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.

Edge states, spin transport, and impurity-induced local density of states in spin-orbit coupled graphene

We study graphene, which has both spin-orbit coupling (SOC), taken to be of the Kane-Mele form, and a Zeeman field induced due to proximity to a ferromagnetic material. We show that a zigzag interface of graphene having SOC with its pristine counterpart hosts robust chiral edge modes in spite of the gapless nature of the pristine graphene; such modes do not occur for armchair interfaces. Next we study the change in the local density of states (LDOS) due to the presence of an impurity in graphene with SOC and Zeeman field, and demonstrate that the Fourier transform of the LDOS close to the Dirac points can act as a measure of the strength of the spin-orbit coupling; in addition, for a specific distribution of impurity atoms, the LDOS is controlled by a destructive interference effect of graphene electrons which is a direct consequence of their Dirac nature. Finally, we study transport across junctions, which separates spin-orbit coupled graphene with Kane-Mele and Rashba terms from pristine graphene both in the presence and absence of a Zeeman field. We demonstrate that such junctions are generally spin active, namely, they can rotate the spin so that an incident electron that is spin polarized along some direction has a finite probability of being transmitted with the opposite spin. This leads to a finite, electrically controllable, spin current in such graphene junctions. We discuss possible experiments that can probe our theoretical predictions.

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.

Stimuli-responsive colorimetric and NIR fluorescence combination probe for selective reporting of cellular hydrogen peroxide

Hydrogen peroxide (H2O2) is a key reactive oxygen species and a messenger in cellular signal transduction apart from playing a vital role in many biological processes in living organisms. In this article, we present phenyl boronic acid-functionalized quinone-cyanine (QCy-BA) in combination with AT-rich DNA (exogenous or endogenous cellular DNA), i.e., QCy-BA subset of DNA as a stimuli-responsive NIR fluorescence probe for measuring in vitro levels of H2O2. In response to cellular H2O2 stimulus, QCy-BA converts into QCy-DT, a one-donor-two-acceptor (D2A) system that exhibits switch-on NIR fluorescence upon binding to the DNA minor groove. Fluorescence studies on the combination probe QCy-BA subset of DNA showed strong NIR fluorescence selectively in the presence of H2O2. Furthermore, glucose oxidase (GOx) assay confirmed the high efficiency of the combination probe QCy-BA subset of DNA for probing H2O2 generated in situ through GOx-mediated glucose oxidation. Quantitative analysis through fluorescence plate reader, flow cytometry and live imaging approaches showed that QCy-BA is a promising probe to detect the normal as well as elevated levels of H2O2 produced by EGF/Nox pathways and post-genotoxic stress in both primary and senescent cells. Overall, QCy-BA, in combination with exogenous or cellular DNA, is a versatile probe to quantify and image H2O2 in normal and disease-associated cells.

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.