Spatially Resolved Confocal Resonant Raman Microscopic Analysis of Anode‐Grown Geobacter sulfurreducens Biofilms

When grown on the surface of an anode electrode, Geobacter sulfurreducens forms a multi‐cell thick biofilm in which all cells appear to couple the oxidation of acetate with electron transport to the anode, which serves as the terminal metabolic electron acceptor. Just how electrons are transported through such a biofilm from cells to the underlying anode surface over distances that can exceed 20 microns remains unresolved. Current evidence suggests it may occur by electron hopping through a proposed network of redox cofactors composed of immobile outer membrane and/or extracellular multi‐heme c‐type cytochromes. In the present work, we perform a spatially resolved confocal resonant Raman (CRR) microscopic analysis to investigate anode‐grown Geobacter biofilms. The results confirm the presence of an intra‐biofilm redox gradient whereby the probability that a heme is in the reduced state increases with increasing distance from the anode surface. Such a gradient is required to drive electron transport toward the anode surface by electron hopping via cytochromes. The results also indicate that at open circuit, when electrons are expected to accumulate in redox cofactors involved in electron transport due to the inability of the anode to accept electrons, nearly all c‐type cytochrome hemes detected in the biofilm are oxidized. The same outcome occurs when a comparable potential to that measured at open circuit (?0.30 V vs. SHE) is applied to the anode, whereas nearly all hemes are reduced when an exceedingly negative potential (?0.50 V vs. SHE) is applied to the anode. These results suggest that nearly all c‐type cytochrome hemes detected in the biofilm can be electrochemically accessed by the electrode, but most have oxidation potentials too negative to transport electrons originating from acetate metabolism. The results also reveal a lateral heterogeneity (x–y dimensions) in the type of c‐type cytochromes within the biofilm that may affect electron transport to the electrode.     

Modeling ExB drift transport in conceptual slot divertor configurations

At DIII-D, a slot divertor concept, called small-angle-slot (SAS), is under development, aiming to enable detachment at relatively low plasma edge density. We report on simulations using the SOLPS-ITER two-dimensional edge code to examine the performance of conceptual “SAS 2” slot configurations. The focus of the analysis is on E  ×  B drift effects on upstream density at detachment (UDD), with detachment marked by electron temperature T_e ≤ 3 eV at the outer strike point (OSP). With toroidal field such that radial E  ×  B drift carries particles from the OSP towards the private flux region (PFR), placing the OSP near the inner slot wall gives ≈20% lower UDD than having the OSP near the outer wall. The inner wall effectively traps the radial E  ×  B drift flux, resulting in low T_e and associated radial electric field in the PFR, and thus small losses from the slot to the inner target via poloidal E  ×  B drift flux. With toroidal field reversed such that radial E  ×  B drift is reversed, OSP placement near the inner wall gives ≈10% lower UDD than OSP placement near the outer wall. Although radial E  ×  B flux is from the OSP towards the outer wall, this flux largely escapes the slot, raising the UDD. A change in the slot shaping is suggested with the goal of eliminating such E  ×  B -driven particle losses from the slot.     

Third body modeling in fretting using the combined finite-discrete element method

A new approach was developed for modeling the effect of the third body on fretting. This was accomplished using the combined finite-discrete element method (FDEM) in which the third body is analyzed as discrete elements while the first bodies are modeled using finite elements. This approach provides a link between large scale models which treat the mass of wear debris as a single or small number of bodies and small scale models which only study a control volume. The FDEM was used to analyze the behavior of third body particles between flat sliding surfaces. When the third body mass is composed of unconnected particles, it behaves as a Newtonian fluid, but this behavior ceases when the particles are connected into platelets. The FDEM was also used to study the behavior of third body particles inside a Hertzian line contact. As the number of particles and platelet size increase the load carried by the worn slip zone grows larger in relationship to the unworn stick zone.     

Collision-induced dissociation mass spectrometry of nonionic surfactants following direct supercritical fluid injection

Direct injection from a capillary supercritical fluid chromatography system was used as an inlet technique for chemical ionization (CI) and low energy collision-induced dissociation (CID) mass spectrometry of a series of low volatility nonionic surfactant mixtures. Characteristic fragment ions produced by CID for various classes of nonionic surfactant molecules were found to depend greatly on the structure of the surfactant hydrophobe. This was the case even when the charge on the molecule appeared localized away from the hydrophobe. Numerous decomposition pathways are suggested by the fragment ions produced. The use of direct supercritical fluid injection as an inlet technique does not appear to influence adversely the ability to produce cm mass spectra. Direct supercritical fluid introduction allows CI to be compared with other ionization mechanisms more commonly used for multifunctional, low volatility samples.     

