Obliquely Propagating Electron Acoustic Shock Waves in Magnetized Plasma

Obliquely propagating electron acoustic shock waves in plasma with stationary ions, cold and superthermal hot electrons are investigated in magnetized plasma. Employing reductive perturbation method, Korteweg-de Vries-Burgers equation (KdVB) is derived in the small amplitude approximation limit. The analytical and numerical calculations of the KdVB equation show the variation of shock waves structure (amplitude, velocity, and width) with different plasma parameters. Particle density (α), superthermal parameter (κ), electron temperature ratio (??), kinetic viscosity (η₀), obliqueness (k_z), and strength of magnetic field (ω_c) significantly modify the properties of the shock waves structures. The present investigation is useful to understand dissipative structures observed in space or laboratory plasma where multielectrons population with superthermal electrons are prevalent.     

Markov ratio decision processes

A finite-state Markov decision process, in which, associated with each action in each state, there are two rewards, is considered. The objective is to optimize the ratio of the two rewards over an infinite horizon. In the discounted version of this decision problem, it is shown that the optimal value is unique and the optimal strategy is pure and stationary; however, they are dependent on the starting state. Also, a finite algorithm for computing the solution is given.     

Enantioselective installation of adjacent tertiary benzylic stereocentres using lithiation–borylation–protodeboronation methodology. Application to the synthesis of bifluranol and fluorohexestrol

1,2-Diaryl ethanes bearing 1,2-stereogenic centres show interesting biological activity but their stereocontrolled synthesis has not been reported forcing a reliance of methods involving diastereomer and enantiomer separation. We have found that this class of molecules can be prepared with very high stereocontrol using lithiation–borylation methodology. The reaction of an enantioenriched benzylic lithiated carbamate with an enantioenriched benzylic secondary pinacol boronic ester gave a tertiary boronic ester with complete diastereo- and enantiocontrol. It was essential to use MgBr₂/MeOH after formation of the boronate complex, both to promote the 1,2-migration and to trap any lithiated carbamate/benzylic anion that formed from fragmentation of the ate complex, anions that would otherwise racemise and re-form the boronate complex eroding both er and dr of the product. When the benzylic lithiated carbamate and benzylic secondary pinacol boronic ester were too hindered, boronate complex did not even form. In these cases, it was found that the use of the less hindered neopentyl boronic esters enabled successful homologation to take place even for the most hindered reaction partners, with high stereocontrol and without the need for additives. Protodeboronation of the product boronic esters with TBAF gave the target 1,2-diaryl ethanes bearing 1,2-stereogenic centres. The methodology was applied to the stereocontrolled synthesis of bifluranol and fluorohexestrol in just 7 and 5 steps, respectively.     

Hemiaminals as substrates for sulfur ylides: direct asymmetric syntheses of functionalised pyrrolidines and piperidines

Phenyl stabilised chiral sulfur ylides react with five-membered-ring hemiaminals to give functionalised pyrrolidines directly with high enantioselectivity. The reaction can be diverted to give piperidines instead by isolation of the intermediate epoxide and treatment with TMSOTf.     

Direct separation of boron from Na- and Ca-rich matrices by sublimation for stable isotope measurement by MC-ICP-MS

An improved technique for precise and accurate determination of boron isotopic composition in Na-rich natural waters (groundwater, seawater) and marine biogenic carbonates was developed. This study used a ‘micro-sublimation’ technique to separate B from natural sample matrices in place of the conventional ion-exchange extraction. By adjusting analyte to appropriate pH, quantitative recovery of boron can be achieved (>98%) and the B procedural blank is limited to <8 pg. An additional mass bias effect in MC-ICP-MS was observed which could not be improved via the standard-sample-standard bracketing or the ‘pseudo internal’ normalization by Li. Therefore a standard other than NBS SRM 951 was used to monitor plasma condition in order to maintain analytical accuracy. An isotope cross-calibration with results from TIMS shows that the space-charge mass bias on MC-ICP-MS can be successfully corrected using off-line mathematical manipulation. Several reference materials, including the seawater IAPSO and two groundwater standards IAEA-B-2 and IAEA-B-3, were used to validate this approach. We found that the δ¹¹B of the reference coral JCp-1 was 24.22 ± 0.28‰, corresponding to seawater pH based on the coral δ¹¹B-pH function.     

Selective hydrophobic pocket binding observed within the carbonic anhydrase II active site accommodate different 4-substituted-ureido-benzenesulfonamides and correlate to inhibitor potency

4-Substituted-ureido benzenesulfonamides showing inhibitory activity against carbonic anhydrase (CA, EC 4.2.1.1) II between 3.3-226 nM were crystallized in complex with the enzyme. Hydrophobic interactions between the scaffold of the inhibitors in different hydrophobic pockets of the enzyme were observed, explaining the diverse inhibitory range of these derivatives.     

Delineation of the factors governing reactivity and selectivity in epoxide formation from ammonium ylides and aldehydes

Diastereoselectivity in reactions of aryl-stabilised ammonium ylides are highly sensitive to the nature of the amine and the ylide substituent. DFT calculations are consistent with a mechanism in which reversibility in betaine formation [despite the high energy (and therefore instability) of ammonium ylides] is finely balanced due to the high barrier to ring closure.     

Reversed-phase liquid chromatography using mandelic acid as an eluent for the determination of uranium in presence of large amounts of thorium

Studies were carried out for the separation of uranium (U) and thorium (Th) on reversed-phase (RP) C₁₈ columns using mandelic acid as an eluent. Retention of thorium–mandelate on the unmodified stationary phase was found to be greater than that of uranyl–mandelate under the pH conditions employed. Th retention capacity of the stationary phase was determined as a function of pH and MeOH content of the mobile phase. The optimised parameters allowing U elution prior to Th were utilized for the determination of small amounts of U in the presence of large amounts of Th. The method has been used for the determination of U in synthetic samples with Th/U amount ratios up to 100,000 (10 μg/g of U) without any pre-separation, employing a particulate C₁₈ column. Effect of concentration of ion interaction reagents (IIRs) on the retention was studied to understand the mechanism of adsorption of their mandelate complexes onto the stationary phase. The experiments conducted unequivocally prove that thorium–mandelate complex is neutral whereas uranyl–mandelate complex is anionic in nature.     

Sustainable feasibility of waste printer ink to magnetically separable iron oxide–doped nanocarbons for styrene oxidation

A simpler cost-effective method for the isolation of magnetically separable ‘self-doped iron oxide nanocarbons’ (FeO-NC) from waste printer ink (used as a carbon source material which is available free of cost) is discussed here. The process involves carbonization of waste printer ink in a muffle furnace at ~600 °C to obtain FeO-NC. The as-prepared FeO-NC has been investigated as an efficient heterogeneous catalyst for the long-known important organic reaction involving transformation of styrene to benzaldehyde in a quantitative yield (~70%). Importantly, FeO-NC were magnetically separable along with good recyclability, which supports the sustainability of reported process.