Mapping Key Residues of ISD11 Critical for NFS1-ISD11 Subcomplex Stability IMPLICATIONS IN THE DEVELOPMENT OF MITOCHONDRIAL DISORDER, COXPD19

Biogenesis of the iron-sulfur (Fe-S) cluster is an indispensable process in living cells. In mammalian mitochondria, the initial step of the Fe-S cluster assembly process is assisted by the NFS1-ISD11 complex, which delivers sulfur to scaffold protein ISCU during Fe-S cluster synthesis. Although ISD11 is an essential protein, its cellular role in Fe-S cluster biogenesis is still not defined. Our study maps the important ISD11 amino acid residues belonging to putative helix 1 (Phe-40), helix 3 (Leu-63, Arg-68, Gln-69, Ile-72, Tyr-76), and C-terminal segment (Leu-81, Glu-84) are critical for in vivo Fe-S cluster biogenesis. Importantly, mutation of these conserved ISD11 residues into alanine leads to its compromised interaction with NFS1, resulting in reduced stability and enhanced aggregation of NFS1 in the mitochondria. Due to altered interaction with ISD11 mutants, the levels of NFS1 and Isu1 were significantly depleted, which affects Fe-S cluster biosynthesis, leading to reduced electron transport chain complex (ETC) activity and mitochondrial respiration. In humans, a clinically relevant ISD11 mutation (R68L) has been associated in the development of a mitochondrial genetic disorder, COXPD19. Our findings highlight that the ISD11 R68A/R68L mutation display reduced affinity to form a stable subcomplex with NFS1, and thereby fails to prevent NFS1 aggregation resulting in impairment of the Fe-S cluster biogenesis. The prime affected machinery is the ETC complex, which showed compromised redox properties, causing diminished mitochondrial respiration. Furthermore, the R68L ISD11 mutant displayed accumulation of mitochondrial iron and reactive oxygen species, leading to mitochondrial dysfunction, which correlates with the phenotype observed in COXPD19 patients.

pi-Electron rich small molecule sensors for the recognition of nitroaromatics

Selective and discriminative detection of -NO2 containing high energy organic compounds such as picric acid (PA), 2,4,6-trinitrotoluene (TNT) and dinitrotoluene (DNT) has become a challenging task due to concerns over national security, criminal investigations and environment protections. Among various known detection methods, fluorescence techniques have gained special attention in recent time. A wide variety of fluorescent chemosensors have been developed for nitroaromatic explosive detection. In this review article, we provide an overview of the recent developments made in small molecule-based turn-off fluorescent sensors for nitroaromatic explosives with special focus on organic and H-bonded supramolecular sensors. The fluorescent sensors discussed in this review are classified and organized according to their functionality and their recognition of nitroaromatics by fluorescence quenching.

Synthesis and electron microscopy of high entropy alloy nanoparticles

This work provides a methodology for synthesizing isolated multi-component, high entropy alloy nanoparticles. Wet chemical synthesis technique was used to synthesis NiFeCrCuCo nanoparticles. As synthesized nanoparticles were spherical with an average size of 26.7 +/- 3.3 nm. Average composition of the as-synthesized nanoparticle dispersion was 26 +/- 2 at% Cr, 14 +/- 2 at% Fe, 10 +/- 0.6 at% Co, 25 +/- 0.1 at% Ni and 25 +/- 1.1 at% Cu. Compositional analysis of the nanoparticles conducted using the compositional line profile analysis and compositional mapping on a single nanoparticle level revealed a fairly uniform distribution of all the five component elements within the nanoparticle volume. Electron diffraction analysis clearly revealed that the structure of as-synthesized nanoparticles was face centered cubic. (C) 2015 Elsevier B.V. All rights reserved.

