Bioactive diterpenoid containing a reversible "spring-loaded" (E,Z)-dieneone Michael acceptor

Three new briarane diterpenoids, briareolate esters L-N (1-3), have been isolated from a gorgonian Briareum asbestinum. Briareolate esters L (1) and M (2) are the first natural products possessing a 10-membered macrocyclic ring with a (E,Z)-dieneone and exhibit growth inhibition activity against both human embryonic stem cells (BG02) and a pancreatic cancer cell line (BxPC-3). Briareolate ester L (1) was found to contain a "spring-loaded" (E,Z)-dieneone Michael acceptor group that can form a reversible covalent bond to model sulfur-based nucleophiles.     

Application of ethyl chloroformate derivatization for solid-phase microextraction–gas chromatography–mass spectrometric determination of bisphenol-A in water and milk samples

A simple and rapid analytical method based on in-matrix ethyl chloroformate (ECF) derivatization has been developed for the quantitative determination of bisphenol-A (BPA) in milk and water samples. The samples containing BPA were derivatised with ECF in the presence of pyridine for 20 s at room temperature, and the non-polar derivative thus formed was extracted using polydimethylsiloxane solid-phase microextraction (SPME) fibres with thicknesses of 100 μm followed by analysis using gas chromatography–mass spectrometry. Three alkyl chloroformates (methyl, ethyl and isobutyl chloroformate) were tested for optimum derivatisation yields, and ECF has been found to be optimum for the derivatisation of BPA. Several parameters such as amount of ECF, pyridine and reaction time as well as SPME parameters were studied and optimised in the present work. The limit of detection for BPA in milk and water samples was found to be 0.1 and 0.01 μg L⁻¹, respectively, with a signal-to-noise ratio of 3:1. The limit of quantitation for BPA in milk and water was found to be 0.38 and 0.052 μg L⁻¹, respectively, with a signal-to-noise ratio of 10:1. In conclusion, the method developed was found to be rapid, reliable and cost-effective in comparison to silylation and highly suitable for the routine analysis of BPA by various food and environmental laboratories.     

A zebrafish scale assay to monitor dioxin-like activity in surface water samples

New regulations on water quality require a close control of the possible biological activities known or unexpected pollutants may bring about. We present here a protocol based on the direct exposure of zebrafish to river water and the analysis of expression of specific genes in their scales to determine the presence of compounds with dioxin-like biological activity. The method does not require the killing of animals and allows detection of the biological activity after a single day of exposure. When tested, the method with real samples from the Llobregat River, clear temporal and spatial variations were observed, demonstrating its suitability for monitoring natural variations in water quality linked to specific discharges. High biological activities were unrelated to the currently checked water quality parameters (macropollutants, turbidity, TOC, etc.), but they did correlate with the presence of micropollutants (estrogens, detergents, etc.) related to domestic and/or industrial runoffs. The scale assay therefore provides a new tool to evaluate water quality changes that cannot be easily derived from the existing standard analytical procedures. It ranks among the very few described protocols able to detect biological effects from natural water samples, without a pre-concentration step, and after only 24 h of exposure.     

Nanoscopic optical sensors based on functional supramolecular hybrid materials

This review highlights how the combination of supramolecular principles and nanoscopic solid structures enables the design of new hybrid sensing ensembles with improved sensitivity and/or selectivity and for the targeting of analytes for which selectivity is hard to achieve by conventional methods. Such ideas are bridging the gap between molecules, materials sciences and nanotechnology. Relevant examples will be detailed, taking into account functional aspects such as (1) enhanced coordination of functionalized solids, (2) enhanced signalling through preorganization, (3) signalling by assembly–disassembly of nanoscopic objects, (4) biomimetic probes utilizing discrimination by polarity and size and (5) distinct switching and gating protocols. These strategies are opening new prospects for sensor research and signalling paradigms at the frontier between nanotechnology, smart materials and supramolecular chemistry.     

On the density of integral sets with missing differences from sets related to arithmetic progressions

For a given set M of positive integers, a problem of Motzkin asks for determining the maximal density μ(M) among sets of nonnegative integers in which no two elements differ by an element of M. The problem is completely settled when |M|?2, and some partial results are known for several families of M for |M|?3, including the case where the elements of M are in arithmetic progression. We consider some cases when M either contains an arithmetic progression or is contained in an arithmetic progression.     

Transcendental values of class group <Emphasis Type="Italic">L</Emphasis>-functions

Let K be an algebraic number field and f a complex-valued function on the ideal class group of K. Then, f extends in a natural way to the set of all non-zero ideals of the ring of integers of K and we can consider the Dirichlet series \({L(s,f) =\sum_{{\mathfrak a}} f({\mathfrak a}){\bf N}({\mathfrak a})^{-s}}\) which converges for \({{\mathfrak R}(s) >1 }\). After extending this function to \({{\mathfrak R}(s)=1}\), and in the case that f does not contain the trivial character, we study the special value L(1, f) when f is algebraic valued and K is an imaginary quadratic field. Applying Kronecker’s limit formula and Baker’s theory of linear forms in logarithms, we derive a variety of results related to the transcendence of this special value.     

Numerical solution of two-dimensional reaction-diffusion Brusselator system

In this paper, polynomial based differential quadrature method (DQM) is applied for the numerical solution of a class of two-dimensional initial-boundary value problems governed by a non-linear system of partial differential equations. The system is known as the reaction-diffusion Brusselator system. The system arises in the modeling of certain chemical reaction-diffusion processes. In Brusselator system the reaction terms arise from the mathematical modeling of chemical systems such as in enzymatic reactions, and in plasma and laser physics in multiple coupling between modes. The numerical results reported for three specific problems. Convergence and stability of the method is also examined numerically.     

New third and fourth order nonlinear solvers for computing multiple roots

We present a new third order method for finding multiple roots of nonlinear equations based on the scheme for simple roots developed by Kou et al. [J. Kou, Y. Li, X. Wang, A family of fourth-order methods for solving non-linear equations, Appl. Math. Comput. 188 (2007) 1031-1036]. Further investigation gives rise to new third and fourth order families of methods which do not require second derivative. The fourth order family has optimal order, since it requires three evaluations per step, namely one evaluation of function and two evaluations of first derivative. The efficacy is tested on a number of relevant numerical problems. Computational results ascertain that the present methods are competitive with other similar robust methods.     

Extensional wave motion in homogenous isotropic thermoelastic plate by using asymptotic method

The present investigation is concerned with the study of extensional wave motion in an infinite homogenous isotropic, thermoelastic plate by using asymptotic method. The governing equation for the extensional wave motions have been derived from the system of three-dimensional dynamical equations of linear coupled theory of thermoelasticity. All coefficients of the differential operator are expressed as explicit functions of the material parameters. The velocity dispersion equation for the extensional wave motion is deduced from the three-dimensional analog of Rayleigh–Lamb frequency equation for thermoelastic plate waves. The approximations for long and short waves and expression for group velocity are also derived. The thermoelastic Rayleigh–Lamb frequency equations for the considered plate are expanded in power series in order to obtain polynomial frequency and velocity dispersion relations whose equivalence is established to that of asymptotic method. The dispersion curves for phase velocity and attenuation coefficient are shown graphically for extensional wave motion of the plates.