Kinetics and Mechanism of the Pyridinolyses of O‐Methyl and O‐Ethyl Phenyl Phosphonochloridothioates in Acetonitrile

Kinetic studies on the reactions of O‐methyl ( 2 ) and O‐ethyl ( 3 ) phenyl phosphonochloridothioates with X‐pyridines have been carried out in acetonitrile at 35.0°C. The pyridinolysis rates of 2 are slightly faster than those of 3 . The substituent effects of X on the pyridinolysis rates of 2 and 3 are similar. The Hammett and Brönsted plots with X in the nucleophiles are biphasic concave upward with a break point at X = 3‐Ph for both substrates. The stepwise mechanism with rate‐limiting leaving group departure from the intermediate is proposed based on the β_X values and biphasic concave upward free energy relationship for both substrates. The biphasic concave upward free energy relationships are rationalized by a frontside nucleophilic attack TSf with more basic pyridines and backside attack TSb with less basic pyridines for both substrates.     

Roles of the Synergistic Reductive O-Methyltransferase GilM and of O-Methyltransferase GilMT in the Gilvocarcin Biosynthetic Pathway

Two enzymes of the gilvocarcin biosynthetic pathway, GilMT and GilM, with unclear functions were investigated by in vitro studies using purified, recombinant enzymes along with synthetically prepared intermediates. The studies revealed GilMT as a typical S-adenosylmethionine (SAM) dependent O-methyltransferase, but GilM was identified as a pivotal enzyme in the pathway that exhibits dual functionality in that it catalyzes a reduction of a quinone intermediate to a hydroquinone, which goes hand-in-hand with a stabilizing O-methylation and a hemiacetal formation. GilM mediates its reductive catalysis through the aid of GilR that provides FADH(2) for the GilM reaction, through which FAD is regenerated for the next catalytic cycle. This unusual synergy eventually completes the biosynthesis of the polyketide-derived defuco-gilvocarcin chromphore.     

Elemental characterisation of strawberry grown in Islamabad by <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-instrumental neutron activation analysis and atomic absorption spectrophotometry and its dietary assessment

Mineral contents of strawberry, collected from different farms of Islamabad were analysed by semi-absolute k ₀-instrumental neutron activation analysis and atomic absorption spectrophotometry. The samples were irradiated at two research reactors located in Pakistan Institute of Nuclear Science & Technology (PINSTECH), Islamabad. The analytical methodologies were validated by analysing reference materials, IAEA-336 (lichen) and IAEA-V-10 (hay powder). In all the samples, a total of 26 elements were quantified, among them 16 elements (Ca, Cd, Cl, Co, Cr, Cs, Fe, K, Mg, Mn, Na, Pb, Ru, Sc, Sr and Zn) were found in all the samples. The determined elemental concentrations in strawberry were compared with the reported values from other countries. In comparison with the mineral contents of other fruits, strawberry stands best source of Mn and the second most important source of K after banana. Intake of trace metals through this source was calculated and it was found that strawberry provides Mn (1.95–3.68 mg/kg), Cr (19.2–46.3 × 10⁻³ mg/kg), Fe (3.45–8.72 mg/kg), K (1,520–1,670 mg/kg) and Mg (100–220 mg/kg), which forms 26, 19, 14, 7 and 7% of the recommended dietary allowances for the respective metals. The daily intake of Cd and Pb were compared with the provisional tolerable weekly intake defined by FAO/WHO.     

Convective heat transfer and MHD effects on Casson nanofluid flow over a shrinking sheet

Current study examines the magnetohydrodynamic (MHD) boundary layer flow of a Casson nanofluid over an exponentially permeable shrinking sheet with convective boundary condition. Moreover, we have considered the suction/injection effects on the wall. By applying the appropriate transformations, system of non-linear partial differential equation along with the boundary conditions are transformed to couple non-linear ordinary differential equations. The resulting systems of non-linear ordinary differential equations are solved numerically using Runge-Kutta method. Numerical results for velocity, temperature and nanoparticle volume concentration are presented through graphs for various values of dimensionless parameters. Effects of parameters for heat transfer at wall and nanoparticle volume concentration are also presented through graphs and tables. At the end, fluid flow behavior is examined through stream lines. Concluding remarks are provided for the whole analysis.     

