Spectroelectrochemical Elucidation of the Kinetics of Two Closely Spaced Electron Transfers

The use of spectroelectrochemistry to facilitate the analysis of an EE mechanism was reported in this work. Using a set of spectra as a function of potential, the spectra of all three oxidation states were determined using evolving window factor analysis. From these spectra, the concentration of each species in solution was determined for each potential. Using these data, the current was calculated. Unlike the direct measurement of current, the current due to each redox process was determined, allowing one to analyze each redox process separate from the other. With the use of the Butler–Volmer equation, the redox potential and the heterogeneous electron transfer parameters were measured. The spectrally determined current has the advantage of determining the current due to each redox process which is not generally possible with voltammetric data when the redox potentials are close together. This method was applied to the spectroelectrochemical reduction of Escherichia coli sulfite reductase hemoprotein (SiR-HP) in a phosphate buffer and in the presence of cyanide. The electrochemical parameters (E°’s, k°’s and α’s) for each electron transfer were calculated for both the uncoordinated and cyanide coordinated species. The rates of electron transfer for the siroheme and iron–sulfur cluster were slower than the rates observed for other heme proteins. This is probably due to the fact that this protein is significantly larger than most of the heme protein previously studied. This approach is a powerful tool for two-electron transfers when the E° values are close together

Use of Evolutionary Factor Analysis in the Spectroelectrochemistry of Escherichia coli Sulfite Reductase Hemoprotein and a Mo/Fe/S Cluster

The deconvolution of spectroelectrochemical data is often quite difficult if the spectra of intermediates are not known. Factor analysis, however, has been shown to be a powerful technique which can make it possible to deconvolute overlapping spectra. In this work, evolving factor analysis will be used to determine the number of intermediates and the spectra of those species for two typical spectroelectrochemical experiments:  linear scan voltammetry and chronoabsorptometry in a thin-layer cell. The first system was the reduction of E. coli sulfite reductase hemoprotein (SiR-HP). Principal factor analysis indicated that three species were present. By using evolving factor analysis, the potential regions where each of the species were present were identified, and their concentrations and spectra were determined by the use of the mass balance equation. The spectra of the one-electron (SiR-HP1-) and two-electron (SiR-HP2-) reduced product were compared with previous work. The second experiment was the chronoabsorptometry of Cl2FeS2MoS2FeCl22- in methylene chloride. This experiment indicated that five species were present during the experiment. The entire set of 61 spectra were fit by assuming that there were 4 species present during the electrolysis. The rate constant for the appearance of subsequent species fit quite well with the rate constant for the disappearance of previous species. The spectra of the intermediates and final product were obtained using evolving factor analysis and a mass balance equation. Identification of the fifth species, which was probably the initial reduction product, Cl2FeS2MoS2FeCl23-, was difficult due to its low concentration and the fact that it was present in the same time region as the starting material

Use of Factor Analysis in Multi‐Electron Spectroelectrochemistry

Spectroelectrochemistry and voltammetry contain both unique and complementary information. For multielectron transfers, information on each electron exchange is only directly accessible in the voltammetric data if the potentials are well separated so that two distinct waves can be observed. If the E°’s are close together, the voltammetric data will contain the sum of the two exchanges which can only be deconvoluted by modeling the system and solving the appropriate equations. On the other hand, the spectroscopic data contains direct information on each electron exchange even when the E°’s are close together. Unfortunately, this information cannot be readily extracted if the intermediate oxidation state does not have a potential region where it is the dominant species. Chemometric methods such as factor analysis though can be used to deduce the spectra of each species even if they don’t dominate in any potential region. Initial work on the application of factor analysis to spectroelectrochemistry has been reported. Traditional methods of electroanalytical analysis are based on models that relate the concentration of electroactive materials to electrode potentials and solution concentrations. The model and parameters are adjusted to obtain the best fit to a model. Chemometric methods such as factor analysis allow the experimenter to determine solution concentrations without knowledge of the precise electrochemical mechanism. The utility of this approach will be demonstrated by the study of a protein, E. coli sulfite reductase hemoprotein, which is capable of transferring two-electrons and the ΔE° values are less than 100 mV, causing the waves to overlap. With these methods more detailed information on the electron transfer rate and associated kinetics processes can be more clearly identified

