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.     

A Negative Deviation from Stern–Volmer Equation in Fluorescence Quenching

A negative deviation from the normal Stern-Volmer equation shown in the fluorescence quenching of doxorubicin by adenosine 5' monophosphate is interpreted in terms of doxorubicin exists in two different conformers in the ground state. An estimate of the Stem-Volmer constant for the excited-state quenching is about 218 M(-1). The fluorescence decay of free doxorubicin is a bi-exponential in polar protic and polar aprotic solvents. In the presence of adenosine 5' monophosphate, doxorubicin shows a tri-exponential decay in water.     

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.     

Development of novel backwash cleaning technique for reverse osmosis in reclamation of secondary effluent

The objective of the study was to further develop a novel cleaning technique for reverse osmosis in reclamation of municipal secondary effluent. This technique is a new backwash method via direct osmosis (DO) by intermittent injection of the high salinity (HS) solution without stopping of high pressure pump and it is environment and membrane friendly technique. In the study, DO-HS trials were carried out with a UF-RO pilot system which was operated on site with the secondary treated effluent as the raw feed. Different operating conditions for DO-HS treatment in the actual process were investigated. It was found that the operation for implementation of the DO-HS cleaning technique developed was easy. For the first time, the actual profiles of HS concentration, DO backwash flow rate, brine flow rate and permeate pressure during DO-HS treatment have been demonstrated. It was observed that turbidity of the brine stream during DO-HS treatment at 3 NTU was 5 times higher than that before DO-HS treatment. The results from this study have confirmed the previous hypothesis with DO-HS treatment that there would be a strong driving force for DO backwash to lift and sweep the foulants from the membrane surface which would be carried over to the brine. The optimal plant operating conditions in terms of RO feed flow rate, HS concentration and HS injection time are ready for the DO-HS method to be adopted and validated in a long-term continuous plant operation.     

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...     

Monte Carlo simulation of boundary layer transition

A statistical method for simulating a boundary layer transition flow is proposed as based on experimental data on the kinematics and dynamics of turbulent spots (Emmons spots) on a flat plate placed in an incompressible fluid. The method determines intermittency with allowance for overlapping spots, which makes it possible to determine the forces on the plate surface and the flow field near the transition region if the mean streamwise velocity field in a developed turbulent boundary layer is known as a function of the Reynolds number. In contrast to multiparameter transition models, this approach avoids the use of nonphysical parameter values.     

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.