A general method for preparation of metal carbenes via solution- and polymer-based approaches

A new general, synthetically simple, and safe method for the preparation of metal carbene complexes, which is based on diphenyl sulfonium salts as carbenoid precursors, has been developed, and its scope and applications were studied. In general, deprotonation of a sulfonium salt with a base results in a sulfur ylide, which, in turn, reacts with an appropriate metal precursor to give the corresponding metal carbene complex. Thus, starting from benzyldiphenylsulfonium salt, the complexes (PCX)Rh=CHPh (X = P, N) were prepared in quantitative yield. Syntheses of Grubbs' catalyst, (PCy(3))(2)Cl(2)Ru=CHPh, and of Werner's carbene, [Os(=CHPh)HCl(CO)(P(i)Pr(3))(2)], were achieved by this method. Novel trans-bisphosphine Rh and Ir carbenes, ((i)Pr(3)P)(2)(Cl)M=CHPh, which could not be prepared by other known methods, were synthesized by the sulfur ylide approach. The method is not limited to metal benzylidenes, as demonstrated by the preparation of the Ru vinyl-alkylidene, (PCy(3))(2)Cl(2)Ru=CH-CH=CH(2), methoxycarbonyl-alkylidene, (PCy(3))(2)Cl(2)Ru=CH(CO(2)Me), and alkylidene (PCy(3))(2)Cl(2)Ru=CH(CH(3)), (PCy(3))(2)Cl(2)Ru=CH(2) compounds. The problem of recycling of starting materials as well as the issue of facile purification of the product metal carbene complex were addressed by the synthesis of a polymer-supported diarylsulfide, the carrier of the carbenoid unit in the process. Based on the sulfur ylide route, a methodology for the synthesis of metallocarbenes anchored to a polymer via the carbene ligand, using a commercial Merrifield resin, was developed.     

Characterization of Commercial Amylases for the Removal of Filter Cake on Petroleum Wells

Drilling fluid has many functions, such as carry cuttings from the hole permitting their separation at the surface, cool and clean the bit, reduce friction between the drill pipe and wellbore, maintain the stability of the wellbore, and prevent the inflow of fluids from the wellbore and form a thin, low-permeable filter cake. Filter cake removal is an important step concerning both production and injection in wells, mainly concerning horizontal completion. The drilling fluids are typically comprised of starch, the most important component of the filter cake. A common approach to remove this filter cake is the use of acid solutions. However, these are non-specific reactants. A possible alternative is the use of enzymatic preparations, like amylases, that are able to hydrolyze starch. Wells usually operate in drastic conditions for enzymatic preparations, such as high temperature, high salt concentration, and high pressure. Thus, the main objective of this work was to characterize four enzymatic preparations for filter cake removal under open hole conditions. The results showed that high salt concentrations (204,000 ppm NaCl) in completion fluid decreased amylolytic activity. All enzymatic preparations were able to catalyze starch hydrolysis at all temperatures tested (30, 65, 80, and 95 °C). An increase of amylolytic activity was observed with the increase of pressure (100, 500 and 1,000 psi) for one commercial amylase.     

Multineutron photonuclear reactions on the <Superscript>197</Superscript>Au isotope

An experiment on irradiation of the ¹⁹⁷Au isotope by a beam of bremsstrahlung γ-rays of maximum energy E _γ ^m = 70 MeV has been carried out at the RTM-70 race-track microtron of the INP MSU. Residual activity spectra of the irradiated sample were measured. Multiparticle photonuclear reactions on the ¹⁹⁷Au nucleus are observed. Photonuclear reactions with emission of as many as six neutrons are observed for the first time.     

Rapid, sensitive DNT vapor detection with UV-assisted photo-chemically synthesized gold nanoparticle SERS substrates

We report rapid, sensitive, and direct detection of 2,4-dinitrotoluene (DNT) vapor using tailored gold nanoparticles (Au-NPs) as the SERS substrate. The Au-NPs were synthesized using the UV-assisted photo-chemical reduction method and subsequently formed a monolayer on the glass slide through polymer-mediated self-assembly. The SERS substrate such prepared has high SERS enhancement, high affinity towards DNT vapor, and rapid response to the DNT adsorption/desorption. We systematically studied the effect of the Au-NP size and surface density on the SERS performance such as enhancement factor and response time. With the optimized SERS substrate, an enhancement factor over 5.6 × 10(6) was achieved. Furthermore, real-time detection of DNT vapor with only 0.35 second data acquisition time was demonstrated using a 12 mW laser. Compared to previously reported results, we achieved two orders of magnitude reduction in detection time and more than one order of magnitude reduction in excitation laser power. The detection limit is estimated to be 0.4 attogram, which corresponds to a sub-ppb DNT concentration in air. This work will lead to the development of ultra-fast and ultra-sensitive SERS devices for explosive identification and monitoring.     

Hybrid Plasma – Prospects for Application in Medicine and Biology

Russian Physics Journal - Different schemes and designs of generators of low-temperature hybrid plasma produced by simultaneous ionization of plasma-generating medium by an electron beam with...     

Present status and prospects for Spin-Echo Small-Angle Neutron Scattering (SESANS) at PIK neutron source

We discuss the present status and the prospects of Spin-Echo Small-Angle Neutron Scattering (SESANS) against the background of the available expertise and the neutron source PIK at PNPI (Gatchina). Two options for SESANS instruments are reviewed: (1) monochromatic with π-flipping permalloy foils and (2) with adiabatic radio frequency spin flippers in a white beam, combined with time-of-flight data collection. A software tool for quantitative prediction of the technical properties of option (2) is developed. For both options, we show that a SESANS instrument which can compete with instruments elsewhere, is realistic. For option (2), we suggest a perspective of spin-echo-length range such that neutron interference experiments become feasible.     

Is it possible to determine the chemical composition of cosmic rays in the “LORD” lunar experiment?

The results of the simulation of cascade radio emission from ultrahigh-energy cosmic rays in the LORD lunar experiment using circularly polarized antennas are presented. It is shown that based on the characteristics of radio emission caused by cascades from protons and iron nuclei in lunar regolith and escaped into vacuum it is impossible to distinguish these cascades in the primary energy region above 10²⁰ eV.     

Multineutron photodisintegration of the 197Au nucleus behind the giant dipole resonance

An experiment in which the gold isotope ¹⁹⁷Au was irradiated with a beam of bremsstrahlung photons having an endpoint energy of E _γ ^m = 67.7 MeV and originating from the RTM-70 racetrack microtron of the Institute of Nuclear Physics at Moscow State University was performed. The gammaray spectra of the residual beta activity of an irradiated sample were measured. Multinucleon photonuclear reactions on ¹⁹⁷Au nuclei were observed in the experiment. Photonuclear reactions on a ¹⁹⁷Au nucleus that involve the emission of up to seven neutrons were recorded for the first time. The experimental results in question suggest the important role of the quasideuteron photodisintegration mechanism in the energy region behind the giant dipole resonance.     

EDX depth profiling by means of effective layers

A new approach is described for depth profiling in stratified multilayer samples by recording energy dependent characteristic x-ray EDX(E ₀ ) curves in a scanning electron microscope. An effective layer technique replaces the x-ray excitation function of the heterogeneous target by an equivalent function of a homogeneous sample. First results of thickness determination are shown and compared to direct measurements of film thickness monitoring (FTM) and atomic force microscopy (AFM).