Group field theory formulation of 3d quantum gravity coupled to matter fields

We present a new group field theory describing 3d Riemannian quantum gravity coupled to matter fields for any choice of spin and mass. The perturbative expansion of the partition function produces fat graphs colored with SU(2) algebraic data, from which one can reconstruct at once a 3-dimensional simplicial complex representing spacetime and its geometry, like in the Ponzano-Regge formulation of pure 3d quantum gravity, and the Feynman graphs for the matter fields. The model then assigns quantum amplitudes to these fat graphs given by spin foam models for gravity coupled to interacting massive spinning point particles, whose properties we discuss.Comment: RevTeX; 28 pages, 21 figure

Nature Versus Nurture: Luminous Blue Variable Nebulae in and near Massive Stellar Clusters at the Galactic Center

Three Luminous Blue Variables (LBVs) are located in and near the Quintuplet Cluster at the Galactic Center: the Pistol star, G0.120-0.048, and qF362. We present imaging at 19, 25, 31, and 37 {\mu}m of the region containing these three LBVs, obtained with SOFIA using FORCAST. We argue that the Pistol and G0.120-0.048 are identical ``twins" that exhibit contrasting nebulae due to the external influence of their different environments. Our images reveal the asymmetric, compressed shell of hot dust surrounding the Pistol Star and provide the first detection of the thermal emission from the symmetric, hot dust envelope surrounding G0.120-0.048. Dust and gas composing the Pistol nebula are primarily heated and ionized by the nearby Quintuplet Cluster stars. The northern region of the Pistol nebula is decelerated due to the interaction with the high-velocity (2000 km/s) winds from adjacent Wolf-Rayet Carbon (WC) stars. With the DustEM code we determine that the Pistol nebula is composed of a distribution of very small, transiently-heated grains (10-~35 {\AA}) and that it exhibits a gradient of decreasing grain size from the south to the north due to differential sputtering by the winds from the WC stars. Dust in the G0.120-0.048 nebula is primarily heated by the central star; however, the nebular gas is ionized externally by the Arches Cluster. Unlike the Pistol nebula, the G0.120-0.048 nebula is freely expanding into the surrounding medium. Given independent dust and gas mass estimates we find that the Pistol and G0.120-0.048 nebulae exhibit similar gas-to-dust mass ratios of ~310 and ~290, respectively. Both nebulae share identical size scales (~ 0.7 pc) which suggests that they have similar dynamical timescales of ~10^5 yrs, assuming a shell expansion velocity of v_exp 60 km/s.Comment: 18 pages, 7 figures, accepted to Ap

The Carboxyl-Terminal Segment of Apolipoprotein A-V Undergoes a Lipid-Induced Conformational Change

Apolipoprotein (apo) A-V is a 343-residue, multidomain protein that plays an important role in regulation of plasma triglyceride homeostasis. Primary sequence analysis revealed a unique tetraproline sequence (Pro293-Pro296) near the carboxyl terminus of the protein. A peptide corresponding to the 48-residue segment beyond the tetraproline motif was generated from a recombinant apoA-V precursor wherein Pro295 was replaced by Met. Cyanogen bromide cleavage of the precursor protein, followed by negative affinity chromatography, yielded a purified peptide. Nondenaturing polyacrylamide gel electrophoresis verified that apoA-V(296-343) solubilizes phospholipid vesicles, forming a relatively heterogeneous population of reconstituted high-density lipoprotein with Stokes’ diameters\u3e17 nm. At the same time, apoA-V(296-343) failed to bind a spherical lipoprotein substrate in vitro. Far-UV circular dichroism spectroscopy revealed the peptide is unstructured in buffer yet adopts significant R-helical secondary structure in the presence of the lipid mimetic solvent trifluoroethanol (TFE; 50% v/v). Heteronuclear multidemensional NMR spectroscopy experiments were conducted with uniformly 15N- and 15N/13C-labeled peptide in 50% TFE. Peptide backbone assignment and secondary structure prediction using TALOSþ reveal the peptide adopts R-helix secondary structure from residues 309 to 334. In TFE, apoA-V(296-343) adopts an extended amphipathic R-helix, consistent with a role in lipoprotein binding as a component of full-length apoA-V

