Radical cyclization of allyl α-bromocarboxylates into λ-butyrolactones. Effect of the ester structure on the cyclization

Allyl dibromoacetate, allyl α-bromopropionate, and allyl phenylbromoacetate undergo cyclization in benzene in the presence of increased concentration of Fe(CO)₅—DMF as the initiating system to give the corresponding bromo-substituted butyrolactones. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2210–2212, December, 1997.     

Correlation between the electric-field effect and weak-link type in YBa2Cu3−x Oy and YBa2Cu3−x Oy /Agx high-T c superconducting ceramics

An experimental study is reported of the effect of an electric field E⩽120 MV/m and of temperature T on the critical current I _c and I-V characteristics of yttrium-based high-T _c superconducting ceramics. The materials studied were copper-deficient ceramics, YBa₂Cu_3−x O_y (D samples), and YBa₂Cu_3−x O_y/Ag_x ceramics [S samples with silver present in amounts equal to the copper deficiency (0⩽x⩽0.4)]. It has been established that in D samples at 77 K, the electric field increases I _c and reduces substantially R for I>I _c, whereas in S samples no field effect is observed. Measurements of the I _c(T) dependence near the critical temperature showed that they can be described for all samples by a relation of the type I _c =const(1−T/T _c )^α, where α≈1 for the D samples, and α≈2 for the S samples. The results obtained suggest that the electric-field effect correlates with the existence in the ceramic of SIS-type weak links at grain boundaries. Fiz. Tverd. Tela (St. Petersburg) 40, 1195–1198 (July 1998)     

Grain size refinement due to relaxation of disclination junction configurations in the course of plastic deformation of polycrystals

A model is proposed for the formation of the substructure in polycrystals during plastic deformation. According to this model, fragmentation of a grain occurs through the formation of a system of diagonal low-angle boundaries, which originate at the edges of a rectangular grain. Misorientation boundaries form through relaxation of a nonsymmetric junction quadrupole disclination configuration accumulated at the grain corners under severe deformation when the disclination strength reaches a certain critical value. The energetics of this process is analyzed. A general case is considered where the disclinations at the junctions of the chosen grain differ in strength. The energetic approach used makes it possible to determine the misorientation angle ω_x of the resulting boundaries corresponding to the maximum energy gain and to find the dependence of this angle on the degree of asymmetry of the quadrupole configuration of junction disclinations. According to the proposed model, the splitting of a grain with a short edge greater than 0.5 μm is energetically favorable and decreases the latent energy of the grain for any ratio between the junction disclination strengths if the grain length-to-width ratio is less than 30. It is shown that the minimum possible grain size in the proposed model does not exceed 0.1 μm.     

Asymptotic Expansions for the Distribution of the Crossing Number of a Strip by Sample Paths of a Random Walk

The complete asymptotic expansions are obtained for the distribution of the crossing number of a strip in n steps by sample paths of an integer-valued random walk with zero mean. We suppose that the Cramer condition holds for the distribution of jumps and the width of strip increases together with n; the results are proven under various conditions on the width growth rate. The method is based on the Wiener–Hopf factorization; it consists in finding representations of the moment generating functions of the distributions under study, the distinguishing of the main terms of the asymptotics of these representations, and the subsequent inversion of the main terms by the modified saddle-point method.     

Wild type and mutant forms of recombinant horseradish peroxidase C expressed inEscherichia coli

Two horseradish peroxidase C (HRPC) mutants with substitutions in the active center, i.e., Phe41→ His and Phel43→ Glu, were compared to the wild-type recombinant enzyme expressed in Escherichia coli in terms of the enzymatic activity and stability under irradiation. Both mutations caused a significant decrease in activity, but it was still possible to follow the effect of mutations on the key steps of the reaction mechanism. Phe41 can be considered a nonpolar barrier separating histidine residues in the active center and providing a firm noncovalent binding with the highly hydrophobic porphyrin ring. The replacement of Phe41 with the ionizable His residue destabilizes the enzyme. The Phel43→ Glu replacement creates a negative charge at the entrance of the heme-binding pocket, and protects the latter from both donor substrates and free radicals. The radiolytic inactivation of the wild-type and mutant forms of recombinant HRP suggested different binding sites for iodide, 2,2′-bis(3-ethylbenzothiasoline-6-sulfonate (ABTS), guaiacol, and o-phenylene diamine. The study of kinetics and inactivation is in agreement with the direct binding of iodide to the heme porphyrin ring. The results also suggest that the ABTS binding site is less accessible than that for o-phenylene diamine.     