Specific characteristics of molten carbonate fuel cell in realization of electrochemical coal oxidation

The test object was a fuel cell with free molten carbonate electrolyte providing realization of direct electrochemical oxidation of solid hydrocarbons. This study involved the effect of the fuel type and dispersion as well as cathode reagent gas mixture composition to the fuel cell functional parameters. The used fuels were dispersed and monolithic graphite, anthracite, and jet coal specimens. The effect of oxygen/carbon dioxide ratio on the mixture fed to cathode to the open circuit cell voltage and achieved current density levels was studied with respect to interrelation of the processes taking place in the cathode and anode units of the fuel cell. A correlation was noted between the specific fuel cell characteristics and hydrogen content in the fuel material. The highest level of current density and specific power was recorded for jet coal characterized with high hydrogen content. The different characteristics of monolithic and dispersed fuel specimens were accounted for by the effect of losses at contacts between particles. Achievement of high current density and specific power was demonstrated by using dispersed coal fuel.     

Validated HPLC–MS–MS method for simultaneous determination of atorvastatin and 2-hydroxyatorvastatin in human plasma—pharmacokinetic study

Cholesterol-reducing statin drugs are the most frequently prescribed agents for reducing morbidity and mortality related to coronary heart disease. In this publication a validated, highly sensitive, and selective isocratic HPLC method is reported for quantitative determination of the major statin drug atorvastatin (ATV) and its metabolite 2-hydroxyatorvastatin (HATV). Detection was performed with an electrospray ionization triple-quadrupole mass spectrometer equipped with an ESI interface operating in positive-ionization mode. Multiple reaction monitoring (MRM) was used for MS–MS detection. The calibration plot was linear in the concentration range 0.10–40.00 ng mL⁻¹ for both ATV and HATV. Inter-day and intra-day precision and accuracy of the proposed method were characterized by measurement of relative standard deviation (RSD) and percentage deviation, respectively; both were less than 8% for both analytes. The limit of quantitation was 0.02 ng mL⁻¹ for ATV and 0.07 ng mL⁻¹ for HATV. The method was used for pharmacokinetic study of ATV and HATV. Pharmacokinetic data for all analytes are also reported.     

A study of the structure and properties of nanostructured ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite powders

The correlation between temperature treatment conditions and the ratio of components in nanostructured fibrous powders with a composition of ZrO₂-Y₂O₃-Al₂O₃ and their porous crystal structure and physicochemical properties is studied. The dependences of the ratio between zirconia tetragonal and monoclynic phases on the treatment temperature and the alumina content are found to have a nonmonotonic character. The growth of zirconia crystallite size is suppressed by introduced nanocrystalline alumina in a temperature range of 600–1200°C, which is caused by the processes of ternary solid solution formation. The bulk and picnometric density values of materials are proportional to the temperature of heat treatment. The temperature dependence of the specific surface and the size of oxide grain particles has an inversely proportional character. With increasing alumina content in the powders, the specific surface increases, while the picnometric and bulk densities decrease.     

Bistability of a “chevron” smectic C* liquid crystal in an external electric field

The system of nonlinear equations describing a surface-stabilized ferroelectric smectic C* liquid crystal in the chevron geometry has been investigated by numerical methods in the framework of the continuum model of liquid crystals. Stable orientational and structural configurations have been studied, and the results obtained have been compared with those derived using simplified models. The height of the potential barrier separating two stable configurations has been determined, and the transition between them under the action of the external electric field has been examined. It has been demonstrated that this effect has a threshold character. The dependence of the threshold field on the film thickness has been analyzed.     

Effect of the nonlinear compression of ultrashort microwave pulses in the process of the amplification by quasistationary electron beams

An effect of the nonlinear compression of ultrashort microwave pulses has been observed in the process of the amplification of quasistationary electron beams. The Cherenkov mechanism of the interaction of a rectangular electron beam with a decelerated wave in a waveguide partially filled with an insulator is used. The experiment has been conducted on a setup consisting of two synchronized RADAN high-current accelerators. The first accelerator supplied a generator of 37-GHz superradiance pulses with a duration of about 300 ps. The second accelerator with a beam current of up to 1.2 kA and an electron energy of about 300 keV was used in an amplifying section. The theoretical analysis shows that the amplification of the electromagnetic pulses (at least by a factor of 4 in the power) is accompanied by a strong decrease in their duration (down to 100 ps).     

On the singular nonlinear self-adjoint eigenvalue problem for differential algebraic systems of equations

The general nonlinear self-adjoint eigenvalue problem for a differential algebraic system of equations on a half-line is examined. The boundary conditions are chosen so that the solution to this system is bounded at infinity. Under certain assumptions, the original problem can be reduced to a self-adjoint system of differential equations. After certain transformations, this system, combined with the boundary conditions, forms a nonlinear self-adjoint eigenvalue problem. Requirements for the appropriate boundary conditions are clarified. Under the additional assumption that the initial data are monotone functions of the spectral parameter, a method is proposed for calculating the number of eigenvalues of the original problem that lie on a prescribed interval of this parameter.