SONTRAC—A low background, large area solar neutron spectrometer

SONTRAC is a scintillating fiber neutron detector designed to measure solar flare neutrons from a balloon or spacecraft platform. The instrument is comprised of alternating orthogonal planes of scintillator fibers viewed by photomultiplier tubes and image intensifier/CCD camera optics. It operates by tracking the paths of recoil protons from the double scatter of 20 to 200 MeV neutrons off hydrogen in the plastic scintillator, thereby providing the necessary information to determine the incident neutron direction and energy. SONTRAC is also capable of detecting and measuring high-energy gamma rays \u3e20 MeV as a “solid-state spark chamber.” The self-triggering and track imaging features of a prototype for tracking in two dimensions have been demonstrated in calibrations with cosmic-ray muons, 14 to ∼65 MeV neutrons and ∼20 MeV protons

Old supernova dust factory revealed at the Galactic center

Dust formation in supernova ejecta is currently the leading candidate to explain the large quantities of dust observed in the distant, early Universe. However, it is unclear whether the ejecta-formed dust can survive the hot interior of the supernova remnant (SNR). We present infrared observations of ~0.02 $M_\odot$ of warm (~100 K) dust seen near the center of the ~10,000 yr-old Sgr A East SNR at the Galactic center. Our findings signify the detection of dust within an older SNR that is expanding into a relatively dense surrounding medium ($n_e$ ~ 100 $\mathrm{cm}^{-3}$) and has survived the passage of the reverse shock. The results suggest that supernovae may indeed be the dominant dust production mechanism in the dense environment of early Universe galaxies.Comment: 25 pages, 5 figures. Includes supplementary materials. Published Online March 19 2015 on Science Expres

N=2 supersymmetric spin foams in three dimensions

We construct the spin foam model for N=2 supergravity in three dimensions. Classically, it is a BF theory with gauge algebra osp(2|2). This algebra has representations which are not completely reducible. This complicates the procedure when building a state sum. Fortunately, one can and should excise these representations. We show that the restricted subset of representations form a subcategory closed under tensor product. The resulting state-sum is once again a topological invariant. Furthermore, within this framework one can identify positively and negatively charged fermions propagating on the spin foam. These results on osp(2|2) representations and intertwiners apply more generally to spin network states for N=2 loop quantum supergravity (in 3+1 dimensions) where it allows to define a notion of BPS states.Comment: 12 page

Modeling Quantum Optical Components, Pulses and Fiber Channels Using OMNeT++

Quantum Key Distribution (QKD) is an innovative technology which exploits the laws of quantum mechanics to generate and distribute unconditionally secure cryptographic keys. While QKD offers the promise of unconditionally secure key distribution, real world systems are built from non-ideal components which necessitates the need to model and understand the impact these non-idealities have on system performance and security. OMNeT++ has been used as a basis to develop a simulation framework to support this endeavor. This framework, referred to as "qkdX" extends OMNeT++'s module and message abstractions to efficiently model optical components, optical pulses, operating protocols and processes. This paper presents the design of this framework including how OMNeT++'s abstractions have been utilized to model quantum optical components, optical pulses, fiber and free space channels. Furthermore, from our toolbox of created components, we present various notional and real QKD systems, which have been studied and analyzed.Comment: Published in: A. F\"orster, C. Minkenberg, G. R. Herrera, M. Kirsche (Eds.), Proc. of the 2nd OMNeT++ Community Summit, IBM Research - Zurich, Switzerland, September 3-4, 201