, both acid–base and redox mechanistic pathways have been explored. The histidine moiety close to hemin group (His18) is mainly responsible for proton abstraction to promote the concerted E2 pathway for KE catalysis when cyt c is in its oxidized form; this has also been confirmed by a H18A mutant of cyt c. However, the redox pathway is predominant under reducing conditions in the presence of dithiothreitol over the pH range 6–7.4. Interestingly, we found almost 750-fold enhanced KE catalysis by cyt c compared to aqueous buffer. Overall, in addition to providing mechanistic insights, the data reveal an unprecedented catalytic property of cyt c that could be of high importance in an evolutionary perspective considering its role in delineating the phylogenic tree and also towards generating programmable designer biocatalysts.     

A Novel High Nitrogen Steel Powder Designed for Minimized Cr2N Precipitations

High nitrogen steels provide excellent mechanical properties and corrosion resistance but are prone to form precipitates which adversely affect the corrosion resistance and toughness. High nitrogen steel powders currently available in the market are not claimed to be precipitate free. It is critical to avoid these precipitates while retaining nitrogen in the dissolved form to realize the value of these powder alloys. However, retaining high level of dissolved nitrogen in steel powder during melt atomization process is very challenging. Instead, solid-state dissolution of nitrogen into the powder alloy followed by rapid cooling may provide a convenient approach to avoid precipitate formation compared to traditional melt processing. This study presents a solution treatment approach to achieve elevated dissolved nitrogen levels (~ 0.4 wt pct) in Fe–Mn–Cr powder alloy with negligible precipitation of nitrides. The influence of starting material, holding time, temperature and cooling rate on the resulting microstructure is presented. A fully austenite matrix with high dissolved nitrogen content resulted in powders with desired mechanical properties.

     

Evidence of Homogeneous Microstructures in Ti6Al4V Alloy During Shear Deformation

Metallurgical and Materials Transactions A - Free-end torsion tests were conducted for Ti6Al4V (Ti64) alloy at temperatures of 298 K, 673 K, and 873 K for different strains ranging from 0.22 to...     

Abrasion Resistance of Field-Assisted Ion-Exchanged Glass

The fracture strength of HF-etched samples was measured as a function of field-assisted K-Na ion exchange depth, as well as the severity of abrasion. As expected, the more severe the abrasion, the greater the depth required to make the strength insensitive to abrasion. An abrasion-independent weakening mechanism that increased with exchange depth was also found to be operative.     

Cationic surfactant-selective potentiometric sensors based on neutral ion-pair carrier complexes

Poly(vinyl chloride) (PVC) membrane electrodes to determine monomer concentrations of tetradecyltrimethylammonium ion (TTA⁺) and hexadecylpyridinium ion (HPy⁺) based on neutral ion-pair carrier complexes of tetradecyltrimethylammonium dodecyl sulfate (TTA⁺-DS⁻) and hexadecylpyridinium dodecyl sulfate (HPy⁺-DS⁻), respectively, are reported here. The electrodes exhibit a Nernstian slope of 59 mV per decade for TTA⁺ and a sub-Nernstian slope of 34.5 mV per decade for HPy⁺ ions. The TTA⁺ ion-selective electrode (ISE) and the HPy⁺-ISE can determine the monomer units down to concentrations as low as 4.0×10⁻⁴M and 1.66×10⁻⁵ M, respectively. The effect of various additives, such as the anionic polyelectrolyte sodium dextran sulfate and macrocyclic β-cyclodextrin, on the surface activity exhibited by the cationic surfactants TTA⁺-DS⁻ and HPy⁺-DS⁻, in the presence of background concentrations of NaCl was also examined with surfactant-selective sensors. The Gibbs free energy of micelle formation (ΔG _m ) of both surfactants in the presence of various additives was calculated and found to be less favorable with respect to an increase in the amount of additives due to less availability of cationic surfactant monomer units. The ion-pair complexes TTA⁺-DS⁻ and HPy⁺-DS⁻ were found to behave as selective carrier compounds in PVC membranes in determining the concentration of monomer units of both TTA⁺ and HPy⁺, respectively. The proposed sensors worked well at a fairly acidic pH of 1–6.5 with response time of 60 s. The sensors responded well to the surfactant ions even in the presence of additives at lower concentration. The lifetime of the sensors is 3 mon.     

A composite numerical scheme for the numerical simulation of coupled Burgers’ equation

In this work, a composite numerical scheme based on finite difference and Haar wavelets is proposed to solve time dependent coupled Burgers’ equation with appropriate initial and boundary conditions. Time derivative is discretized by forward difference and then quasilinearization technique is used to linearize the coupled Burgers’ equation. Space derivatives discretization with Haar wavelets leads to a system of linear equations and is solved using Matlab7.0. Convergence analysis of proposed scheme exhibits that the error bound is inversely proportional to the resolution level of the Haar wavelet. Finally, the adaptability of proposed scheme is demonstrated by numerical experiments and shows that the present composite scheme offers better accuracy in comparison with other existing numerical methods.     

Design of novel compact anti-stiction and low insertion loss RF MEMS switch

A novel torsional RF MEMS capacitive switch design on silicon substrate is presented. The optimized switch topology such as reduction in up-state capacitance results in insertion loss better than ?0.1 dB till 20 GHz. Off to on state capacitance ratio is also improved by 18 fold and isolation is better than ?43 dB at 9.5 GHz. The achieved on state return loss is ?38 dB as compared to ?21 dB at 9.5 GHz. An optimized reduction in contact area and use of floating metal layer increases the switching speed from 56 to 46 μsec. It also increases the switch reliability by alleviating the stiction.     

Analysis and optimization of fixture under dynamic machining condition with chip removal effect

Dynamic interactions in the tool–workpiece and workpiece–fixture systems significantly impinge on the quality of finished workpieces. The presented simulation system integrates the effects of workpiece fixture dynamics with the other factors contributing to the machining process dynamics. It provides more accurate prediction of the process output which helps in the design of the optimum fixture configuration prior to the production stage. Modelling of the frictional contact behaviour between the fixture element and the workpiece helps to improve the prediction accuracy of the simulation system which accelerates the convergence to the optimum fixture configuration design and consequently improves the machined part dimensional accuracy and geometric integrity. The developed simulation is capable of modelling complicated part geometries by interfacing with commercial ANSYS.V10^® packages. This research work minimizes the deformation of workpiece using integrated optimization tool of Genetic algorithm (GA) and ANSYS Parametric Design Language (APDL) of finite element analysis. The same layouts given by the above optimization tool are used in the experimental setup and it is found that the improved geometric tolerance of squarness and flatness of the given workpiece. The chip removal effect and frictional contact between the workpiece and the fixture elements are taken into account based on element death technique and nonlinear finite-element analysis. A Case study of an open slot milling process illustrates the application of the proposed improved geometric tolerance approach.