Neutron diffraction, Mossbauer effect and Electron Paramagnetic Resonance studies on multiferroic Pb(Fe2/3W1/3)O-3

Multiferroic Pb(Fe2/3W1/3)O-3 ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mossbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mossbauer spectra confirms the trivalent state of iron (Fe3+). The Mossbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe3+ ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe2/3W1/3)O-3 ceramic at 300 K. Considering neutron diffraction, Mossbauer and EPR results together, it may be stated here that Pb(Fe2/3W1/3)O-3 exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

Luffa acutangula agglutinin: Primary structure determination and identification of a tryptophan residue involved in its carbohydrate-binding activity using mass spectrometry

A lectin from phloem exudates of Luffa acutangula (ridge gourd) was purified on chitin affinity chromatography and characterized for its amino acid sequence and to study the role of tryptophan in its activity. The purified lectin was subjected to various proteolytic digestions, and the resulting peptides were analyzed by liquid chromatography coupled electrospray ionization ion trap mass spectrometer. The peptide precursor ions were fragmented by collision-induced dissociation or electron transfer dissociation experiments, and a manual interpretation of MS/MS was performed to deduce amino acid sequence. This gave rise to almost complete sequence coverage of the lectin which showed high-sequence similarity with deduced sequences of phloem lectins present in the database. Chemical modification of lysine, tyrosine, histidine, arginine, aspartic acid, and glutamic acid residues did not inhibit the hemagglutinating activity. However, the modification of tryptophan residues using N-bromosuccinimide showed the loss of hemagglutinating activity. Additionally, the mapping of tryptophan residues was performed to determine the extent and number of residues modified, which revealed that six residues per molecule were oxidized suggesting their accessibility. The retention of the lectin activity was seen when the modifications were performed in the presence of chitooligosaccharides due to protection of a tryptophan residue (W-102) in the protein. These studies taken together have led to the identification of a particular tryptophan residue (W-102) in the activity of the lectin. (c) 2015 IUBMB Life, 67(12):943-953, 2015

Microstructure Formation in Dissimilar Metal Welds: Electron Beam Welding of Ti/Ni

We present results for electron beam welding of a binary Ti/Ni dissimilar metal couple. The difference in physical properties of the base metals and metallurgical features (thermodynamics and kinetics) of the system influence both macroscopic transport and microstructure development in the weld. Microstructures near the fusion interfaces are markedly different from those inside the weld region. At the Ti side, Ti2Ni dendrites are observed to grow toward the fusion interface, while in the Ni side, layered growth of gamma-Ni, Ni3Ti, and Ni3Ti + NiTi eutectic is observed. Different morphologies of the latter eutectic constitute the predominant microstructure inside the weld metal region. These results are compared and contrasted with those from laser welding of the same binary couple, and a scheme of solidification is proposed to explain the observations. This highlights notable departures from welding of similar and other dissimilar metals such as a significant asymmetry in heat transport that governs progress of solidification from each side of the couple, and a lack of unique liquidus isotherm characterizing the liquid-solid front.

Polyketide Quinones Are Alternate Intermediate Electron Carriers during Mycobacterial Respiration in Oxygen-Deficient Niches

Mycobacterium tuberculosis (Mtb) adaptation to hypoxia is considered crucial to its prolonged latent persistence in humans. Mtb lesions are known to contain physiologically heterogeneous microenvironments that bring about differential responses from bacteria. Here we exploit metabolic variability within biofilm cells to identify alternate respiratory polyketide quinones (PkQs) from both Mycobacterium smegmatis (Msmeg) and Mtb. PkQs are specifically expressed in biofilms and other oxygen-deficient niches to maintain cellular bioenergetics. Under such conditions, these metabolites function as mobile electron carriers in the respiratory electron transport chain. In the absence of PkQs, mycobacteria escape from the hypoxic core of biofilms and prefer oxygenrich conditions. Unlike the ubiquitous isoprenoid pathway for the biosynthesis of respiratory quinones, PkQs are produced by type III polyketide synthases using fatty acyl-CoA precursors. The biosynthetic pathway is conserved in several other bacterial genomes, and our study reveals a redox-balancing chemicocellular process in microbial physiology.

Measuring the magnetic-field-dependent chemical potential of a low-density three-dimensional electron gas in n-GaAs and extracting its magnetic susceptibility

