X-ray absorption spectroscopic characterization of the molybdenum site of Escherichia coli dimethyl sulfoxide reductase

Structural studies of dimethyl sulfoxide (DMSO) reductases were hampered by modification of the active site during purification. We report an X-ray absorption spectroscopic analysis of the molybdenum active site of Escherichia coli DMSO reductase contained within its native membranes. The enzyme in these preparations is expected to be very close to the form found in vivo. The oxidized active site was found to have four Mo-S ligands at 2.43 A, one Mo=O at 1.71 A, and a longer Mo-O at 1.90 A. We conclude that the oxidized enzyme is a monooxomolybdenum(VI) species coordinated by two molybdopterin dithiolenes and a serine. The bond lengths determined for E. coli DMSO reductase are very similar to those determined for the well-characterized Rhodobacter sphaeroides DMSO reductase, suggesting similar active site structures for the two enzymes. Furthermore, our results suggest that the form found in vivo is the monooxobis(molybdopterin) species.     

Calcium oxalate crystals in tomato and tobacco plants: morphology and in vitro interactions of crystal-associated macromolecules

Plants form calcium oxalate crystals with unique morphologies under well-controlled conditions. We studied the morphology of single calcium oxalate monohydrate (whewellite) crystals extracted from tomato and tobacco leaves. These crystals have a pseudotetrahedral shape. We identified the (101), (101) or (102), (110), and (hk0) faces as stable faces. The morphology is chiral with unique handedness. We also show that calcium oxalate monohydrate crystals isolated from tomato, tobacco, and bougainvillea leaves contain macromolecules rich in Gly, Glx, and Ser. Crystal-associated macromolecules extracted from tomato and tobacco influence the morphology of calcium oxalate monohydrate crystals grown in vitro, promoting preferential development of the [120] faces. Furthermore, crystal-associated macromolecules from tobacco promote nucleation of calcium oxalate monohydrate crystals, whereas model polypeptides do not have any significant effect on nucleation. These results imply an active role of the crystal-associated macromolecules in the formation of pseudotetrahedral shapes in vitro, and these properties may in part be responsible for the unique chiral morphology of the natural pyramidal-shaped crystals.     

High-efficiency blue generation by frequency doubling of femtosecond pulses in a thick nonlinear crystal

We have demonstrated highly efficient frequency doubling of femtosecond pulses in a thick, noncritically phase-matched KNbO(3) crystal under conditions of large group-velocity mismatch. At low power we observed a slope efficiency of ~300% nJ (-1) for harmonic conversion, and at higher powers we generated 170 mW of second-harmonic blue output for 300 mW of input light. Furthermore, we have shown that the focusing dependence for our conditions of large group-velocity mismatch is considerably different from that obtained for frequency doubling of continuous-wave light. We have also demonstrated that one can tune the spectral width of the generated blue light by varying the focusing conditions.     

THE AQUEOUS PHOTOLYSIS OF ETHYLENE GLYCOL ADSORBED ON GOETHITE

Abstract— Suspensions of goethite (α-FeOOH) were photolyzed in aerated ethylene glycol-water solutions at pH 6.5, with ultraviolet light in the wavelength range300–400 nm. Under these conditions, formaldehyde and glycolaldehyde were detected as photoproducts. Quantum yields of formaldehyde production ranged from 1.9 7times; 10^-5 to 2.9 × 10^-4 over the ethylene glycol concentration range of 0.002-2.0 mol/ℓ, and gave evidence that the reaction occurred at the goethite surface. Quantum yields of glycolaldehyde were 20% less than those of formaldehyde, and displayed a concentration-dependent relationship with ethylene glycol similar to that of formaldehyde. Immediately after photolysis, Fe²⁺ was measured to be 4.6 × 10^-7 mol/ℓ in an aerated suspension containing 1.3 mol/ℓ ethylene glycol, and 8.5 × 10^-6 mol/ℓ in the corresponding deoxygenated suspension. Glycolaldehyde was not generated in the deoxygenated suspensions. These results are consistent with a mechanism involving the transfer of an electron from an adsorbed ethylene glycol molecule to an excited state of Fe³⁺ (Iron[III]) in the goethite lattice, to produce Fe²⁺ and an organic cation. In a series of reactions involving O₂, FeOOH, and Fe²⁺, the organic cation decomposes to form formaldehyde and the intermediate radicals "OH and" CH₂OH. OH reacts further with ethylene glycol in the presence of O₂ to yield glycolaldehyde. Aqueous photolysis of ethylene glycol sorbed onto goethite is typical of reactions that can occur in the aquatic environment.     

