NAD/NADH as a model redox system: Mechanism, mediation, modification by the environment

The biologically important redox couple, [beta]-nicotinamide adenine dinucleotide/1,4,[beta]-dihydronicotinamide adenine dinucleotide, provides a grossly reversible prototype system for an overall electrode reaction consisting of two successive one-electron (1 e-) transfer steps coupled with (a) dimerization of an intermediate free radical product, (b) protonation-deprotonation of an intermediate product, (c) other chemical reactions, (d) adsorption of reactant, intermediate and product species, and (e) mediation by electrode surface species. Cathodic reduction of NAD+ proceeds through two 1 e- steps well separated in potential; protonation of the free radical produced on the first step occurs prior to the second electron-transfer; a first-order chemical reaction coupled to the latter may involve rearrangement of an initial dihydro product to 1,4-NADH (and some 1,6-NADH). In the apparently single stage 2 e- anodic oxidation of NADH, the initial step is an irreversible heterogeneous electron transfer, which proceeds to at least some extent through mediator redox systems located close to the electrode surface; the resulting cation radical, NADH+[middle dot], loses a proton (first order reaction) to form a neutral radical, NAD[middle dot], which may participate in a second heterogeneous electron transfer (ECE mechanism) or may react with NADH+[middle dot] (disproportionation mechanism DISP 1 or half-regeneration mechanism) to yield NAD+.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/23943/1/0000190.pd

306 - Nucleotides and related substances: Conformation in solution and at solution|electrode interfaces

The problems involved in inferring conformation and orientation from electrochemical measurements are considered as are the implications of extrapolating the results for relatively simple nucleotides to biopolymers. The determination of conformation, e.g., shape in solution -- more particularly, when approaching the electrode -- largely depends on estimation of the effective molecular cross-section as reflected in the experimentally measured diffusion coefficient, D; for example, formation of associated species as in base stacking is usually reflected in a variation in D and, often, in redox potential. The determination of conformation at the solution|electrode interface is often intimately connected with the state and orientation of an adsorbed species -- more particularly of its electroactive and adsorption sites -- relative to the electrode surface. Current trends in inferring such interfacial conformation for DNA and derived large nucleic acid species are summarized; the adsorption pattern seen on oxidation of NADH at carbon electrodes is reviewed.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/23299/1/0000237.pd

Advanced radiometric and interferometric milimeter-wave scene simulations

Smart munitions and weapons utilize various imaging sensors (including passive IR, active and passive millimeter-wave, and visible wavebands) to detect/identify targets at short standoff ranges and in varied terrain backgrounds. In order to design and evaluate these sensors under a variety of conditions, a high-fidelity scene simulation capability is necessary. Such a capability for passive millimeter-wave scene simulation exists at TRW. TRW's Advanced Radiometric Millimeter-Wave Scene Simulation (ARMSS) code is a rigorous, benchmarked, end-to-end passive millimeter-wave scene simulation code for interpreting millimeter-wave data, establishing scene signatures and evaluating sensor performance. In passive millimeter-wave imaging, resolution is limited due to wavelength and aperture size. Where high resolution is required, the utility of passive millimeter-wave imaging is confined to short ranges. Recent developments in interferometry have made possible high resolution applications on military platforms. Interferometry or synthetic aperture radiometry allows the creation of a high resolution image with a sparsely filled aperture. Borrowing from research work in radio astronomy, we have developed and tested at TRW scene reconstruction algorithms that allow the recovery of the scene from a relatively small number of spatial frequency components. In this paper, the TRW modeling capability is described and numerical results are presented

First spectra of the W UMa system V524 Monocerotis

We present the first high-resolution spectra of the W UMa contact binary V524 Mon. The spectra of the two components are very similar, resembling a G5 and a K0. We find the radial velocities and rotational velocities consistent with corotation. We estimate the radii and the masses and derive a mass ratio M_2/M_1 = 2.1. We confirm that V524 Mon is a W-type contact system, likely enclosed in a common convective envelope, as found by Samec & Loflin (2003). We do not find evidence for the expected level of emission in the chromospheric CaII H and K lines, neither H_alpha, indicating that the magnetic activity is much weaker than expected or that other processes are hampering chromospheric emission.Comment: 5 pages, 3 figures. Accepted for A&A (in press

SS Ari: a shallow-contact close binary system

Two CCD epochs of light minimum and a complete R light curve of SS Ari are presented. The light curve obtained in 2007 was analyzed with the 2003 version of the W-D code. It is shown that SS Ari is a shallow contact binary system with a mass ratio $q=3.25$ and a degree of contact factor f=9.4(\pm0.8%). A period investigation based on all available data shows that there may exist two distinct solutions about the assumed third body. One, assuming eccentric orbit of the third body and constant orbital period of the eclipsing pair results in a massive third body with $M_3=1.73M_{\odot}$ and P_3=87.0$yr. On the contrary, assuming continuous period changes of the eclipsing pair the orbital period of tertiary is 37.75yr and its mass is about$0.278M_{\odot}$. Both of the cases suggest the presence of an unseen third component in the system.Comment: 28 pages, 9 figures and 5 table

Lignin-first biorefining of Nordic poplar to produce cellulose fibers could displace cotton production on agricultural lands

Here, we show that lignin-first biorefining of poplar can enable the production of dissolving cellulose pulp that can produce regenerated cellulose, which could substitute cotton. These results in turn indicate that agricultural land dedicated to cotton could be reclaimed for food production by extending poplar plantations to produce textile fibers. Based on climate-adapted poplar clones capable of growth on marginal lands in the Nordic region, we estimate an environmentally sustainable annual biomass production of similar to 11 tonnes/ha. At scale, lignin-first biorefining of this poplar could annually generate 2.4 tonnes/ha of dissolving pulp for textiles and 1.1 m(3) biofuels. Life cycle assessment indicates that, relative to cotton production, this approach could substantially reduce water consumption and identifies certain areas for further improvement. Overall, this work highlights a new value chain to reduce the environmental footprint of textiles, chemicals, and biofuels while enabling land reclamation and water savings from cotton back to food production

Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction

The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing ‘pseudo-single-crystal’ electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe2+/3+ couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe2+ oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale

Proton-Coupled Oxygen Reduction at Liquid-Liquid Interfaces Catalyzed by Cobalt Porphine

Cobalt porphine (CoP) dissolved in the organic phase of a biphasic system is used to catalyze O2 reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O2. The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, CoP, Fc, or O2