anti-Selective aldol reactions of chiral alcohol substituted γ-benzyloxyl vinylogous urethanes and the synthesis of 3-benzyloxyl-4-hydroxylalkan-2-ones

The anti-selective aldol reaction of chiral alcohol-substituted γ-benzyloxy vinylogous urethanes is described. The use of (1S,2R,4R)-1-(hydroxydiphenylmethyl)-7,7-dimethylbicyclo[2,2,1]-heptan-2-ol as a chiral auxiliary in the aldol reaction of a vinylogous urethane enolate was found to provide anti-products in good yields with moderate to excellent enantioselectivities. The major anti-vinylogous urethane lactones were transformed into 3-benzyloxyl-4-hydroxylalkan-2-ones in good yields.     

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3− and SO32− in Aqueous Solution

The kinetics and mechanism of the reaction of S^IV (SO₃^2?+HSO₃^?) with a ruthenium(VI) nitrido complex, [(L)Ru^VI(N)(OH₂)]⁺ (Ru^VIN, L=N,N′‐bis(salicylidene)‐o‐cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO₃^? and SO₃^2? by Ru^VIN. A deuterium isotope effect of 4.7 is observed in the HSO₃^? pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N?S bond formation (partial N‐atom transfer) between Ru^VIN and HSO₃^? and H⁺ transfer from HSO₃^? to a H₂O molecule.     

Ag/Ni Metallization Bilayer: A Functional Layer for Highly Efficient Polycrystalline SnSe Thermoelectric Modules

The structural and electrical characteristics of Ag/Ni bilayer metallization on polycrystalline thermoelectric SnSe were investigated. Two difficulties with thermoelectric SnSe metallization were identified for Ag and Ni single layers: Sn diffusion into the Ag metallization layer and unexpected cracks in the Ni metallization layer. The proposed Ag/Ni bilayer was prepared by hot-pressing, demonstrating successful metallization on the SnSe surface without interfacial cracks or elemental penetration into the metallization layer. Structural analysis revealed that the Ni layer reacts with SnSe, forming several crystalline phases during metallization that are beneficial for reducing contact resistance. Detailed investigation of the Ni/SnSe interface layer confirms columnar Ni-Sn intermetallic phases [(Ni₃Sn and Ni₃Sn₂) and Ni_5.63SnSe₂] that suppress Sn diffusion into the Ag layer. Electrical specific-contact resistivity (5.32 × 10^?4 Ω cm²) of the Ag/Ni bilayer requires further modification for development of high-efficiency polycrystalline SnSe thermoelectric modules.     

Residual determination and risk assessment of buprofezin in plum (Prunus domestica) grown in open‐field conditions following the application of three different formulations

This study was conducted to characterize the residual level and perform a risk assessment on buprofezin formulated as an emulsifiable concentrate, wettable powder, and suspension concentrate over various treatment schedules in plum (Prunus domestica). The samples were extracted with an AOAC quick, easy, cheap, effective, rugged, and safe, ‘QuEChERS’, method after major modifications. As intrinsic interferences were observed in blank plum samples following dispersive‐solid phase extraction (consisting of primary secondary amine and C₁₈ sorbents), amino cartridges were used for solid‐phase extraction. Analysis was carried out using liquid chromatography with diode array detection and confirmed by liquid chromatography–tandem mass spectrometry. The method showed excellent linearity with determination coefficient (R² = 1) and satisfactory recoveries (at two spiking levels, 0.5 and 2.5 mg/kg) between 90.98 and 94.74% with relative standard deviation (RSD) ≤8%. The limit of quantification (0.05 mg/kg) was considerably lower than the maximum residue limit (2 mg/kg) set by the Codex Alimentarius. Absolute residue levels for emulsifiable concentrates were highest, perhaps owing to the dilution rate and adjuvant. Notably, all formulation residues were lower than the maximum residue limit, and safety data proved that the fruits are safe for consumers. Copyright © 2016 John Wiley & Sons, Ltd.     

Media as Educator,Media as Disruptor: Conceptualizing the Role of Social Context in Media Effects

We document how social contexts serve to refract media effects. We theorized the relationship between media use and individual‐level knowledge (and attitude) would be stronger when community‐level knowledge (and attitude) was low than when it was high. Data come from a national survey (N = 12,608 women and 1,237 men) conducted in Nepal. Knowledge and stigma toward people living with HIV were the 2 dependent variables. Hypotheses were tested 12 times: across the use of 3 media (newspaper, radio, television) × 2 study outcomes (knowledge and attitudes) × 2 genders. Predicted interactions were supported in 9 of the 12 tests. Findings point to the need to take into account the role of community factors in theorizing about media effects.     

ESR Studies of λ-Irradiated Poly[3,3-bis(chloromethyl)oxetane]

Poly[3,3-bis(chloromethyl)] oxetane in vacuo, after λ-irradiation at 77°K and room temperature, showed ESR spectra consisting of a triplet (hfs of 22.0G) and a doublet (hfs of 17.8G), respectively. The triplet ESR spectrum is attributed to the -CH₂-C(CH₂Cl)-CH₂ -O- radical and the doublet ESR spectrum is attributed to the -CH₂-C(CH₂Cl)₂-CH-O- radical. The G values for formation of radicals are estimated to be 0.3 and 0.5 at 298 and 77°K, respectively.     

Patterning Surfaces for Controlled Platelet Adhesion and Detection of Dysfunctional Platelets

Platelets play a fundamental role in thrombus formation and in the pathogenesis of arterial thrombosis. Patterning surfaces for controlled platelet adhesion paves the way for adhesion and activation mechanisms in platelets and detection of platelet functional defects. Here, a new and simple method based on controlled polymerization of 2‐methacryloyloxyethyl phosphorylcholine (MPC) on the surface of styrene‐block‐(ethylene‐co‐butylene)‐block‐styrene (SEBS) is shown. The competition between polymerization and degradation enables platelet adhesion on SEBS to be switched on and off. The adhesive sites of the platelets can be down to single cell level, and the dysfunctional platelets can be quantitatively detected.

     

Quantitative LC–MS/MS method in urine for the detection of drugs used to reverse the effects of chemical castration

The chemical castration law, which targets child molesters with recidivism, was introduced in Korea in 2011. For this, leuprolide, a gonadotropin-releasing hormone agonist, is used to decrease testosterone production and suppress libido. In order to achieve efficient law enforcement, it is necessary to monitor intentional ingestion of drugs that antagonize the effect of leuprolide. Therefore, an analytical method for the simultaneous detection of mirodenafil, sildenafil, tadalafil, udenafil, vardenafil, icariin, alprostadil, and yohimbine, which are the major impotence treatment drugs, legitimately or otherwise, in Korea, as well as their selected metabolites, in human urine was established and validated using liquid chromatography–tandem mass spectrometry (LC–MS/MS). First, different sample preparation methods, two solid-phase extractions with different cartridges and protein precipitation, were compared and protein precipitation was chosen for the entire study because it showed better matrix effects and recoveries. Thus, the drugs and metabolites in urine were extracted by protein precipitation and then filtered and analyzed by LC–MS/MS with polarity switching electrospray ionization. The validation results of selectivity, matrix effect, recovery, linearity, intra- and inter-assay precision and accuracy were satisfactory. The limits of detection ranged from 0.25 to 10 ng/mL, and the limits of quantification were 2.5 to 50 ng/mL. The drugs and metabolites in urine did not show any degradation under storage for 7 and 15 days at 4 and ?20 °C as well as after three freeze–thaw cycles. The developed method will be very useful for monitoring the illegal use of impotence treatment drugs.