We report the magnetic-field-dependent shift of the electron chemical potential in bulk, n-type GaAs at room temperature. A transient voltage of similar to 100 mu V was measured across a Au-Al2O3-GaAs metal-oxide-semiconductor capacitor in a pulsed magnetic field of similar to 6 T. Several spurious voltages larger than the signal that had plagued earlier researchers performing similar experiments were carefully eliminated. The itinerant magnetic susceptibility of GaAs is extracted from the experimentally measured data for four different doping densities, including one as low as 5 x 10(15) cm(-3). Though the susceptibility in GaAs is dominated by Landau-Peierls diamagnetism, the experimental technique demonstrated can be a powerful tool for extracting the total free carrier magnetization of any electron system. The method is also virtually independent of the carrier concentration and is expected to work better in the nondegenerate limit. Such experiments had been successfully performed in two-dimensional electron gases at cryogenic temperatures. However, an unambiguous report on having observed this effect in any three-dimensional electron gas has been lacking. We highlight the 50 year old literature of various trials and discuss the key details of our experiment that were essential for its success. The technique can be used to unambiguously yield only the itinerant part of the magnetic susceptibility of complex materials such as magnetic semiconductors and hexaborides, and thus shed light on the origin of ferromagnetism in such systems.

Negative Cooperativity and High Affinity in Chitooligosaccharide Binding by a Mycobacterium smegmatis Protein Containing LysM and Lectin Domains

LysM domains have been recognized in bacteria and eukaryotes as carbohydrate-binding protein modules, but the mechanism of their binding to chitooligosaccharides has been underexplored. Binding of a Mycobacterium smegmatis protein containing a lectin (MSL) and one LysM domain to chitooligosaccharides has been studied using isothermal titration calorimetry and fluorescence titration that demonstrate the presence of two binding sites of nonidentical affinities per dimeric MSL-LysM molecule. The affinity of the molecule for chitooligosaccharides correlates with the length of the carbohydrate chain. Its binding to chitooligosaccharides is characterized by negative cooperativity in the interactions of the two domains. Apparently, the flexibility of the long linker that connects the LysM and MSL domains plays a facilitating role in this recognition. The LysM domain in the MSL-LysM molecule, like other bacterial domains but unlike plant LysM domains, recognizes equally well peptidoglycan fragments as well as chitin polymers. Interestingly, in the case presented here, two LysM domains are enough for binding to peptidoglycan in contrast to the three reportedly required by the LysM domains of Bacillus subtilis and Lactococcus lactis. Also, the affinity of the MSL-LysM molecule for chitooligosaccharides is higher than that of LysM-chitooligosaccharide interactions reported so far.

Electron mobility in few-layer MoxW1-xS2

Heterostructures of two-dimensional (2D) layered materials are increasingly being explored for electronics in order to potentially extend conventional transistor scaling and to exploit new device designs and architectures. Alloys form a key underpinning of any heterostructure device technology and therefore an understanding of their electronic properties is essential. In this paper, we study the intrinsic electron mobility in few-layer MoxW1-xS2 as limited by various scattering mechanisms. The room temperature, energy-dependent scattering times corresponding to polar longitudinal optical (LO) phonon, alloy and background impurity scattering mechanisms are estimated based on the Born approximation to Fermi's golden rule. The contribution of individual scattering rates is analyzed as a function of 2D electron density as well as of alloy composition in MoxW1-xS2. While impurity scattering limits the mobility for low carrier densities (<2-4x10(12) cm(-2)), LO polar phonon scattering is the dominant mechanism for high electron densities. Alloy scattering is found to play a non-negligible role for 0.5 < x < 0.7 in MoxW1-xS2. The LO phonon-limited and impurity-limited mobilities show opposing trends with respect to alloy mole fractions. The understanding of electron mobility in MoxW1-xS2 presented here is expected to enable the design and realization of heterostructures and devices based on alloys of MoS2 andWS(2).

Electron mobility in few-layer MoxW1-xS2

Heterostructures of two-dimensional (2D) layered materials are increasingly being explored for electronics in order to potentially extend conventional transistor scaling and to exploit new device designs and architectures. Alloys form a key underpinning of any heterostructure device technology and therefore an understanding of their electronic properties is essential. In this paper, we study the intrinsic electron mobility in few-layer MoxW1-xS2 as limited by various scattering mechanisms. The room temperature, energy-dependent scattering times corresponding to polar longitudinal optical (LO) phonon, alloy and background impurity scattering mechanisms are estimated based on the Born approximation to Fermi's golden rule. The contribution of individual scattering rates is analyzed as a function of 2D electron density as well as of alloy composition in MoxW1-xS2. While impurity scattering limits the mobility for low carrier densities (<2-4x10(12) cm(-2)), LO polar phonon scattering is the dominant mechanism for high electron densities. Alloy scattering is found to play a non-negligible role for 0.5 < x < 0.7 in MoxW1-xS2. The LO phonon-limited and impurity-limited mobilities show opposing trends with respect to alloy mole fractions. The understanding of electron mobility in MoxW1-xS2 presented here is expected to enable the design and realization of heterostructures and devices based on alloys of MoS2 andWS(2).