COMPOSITION OF INDOOR AEROSOLS AT EMPEROR QIN''''S TERRA-COTTA MUSEUM, XI''''AN, CHINA, DURING SUMMER, 2004

Particle samples were collected in August 2004 both inside and outside Emperor Qin's Terra-Cotta Museum in Xi'an, China. Mass and chemical composition of total suspended particles (JSP, particles with aerodynamic diameter less than-30μm), PM2.5(particles with aerodynamic diameter <2.5μm) were determined. The average levels of indoor PM2.5 and TSP were 108.4 and 172.4 μg·m-3, respectively, with PM2.5 constituting 62.9% of the TSP mass. Sulfate ((32.4±6.2)%), organics ((27.7±8.0)%), and geological material ((12.5±3.4)%) dominated indoor PM2.5, followed by ammonium ((8.9±2.8)%), nitrate ((7.0±2.9)%), and elemental carbon (EC, (3.9±1.5)%). Particle size distribution varied with the number of tourists in the museum. The size of sulfate, organics, EC, nitrate, and ammonium was found to vary in the range of 0.43 to 3.3 μm in fraction. Ion balance indicated that the aerosol was acidic, with insufficient ammonium ions to neutralize the sulfuric and nitric acids. High concentrations of acidic aerosols will erode the Terra-cotta warriors and horses especially in the summer season with high temperature (30℃) and relative humidity (70%) and undesirable solar radiation inside the museum. More attention should be paid to protecting these precious antiques made 2000 years ago.     

Specific features of formyl- and acetylferrocene oxidation with peroxides in water and organic solvents

Specific features of formyl- and acetylferrocene oxidation with peroxides ROOR (R = H, tert-C₄H₉) in different solvents are studied. It is shown that despite of the presence in complexes of strong electronacceptor substituents they can be oxidized with hydrogen peroxide in the absence of strong Brønsted acids. Dilution of water with organic solvent leads to deceleration and complete standstill of the reaction. In the absence of acids the second order of the process with respect to peroxide and first one with respect to the metal complex was evaluated. In the presence of perchloric or trifluoroacetic acid the order with respect to peroxide decreases to the first one. The dependence of the reaction rate on the concentration of acid has an extremum point. The activity of other peroxides in the reaction with the above-mentioned compounds is significantly lower than the activity of hydrogen peroxide. Probable alternative mechanisms of oxidation of the abovementioned ferrocenes with hydrogen peroxide in the presence and in the absence of acids differing in the way of coordination of reagents with one another and considering direct participation of substituent in the oxidation is suggested.     

Synthesis and antiviral activity of adamantyl-containing phosphonous and phosphinic acids

The method of adamantly-containing phosphonous and phosphinic acids preparation, based on radical addition of hypophosphorous acid and sodium hypophosphite to unsaturated derivatives of adamantane, has been developed. Unsymmetrical phosphinic acids have been prepared by reacting bistrimetylsilyl esters of phosphonous acids with halides. The obtained phosphinic acids exhibit antiviral activity against herpes simplex virus, influenza A (H5N1), respiratory syncytial virus, and adenovirus.     

Investigation of the 13C(d,α)11B reaction mechanism at Ed = 15.3 MeV

The differential cross section of the ¹³C(d, α)¹¹B reaction at E _d = 15.3 MeV with the formation of ¹¹B nucleus in the ground and three low-lying excited states have been measured. The experimental data are compared with the results of calculations under the assumption of different reaction mechanisms: deuteron pick-up, ⁹Be-cluster exchange, two-step consecutive cluster transfer, and compound nucleus formation. Original Russian Text ? L.I. Galanina, N.S. Zelenskaya, I.A. Konyukhova, V.M. Lebedev, N.V. Orlova, A.V. Spassky, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 6, pp. 853–856.