Dimerisation Process of Silybin‐Type Flavonolignans: Insights from Theory

Natural polyphenols are known to be oxidized by free radicals, which partially explains the antioxidant properties of a number of these compounds. This oxidation may also be used to synthesise new compounds of biological interest, for example, dimers. The present theoretical study describes the existing experimental evidence showing that silybin and dehydrosilybin [natural polyphenols isolated from milk thistle (Silybum marianum)] form dimers regioselectively. Based on DFT calculations, thermodynamic and kinetic values were computed in order to better understand the physicochemical behaviour of these dimerisation processes. Calculations showed that after H‐atom transfer (from polyphenol to radical), dimerisation could proceed in two steps: 1) bond formation and, when possible, 2) tautomerisation reorganisation. The former step is the limiting step, while the latter is crucial for the process to be thermodynamically favourable (ΔG<0). If this rearrangement is impossible then dimerisation is not feasible, or at least becomes a minor process (e.g., dehydrosilybin dimerisation after H‐atom abstraction from the 3‐OH group). This explains the regioselectivity of polyphenol dimerisation.     

Biodegradation of tobacco waste by composting: Genetic identification of nicotine-degrading bacteria and kinetic analysis of transformations in leachate

The tobacco industry produces large quantities of solid and liquid waste. This waste poses a significant environmental problem, as some major components are harmful and toxic. The aim of this work is to isolate and identify the nicotine-degrading microorganisms in the composting of tobacco waste. The bioremediation process for the detoxification of waste was carried out in a column reactor at an airflow-rate of 0.4 L min^?1 kg^?1. The concentrations of nicotine and number of CFU in the samples taken from reactor were monitored over nineteen days. After nineteen days, 89.8 % of nicotine conversion was obtained. A nicotine-degrading bacterium, strain FN, was isolated from the composting mass and identified as Pseudomonas aeruginosa on the basis of morphology, 16S rDNA sequence, and the phylogenetic characteristics. To confirm that the isolated Pseudomonas aeruginosa FN is the actual nicotine degrader, batch experiments were performed using tobacco leachate. It was confirmed that the strain FN possesses a considerable capacity to degrade nicotine with simultaneous COD removal. The Monod kinetic model for single substrate was applied to obtain the substrate degradation rate and half saturation constant.     

Estimation over Curves of the Functions Given by Dirichlet Series on a Half-Plane

We study the maximal term of the Hadamard composition of Dirichlet series with real exponents. We obtain a lower estimate for the sum of a Dirichlet series over a curve arbitrarily approaching the convergence line.     

On algebras with unique essentiallyn-ary operations

In this paper we characterize the class of algebras with one fundamental operation having for every nonnegative integern exactly one essentiallyn-ary polynomial.Presented by Joel Berman.     

粗粒土与结构接触面受载过程中的损伤

进行了粗粒上与结构接触面单调和循环加载试验,基于宏细观测量结果,扩展了损伤概念以描述该类接触面在受载过程中的物态演化,及由于物态演化导致的力学特性从初始状态到最终稳定状态的连续变化过程.揭示了接触面损伤的细观物理基础主要是接触面内土的颗牲破碎和剪切压密这两种物态演化;指出接触面的剪胀体应变可以划分为可逆性和不可逆性剪胀体应变两部分,其中不可逆性剪胀体应变可作为接触面损伤发展的宏观量度,因此其归一化形式可作为一种损伤因子的定义;提出了建立粗粒土与结构接触面一种损伤本构关系的基本思路.     