Development of a spin polarized low energy electron diffraction system

We have designed and constructed a spin polarized low energy electron diffraction system working in the reflected electron pulse counting mode. This system is capable of measuring asymmetries due to spin-orbit and exchange interactions. Photoemission from a strained GaAs/GaAsP super lattice is used as the source of spin polarized electrons. Spin-orbit asymmetry is evaluated for Ir(100) single crystal at various energies. Subsequently, exchange asymmetry has been evaluated on 40 monolayer Fe deposited on Ir(100). This instrument proves to be useful in understanding structure and magnetism at surfaces. (C) 2016 AIP Publishing LLC.

Observation of Size-Dependent Electron-Phonon Scattering and Temperature-Dependent Photoluminescence Quenching in Triangular-Shaped Silver Nanoparticles

Research studies on plasmonic properties of triangular-shaped silver nanoparticles might lead to several interesting applications. However, in this work, triangular-shaped silver nanoparticles have been synthesized by simple solvothermal technique and reported the effect of size on the electron-phonon scattering in the synthesized materials by analyzing their temperature-dependent photoluminescence (PL) emission characteristics. It has been observed that total integrated PL emission intensity is quenched by 33 % with the increase in temperature from 278 to 323 K. The observed decrease in PL emission intensity has been ascribed to the increase of electron-phonon scattering rate with the increase in temperature. The values of electron-phonon coupling strength (S) for synthesized samples have been evaluated by theoretical fitting of the experimentally obtained PL emission data. Smaller sized triangular nanoparticle has been found to exhibit stronger temperature dependence in PL emission, which strongly suggests that smaller sized triangular silver nanostructures have better electron-phonon coupling.

Electron transfer amongst flavo- and hemo-proteins: diffusible species effect the relay processes, not protein-protein binding

Hitherto, electron transfer (ET) between redox proteins has been deemed to occur via donor-acceptor binding, and diffusible reactive species are considered as deleterious side-products in such systems. Herein, ET from cytochrome P450 reductase (CPR, an animal membrane flavoprotein) and horseradish peroxidase (HRP, a plant hemoprotein) to cytochrome c (Cyt c, a soluble animal hemoprotein) was probed under diverse conditions, using standard assays. ET in the CPR-Cyt c system was critically inhibited by cyanide and sub-equivalent levels of polar one-electron cyclers like copper ions, vitamin C/Trolox and superoxide dismutase. In the presence of lipids, inhibition was also afforded by amphipathic molecules vitamin E, palmitoyl-vitamin C and the membrane hemoprotein, cytochrome b(5). Such nonspecific inhibition (by diverse agents in both aqueous and lipid phases) indicated that electron transfer/relay was effected by small diffusible agents, whose lifetimes are shortened by the diverse radical scavengers. When CPR was retained in a dialysis membrane and Cyt c presented outside in free solution, ET was still observed. Further, HRP (taken at nM levels) catalyzed oxidation of a phenolic substrate was significantly inhibited upon the incorporation of sub-nM levels of Cyt c. The findings imply that CPR-Cyt c or HRP-Cyt c binding is not crucial for ET. Further, fundamental quantitative arguments (based on diffusion/collision) challenge the erstwhile protein-protein binding-assisted ET hypothesis. It is proven beyond reasonable doubt that mobile and diffusible electron carriers (ions and radicals) serve as ``redox-relay agents'' in the biological ET models/setup studied.

Electron-hole asymmetry in the electron-phonon coupling in top-gated phosphorene transistor

Using in situ Raman scattering from phosphorene channel in an electrochemically top-gated field effect transistor, we show that phonons with A(g) symmetry depend much more strongly on concentration of electrons than that of holes, wheras phonons with B-g symmetry are insensitive to doping. With first-principles theoretical analysis, we show that the observed electon-hole asymmetry arises from the radically different constitution of its conduction and valence bands involving pi and sigma bonding states respectively, whose symmetry permits coupling with only the phonons that preserve the lattice symmetry. Thus, Raman spectroscopy is a non-invasive tool for measuring electron concentration in phosphorene-based nanoelectronic devices.