Optical control of coherent interactions between electron spins in InGaAs quantum dots

Coherent interactions between spins in quantum dots are a key requirement for quantum gates. We have performed pump-probe experiments in which pulsed lasers emitting at different photon energies manipulate two distinct subsets of electron spins within an inhomogeneous InGaAs quantum dot ensemble. The spin dynamics are monitored through their precession about an external magnetic field. These measurements demonstrate spin precession phase shifts and modulations of the magnitude of one subset of oriented spins after optical orientation of the second subset. The observations are consistent with results from a model using a Heisenberg-like interaction with μeV strength.     

Theoretical studies on aromaticity of selected hydroxypyrones. Part 3#. Chelatoaromaticity phenomenon in metalcomplexes of hydroxypyrones

The aim of this project is to study the aromatic properties of various forms (neutral, cationic, and anionic) of selected hydroxypyrones (pyromeconic acid, maltol, and ethylmaltol) and their metalcomplexes with aluminum, gallium, and indium ions. Aromaticity of hydroxypyrone metalcomplexes is important because it can influence the stability of such complexes, which is crucial for their applications in medicinal and environmental chemistry. Results from ten different indices of aromaticity (HOMA, NICS(0), NICS(1), NICS_scan, ASE_iso, PDI, FLU, I_ring, MCI, and KMCI) show that aromaticity in hydroxypyrones decreases in the order cations > neutral molecules > anions. Performed calculations situate the aromaticities of ligands in metalcomplexes close to their respective cations. This means that complexation causes a significant increase of the aromaticity of ligands, which stabilizes formed chelatocomplexes. On the other hand, we clearly show that rings that are involved in binding metal ions are not aromatic. Copyright © 2010 John Wiley & Sons, Ltd.     

Factorization of Lipschitz functions and absolute convergence of Vilenkin-Fourier series

LetG be a Vilenkin group (i.e., an infinite, compact, metrizable, zero-dimensional Abelian group). Our main result is a factorization theorem for functions in the Lipschitz spaces \(\mathfrak{L}\mathfrak{i}\mathfrak{p}\) (α,p; G). As colloraries of this theorem, we obtain (i) an extension of a factorization theorem ofY. Uno; (ii) a convolution formula which says that \(\mathfrak{L}\mathfrak{i}\mathfrak{p} (\alpha , r; G) = \mathfrak{L}\mathfrak{i}\mathfrak{p} (\beta , l; G)*\mathfrak{L}\mathfrak{i}\mathfrak{p} (\alpha - \beta , r; G)\) for 0<β<α<∞ and 1≤r≤∞; and (iii) an analogue, valid for allG, of a classical theorem ofHardy andLittlewood. We also present several results on absolute convergence of Fourier series defined onG, extending a theorem ofC. W. Onneweer and four results ofN. Ja. Vilenkin andA. I. Rubinshtein. The fourVilenkin-Rubinshtein results are analogues of classical theorems due, respectively, toO. Szász, S. B. Bernshtein, A. Zygmund, andG. G. Lorentz.     

Certification with optimal control strategies

The optimal control methodology called concentration-of-measure optimal control (COMOC), seeks to minimise a concen- tration-of-measure upper bound on the probability of failure of an uncertain system. This bound is computed for a system characterised by a single performance measure depending on random inputs. This work considers controlled multibody dynamics taking place in an uncertain environment. The goal is to quantify uncertainty in a controlled robot manoeuvre and to minimise the probability of failure with regard to a performance measure. First, a deterministic optimal control problem is solved, yielding state and control trajectories that minimise an objective function. Boundary conditions for the optimal control problem are chosen such that the system performs ideally in the sense of the performance measure. Secondly, the obtained manoeuvre is reconsidered in the presence of uncertainty. Using a concentration-of-measure inequality, a rigorous upper bound for the probability of failure is derived. Finally, an optimisation is performed that searches for a control sequence (in the neighbourhood of the given one), that minimises the probability of failure. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)