Generation of palladium clusters on Au(111) electrodes: Experiments and simulations

The properties of palladium clusters, generated with the electrochemical scanning tunneling microscope, have been investigated both by experiments and by computer simulations. The clusters are found to be larger and more stable if the tip is moved further towards the electrode surface in the generation process. The simulations suggest that the larger clusters consist of a palladium - gold mixture, which is more stable than pure palladium. Dissolution of the clusters occurs from the edges rather than layer by layer

Studies on the biodegradation of fosfomycin: Synthesis of 13C-labeled intermediates, feeding experiments with rhizobium huakuii PMY1, and Isolation of Labeled Amino Acids from Cell Mass by HPLC

Racemic (1R*,2R*)-1,2-dihydroxy-[1- ^{13C ₁]propylphosphonic acid and 1-hydroxy-[1- 13C ₁]acetone were synthesized and fed to R. huakuii PMY1. Alanine and a mixture of valine and methionine were isolated as their N-acetyl derivatives from the cell hydrolysate by reversed-phase HPLC and analyzed by NMR spectroscopy. It was found that the carbon atoms of the respective carboxyl groups were highly 13C-labeled (up to 65 %). Hydroxyacetone is therefore considered an obligatory intermediate of the biodegradation of fosfomycin by R. huakuii PMY1.}

A Density Functional Theory Study on the Active Center of Fe-Only Hydrogenase: Characterization and Electronic Structure of the Redox States

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z) (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fed at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(l) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(l)-Fe(l) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride, Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(l) species, but cannot bond with the Fe(l)-Fe(l) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (1) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(l)-Fe(l) complexes; and (iii) in the e(g)-2pi orbital more charge accumulates between the bridging CO and the Fe(d) than between the bridging CO and the Fe(p), and the occupation increase in this orbital will enhance the bonding between the bridging CO and the Fe(d), leading to the bridging-CO shift toward the Fe(d).

The diversity of extradiol dioxygenase (edo) genes in cresol degrading rhodococci from a creosote-contaminated site that express a wide range of degradative abilities.

Analysis of the bacterial population of soil surface samples from a creosote-contaminated site showed that up to 50% of the culturable micro-organisms detected were able to utilise a mixture of cresols. From fifty different microbial isolates fourteen that could utilise more than one cresol isomer were selected and identified by 16S rRNA analysis. Eight isolates were Rhodococcus strains and six were Pseudomonas strains. In general, the Rhodococcus strains exhibited a broader growth substrate range than the Pseudomonas strains. The distribution of various extradiol dioxygenase (edo) genes, previously associated with aromatic compound degradation in rhodococci, was determined for the Rhodococcus strains by PCR detection and Southern-blot hybridization. One strain, Rhodococcus sp. I1 exhibited the broadest growth substrate range and possessed five different edo genes. Gene disruption experiments indicated that two genes (edoC and edoD) were associated with isopropylbenzene and naphthalene catabolism respectively. The other Rhodococcus strains also possessed some of the edo genes and one (edoB) was present in all of the Rhodococcus strains analysed. None of the rhodococcal edo genes analysed were present in the Pseudomonas strains isolated from the site. It was concluded that individual strains of Rhodococcus possess a wide degradative ability and may be very important in the degradation of complex mixtures of substrates found in creosote.

Microcontroller based double beam modulation system for atomic scattering experiments

Double beam modulation is widely used in atomic collision experiments in the case where the noise arising froth each of the beams exceeds the measured signal. A method for minimizing the statistical uncertainty in a measured signal in a given time period is discussed, and a flexible modulation and counting system based on a low cost PIC microcontroller is described. This device is capable of modifying the acquisition parameters in real time during the course of an experimental run. It is shown that typical savings in data acquisition time of approximately 30% can be achieved using this optimized modulation scheme.

The influence of compliant surfaces on bypass transition', Experiments in Fluids

The objective of the work was to investigate the effect of compliant surfaces on the receptivity and bypass transition of a boundary layer. Hot wire measurements in the pre-transitional and transitional boundary layers on nine different compliant and one rigid surface with identical geometries were made. The experiments were conducted in air and the compliant surfaces were manufactured from gelatine covered by a 10 lm protective PVC film. The laminar boundary layer profiles and growth rate results were the same for all the surfaces. However, the receptivity of the laminar boundary layer to freestream disturbances increased close to the leading edge of each compliant surface. Further downstream the majority of the compliant surfaces were successful in reducing the receptivity to a value below that for the rigid surface. The transition onset position on the compliant surfaces ranged from 3% downstream to 20% upstream of the rigid surface position. It was concluded that compliant surfaces with optimum properties can reduce receptivity and delay transition.

Quasi-isochoric ion beam heating using dynamic confinement in spherical geometry for X-ray scattering experiments in WDM regime

Extreme states of matter such as Warm Dense Matter “WDM” and Dense Strongly Coupled Plasmas “DSCP” play a key role in many high energy density experiments, however creating WDM and DSCP in a manner that can be quantified is not readily feasible. In this paper, isochoric heating of matter by intense heavy ion beams in spherical symmetry is investigated for WDM and DSCP research: The heating times are long (100 ns), the samples are macroscopically large (mm-size) and the symmetry is advantageous for diagnostic purposes. A dynamic confinement scheme in spherical symmetry is proposed which allows even ion beam heating times that are long on the hydrodynamic time scale of the target response. A particular selection of low Z-target tamper and x-ray probe radiation parameters allows to identify the x-ray scattering from the target material and use it for independent charge state measurements Z* of the material under study.

Wide angle crystal spectrometer for angularly and spectrally resolved x-ray scattering experiments

A novel wide angle spectrometer has been implemented with a highly oriented pyrolytic graphite crystal coupled to an image plate. This spectrometer has allowed us to look at the energy resolved spectrum of scattered x rays from a dense plasma over a wide range of angles ( ~ 30°) in a single shot. Using this spectrometer we were able to observe the temporal evolution of the angular scatter cross section from a laser shocked foil. A spectrometer of this type may also be useful in investigations of x-ray line transfer from laser-plasmas experiments.

Observation of Collisionless Shocks in Laser-Plasma Experiments

The propagation in a rarefied plasma (n(e)less than or similar to 10(15) cm(-3)) of collisionless shock waves and ion-acoustic solitons, excited following the interaction of a long (tau(L)similar to 470 ps) and intense (I similar to 10(15) W cm(-2)) laser pulse with solid targets, has been investigated via proton probing techniques. The shocks' structures and related electric field distributions were reconstructed with high spatial and temporal resolution. The experimental results were interpreted within the framework of the nonlinear wave description based on the Korteweg-de Vries-Burgers equation.