Polymorphism in PbBiOXO4 compounds (X=V, P, As): Part II—PbBiOPO4 and PbBiOAsO4 structures and characterization of related solid solutions

Reinvestigation of PbBiOXO₄ (X=V, P, As) thermal behaviour revealed a phase transition for V- and P-compounds, but no transition for the As-compound. As shown by single-crystal X-ray diffraction and high-resolution neutron powder diffraction, α-PbBiOVO₄ transforms to β-PbBiOVO₄ at 550 °C. The two PbBiOPO₄ varieties are isomorph to the vanadate forms, while PbBiOAsO₄ adopts the β-type structure whatever the temperature. PbBiP_1−xOAs_xO₄ and PbBiV_1−xOM_xO₄ (M=As, P, Cr, Mn) solid solutions display both triclinic and monoclinic domains, and the α→β transition temperature is a function of the substitution rate. The ionic conductivity of these compounds was investigated by impedance spectroscopy. The analysis of free space in the β-PbBiOVO₄ structure allows to propose a one-dimensional oxygen diffusion pathway along [010] when the temperature increases.     

Extraction and Characterization of Chitin,Chitosan, and Protein Hydrolysates Prepared from Shrimp Waste by Treatment with Crude Protease from <Emphasis Type="Italic">Bacillus cereus</Emphasis> SV1

Chitin is a polysaccharide found in abundance in the shell of crustaceans. In this study, the protease from Bacillus cereus SV1 was applied for chitin extraction from shrimp waste material of Metapenaeus monoceros. A high level of deproteinization 88.8% ± 0.4 was recorded with an E/S ratio of 20. The demineralization was completely achieved within 6 h at room temperature in HCl 1.25 M, and the residual content of calcium in chitin was below 0.01%. ¹³C CP/MAS-NMR spectral analysis of chitin prepared by the enzymatic deproteinization of shrimp wastes was found to be similar to that obtained by alkaline treatment and to the commercial α-chitin. The degree of N-acetylation, calculated from the spectrum, was 89.5%. Chitin obtained by treatment with crude protease from B. cereus was converted to chitosan by N-deacetylation, and the antibacterial activity of chitosan solution against different bacteria was investigated. Results showed that chitosan solution at 50 mg/mL markedly inhibited the growth of most Gram-negative and Gram-positive bacteria tested. Furthermore, the antioxidant potential of the protein hydrolysates obtained during enzymatic isolation of chitin was evaluated using various in vitro assays. All the samples exerted remarkable antioxidant activities. These results suggest that enzymatic deproteinization of the shrimp shell wastes, using B. cereus SV1 protease, could be applicable to the chitin production process.     

A generalized urn with multiple drawing and random addition

Annals of the Institute of Statistical Mathematics - In this paper, we consider an unbalanced urn model with multiple drawing. At each discrete time step n, we draw m balls at random from an urn...     

Polymorphism in PbBiOXO4 compounds (X=V, P, As). Part I: Crystal structures of α- and β-PbBiOVO4

Reinvestigation of PbBiOVO₄ thermal behaviour revealed a phase transition. As shown by single-crystal X-ray diffraction and high-resolution neutron powder diffraction, α-PbBiOVO₄ transforms to β-PbBiOVO₄ at 550 °C. At 25 °C, α-PbBiOVO₄ is triclinic, S.G. P-1, Z=2, with a=5.6088(3), b=7.1109(3), c=7.2978(3) Å, α=108.957(2), β=111.889(2), and γ=94.833(2)°. Above 550 °C, β-PbBiOVO₄ is monoclinic, S.G. C2/m, Z=4, with a=13.61(1), b=5.64(1), c=7.18(1) Å, and β=113.75(1)°. Both structures are built upon (O₂Bi₂Pb₂)_∞ chains parallel to the [100] direction in the α polymorph and [001] in the β-polymorph. These chains are undulated in α and linear in β. In both structures, VO₄ tetrahedra are organized in two sets of rows parallel to (O₂Bi₂Pb₂)_∞ chains, thus building layers of (OBiPb) sandwiched by two layers of VO₄ oriented head to tail; VO₄ displays different orientations in α- and β-PbBiOVO₄.     

Comparative study of kinetics isomerization of substituted polyacetylene (Cl,F and I): Ab initio and DFT calculations

Ab initio and DFT methods were used to investigate the interconversions of substituted polyacetylene conformers C₁₀H₆X₆ (X=F, Cl and I) in the vapour phase. The rates of this geometrical isomerization have been calculated and the Arrhenius parameters evaluated. In the case of unsubstituted polyacetylene as the reference, the B3LYP Arrhenius parameters obtained are A₁=2.99 × 10¹⁷ s^–1 and E_a=17.30 kcal mol^–1. The values of the equilibrium constant for the reaction have also been determined at various temperatures between 300 and 500 K and the value of the energies change calculated. The results also suggest that the straightforward kinetics characterizing the majority of substituted polyacetylene isomerizations above 300 K. The isomerization energies are positive and the barrier heights ΔE_barrier are expected to be sensitive for the magnitude of halogens effects. According to geometries features the Cis → Trans isomerization in the gas phase occurs by a rotational mechanism.