Zur ma?analytischen Bestimmung von Wolfram und Uran

Zusammenfassung Die für die technische Bestimmung von Molybdän brauchbare fällungsanalytische Titration mit Silbernitrat und potentiometrischer Endpunktsanzeige ist für Wolfram und Uran wegen der ungünstigeren Löslichkeitsverhältnisse nicht brauchbar.Die Reduktion im Silberreduktor und anschließende Titration mit Dichromat anstatt mit dem bisher verwendeten Cer(IV)-sulfat mit Endpunktsanzeige durch Farbumschlag (Diphenylamin) oder auf potentiometrischem Wege ist für Uran bei Einhaltung entsprechender Arbeitsbedingungen (Reduktion in 4 n Salzsäure bei 60°C, 2 · 10^–3 Mol Uran/l als obere Grenze bei der Titration) gut verwendbar. Der Silberreduktor hat jedoch keine erkennbaren Vorteile gegenüber dem Bleireduktor.Für Wolfram ist diese Methode wegen der ungünstigen Lage der Redoxpotentiale nicht brauchbar.     

Optimization of Graphene Layers Grown on Pt/Ti/SiO2 by Hot Filament Chemical Vapor Deposition

Large area single and bilayer graphene are grown on Pt/Ti/SiO₂ substrates by hot filament chemical vapor deposition (HFCVD) with and without the assistance of Cu foil. The quality and number of graphene layers deposited on the substrate are assessed by Raman Spectroscopy. Atomic Force Microscopy (AFM) is used for assessing the surface topography of the graphene films grown on the Pt/Ti/SiO₂ substrates. The microstructure and elemental analyses are performed by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The results show that bilayer graphene growth is facilitated by a copper foil placed nearby Pt/Ti/SiO2 substrate and by a high filament temperature in the HFCVD reactor. Monolayer graphene grows only when no copper foil is placed near the Pt/Ti/SiO₂ substrate at a low filament temperature. The approach paves a novel pathway towards the layer-controlled growth of graphene on Pt/Ti/SiO₂ substrates by HFCVD for frontier applications.     

Scattering by small defects in the neighbourhood of a fluid-solid interface

The scattering of incident plane elastic waves by a varietyof different defects that lie upon a fluid-solid interface isconsidered here using matched asymptotic expansions. The expansionscheme is developed in terms of a parameter , the ratio of typicaldefect length scale to a typical wavelength of the incidentfield, taken to be small. Three different canonical situations occur and these are illustratedvia three specific examples treated here: a rigid strut, anedge crack, and a rigid strip. In each case the leading-ordermatching is performed to identify the leading-order contributionof the defect to the acoustic field in the far field. In particular,each defect is identified with a source of dipole response ininterfacial stress of displacement. It is shown in the limit as s<<s1 that in the inner problemsthe fluid and solid pieces uncouple in a particularly convenientmanner allowing analytical solutions to be deduced. These arethen matched with appropriate outer solutions.     

Runge–Kutta–Nyström‐type parallel block predictor–corrector methods

This paper describes the construction of block predictor–corrector methods based on Runge–Kutta–Nyström correctors. Our approach is to apply the predictor–corrector method not only with stepsize h, but, in addition (and simultaneously) with stepsizes a _i h, i = 1 ...,r. In this way, at each step, a whole block of approximations to the exact solution at off‐step points is computed. In the next step, these approximations are used to obtain a high‐order predictor formula using Lagrange or Hermite interpolation. Since the block approximations at the off‐step points can be computed in parallel, the sequential costs of these block predictor–corrector methods are comparable with those of a conventional predictor–corrector method. Furthermore, by using Runge–Kutta–Nyström corrector methods, the computation of the approximation at each off‐step point is also highly parallel. Numerical comparisons on a shared memory computer show the efficiency of the methods for problems with expensive function evaluations.     

Impurity distribution and electrical characteristics of boron-doped Si1−x Ge x /Si p +/N heterojunction diodes produced using pulsed UV-laser-induced epitaxy and Gas-immersion laser doping

A two-step pulsed UV-laser process which independently controls the metallurgical and electrical junction depth of a Si_1–x Ge _x /Si heterojunction diode has been implemented. Pulsed Laser-Induced Epitaxy (PLIE) combined with Gas-immersion Laser Doping (GILD) are used to fabricate boron-doped heteroepitaxial p ⁺/N Si_1–x Ge _x /Si layers and diodes. Borontrifluoride is used as the gaseous dopant source in the GILD process step. Boron incorporation and activation are investigated as a function of laser energy fluence and the number of laser pulses using SIMS and Halleffect measurements. The dose of incorporated dopant is on the order of 10¹³ cm^–2 per pulse. The B profiles obtained are flat except for a peak at the interface resulting from segregation effects. The B and Ge distributions are compared with shifts in the turn-on voltage of p ⁺/N Si_1–x /Si heterojunction diodes produced by the process. The GILD/PLIE process is spatially selective with the resulting diodes fabricated being quasiplanar. Hole mobilities in the heavily doped Si_1–x Ge _x films are found to be slightly lower than in comparable Si films.Presently at the Oregon Graduate Institute, Beaverton, OR 97006, USA