Identification and separation of saxitoxins using hydrophilic interaction liquid chromatography coupled to traveling wave ion mobility‐mass spectrometry

The aim of this work was to develop a reliable and efficient analytical method to characterise and differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) and non‐sulphated analogues. For this purpose, hydrophilic interaction liquid chromatography (HILIC) was used to separate sulphated analogues. We also resorted to ion mobility spectrometry to differentiate the STX analogues because this technique adds a new dimension of separation based on ion gas phase conformation. Positive and negative ionisation modes were used for gonyautoxins while positive ionisation mode was used for non‐sulphated analogues. Subsequently, the coupling of these three complementary techniques, HILIC‐IM‐MS, permitted the separation and identification of STX analogues; isomer differentiation was achieved in HILIC dimension while non‐sulphated analogues were separated in the IM‐MS dimension. Additional structural characteristics concerning the conformation of STXs could be obtained using IM‐MS measurements. Thus, the collision cross sections (CCS) of STXs are reported for the first time in the positive ionisation mode. These experimental CCSs correlated well with the calculated CCS values using the trajectory method. Copyright © 2015 John Wiley & Sons, Ltd.     

Bifurcations et solutions multiples en cavité 3D différentiellement chaufféeBifurcations and multiple solutions in a differentially heated cubic cavity

In this paper, a differentially heated square/cubic cavity is studied by performing three-dimensional direct numerical simulations. The first bifurcation observed at $\text{R}{}_{\mathrm{a}}\text{≈3.2×10}{}^7$ is due to the 3D vortex structures generated at the end regions of vertical boundary layers near the median plane. The main results of this Note are that the flow returns to a steady state for higher values of the Rayleigh number $\text{R}{}_{\mathrm{a}}$ (7×10⁷ and 10⁸ for example) still exhibiting these 3D vortex structures, and that multiple steady flows which differ by their symmetry properties, are obtained for $\text{R}{}_{\mathrm{a}}\text{=10}{}^8$. However, the flow reverts to unsteadiness for $\text{R}{}_{\mathrm{a}}\text{=3×10}{}^8$. In this latter case, the instability is due to the vertical boundary layers. To cite this article: G. de Gassowski et al., C. R. Mecanique 331 (2003).     

Thermodynamic and NMR study of aggregation of dodecyltrimethylammonium chloride in aqueous sodium salicylate solution

The complex aggregation processes of dodecyltrimethylammonium chloride (DTAC) have been studied in dilute solutions of sodium salicylate (NaSal) by isothermal titration calorimetry and electrical conductivity at temperatures between 278.15 K and 318.15 K. A structural transformation that was dependent on the concentrations of DTAC and NaSal was observed. The micellization process in dilute solutions of DTAC has been subjected to a detailed thermodynamic analysis and shown to occur at considerably lower critical micelle concentrations than reported for DTAC in water and NaCl solutions. Gibbs free energy, Δ _mic G ^o, and entropy, Δ _mic S ^o, were deduced by taking into account the degree of micelle ionization, β, estimated from conductivity measurements. From the temperature dependence of the enthalpy of micellization, Δ _mic H ^o, the heat capacities of micellization, D_mic c_p^o {\Delta_{{{\rm mic} }}}c_p^o were determined and discussed in terms of the removal of large areas of non-polar surface from contact with water upon micellization. The process is exothermic at all temperatures, indicating, in addition to the hydrophobic effect, the presence of strong interactions between surfactant and salicylate ions. These were confirmed by ¹H NMR spectroscopy and diffusion NMR experiments. Salicylate ions not only interact with the headgroups but also insert further into the micelle core. At c _NaSal/c _DTAC > 2.5, the structural rearrangements occur even at relatively low concentrations of NaSal.     

Unraveling the relationship between structure and stabilization of triarylpyridines as G-quadruplex binding ligands

A series of novel 2,4,6-triarylpyridines have been synthesized and their interactions with intramolecular G-quadruplexes have been measured by F?rster Resonance Energy Transfer (FRET) melting and Fluorescent Intercalator Displacement (FID) assays. A few of these compounds exhibit stabilization of G4-DNA that is comparable to other benchmark G4-DNA ligands with fair to excellent G4-DNA vs. duplex selectivity and significant cytotoxicity towards HeLa cells. The nature of the 4-aryl substituents along with side chain length governs the G4-DNA stabilization ability of the compounds. In addition, we demonstrate that there is a strong correlation between the ability of the compounds to stabilize the same G4-DNA sequence in K(+) and Na(+) conditions and a strong correlation between the ability of the compounds to stabilize different G4-DNA sequences in K(+) or Na(+) buffer.