A sorbent tube for oral malodour monitoring

Volatile sulphur compounds (VSCs) and particularly hydrogen sulphide are considered as the predominant gases causing oral malodour. In this paper, a simple alarm sensor has been developed for VSCs determination in mouth air. The device consists of a glass tube packed with a solid sensing phase. The VSCs react with the sensing phase to produce a change in the colour of the sensor visible with a naked eye.Different “reagents” were investigated to develop the sensing phase (neocuproine + Cu(II), bathocuproine + Cu(II), resazurin, 2,6-dichlorophenolindophenol and lead acetate), finding the neocuproine + Cu(II) as the best for our purposes. Also, different substrates such as Amberlite XAD-4 and XAD-7 and different trademarks of silica gel were tested as solid supports, being selected the silica gel.A device consisting of a glass tube packed with the sensing phase was optimized and tested with halitosis patients as a rapid illness test and the results compared with those obtained with a commercially available instrument, the Halimeter™, used for the determination of VSCs in mouth air. The results exhibited acceptable agreement between the proposed “qualitative” alarm sensor and a commercially available technique selected as reference, showing the possibility of using this “visual sensor” to control the halitosis and its evolution with an eventual treatment, by the own patient.     

Analytical applications of organized assemblies for on-line spectrometric determinations: present and future

An amphiphile (surfactant) spread on water can lead to the formation of different aggregates: vesicles, miscelles, emulsions or microemulsions; depending on its concentration; its molecular structure and/or the experimental conditions. Such aggregates, (a) may concentrate products, reactants or analytes and so improve the analytical sensitivity and (b) may solubilize such substances and so favorably change the analytical selectivity. Bilayer membrane vesicles for instance, apart from their wide applications in cosmetic and pharmaceutical industries, have a great analytical potential due to their ability to (i) reversibly sequester metal ions avoiding matrix interference and (ii) improve cold vapor (Hg and Cd) and hydride (As, Se, Pb) chemical generation. Micellar solutions have also found wide applications in different areas of analytical chemistry, showing their capacity to concentrate and separate a significant variety of analytes. Among the numerous micelle-based separation techniques, cloud point extraction offers an excellent enrichment factor for metal ions, allowing their quantification at microgram/litre levels. Also agitating a mixture of water, oil and one or more surfactants under controlled experimental conditions, a cloudy mixture (emulsion) or a transparent solution (microemulsion) can be formed. Adequate formulation is necessary in order to obtain a stable organized media. To fulfill this requirement, a major effort is necessary in order to shorten the gap between the current knowledge on this topic and the promising field of applications that await development. Recent publications show that self-assembly structures from highly viscous samples can be accomplished on-line with the advantages of drastically reducing the time of analysis and assuring the absolute control over the stability of the aggregate. Flow systems allow effective mixing of samples with added surfactant and provide continuous pumping of the resulting mixture to sensitive detectors for the on-line determination of different analytes in complex samples.     

Use of electron density critical points as chemical function-based reduced representations of pharmacological ligands

In this paper, we propose a reduced representation of molecules of pharmacological interest based on their chemical functions. The proposed representations of the molecules are obtained by a topological analysis of their electron density maps at medium resolution, leading to graphs of critical points. The distribution of the different types of critical points are compared at various levels of resolution for a training set of 22 molecules in order to define the optimal resolution level leading to the best representation of the various chemical functions. The reduced representations can in the future be used for molecular similarity research and pharmacophore proposals.     

Variational transition state theory as a tool to determine kinetic selectivity in reactions involving a valley-ridge inflection point

Variational transition state theory has been used to calculate the kinetic isotope effects affecting product ratios in the reaction between (1)O(2) and d(6)-tetramethylethylene. The minimum energy path on the potential energy surface for this process reaches a valley-ridge inflection point and then bifurcates leading to the two final products. Using canonical variational transition state theory, two distinct dynamical bottlenecks were located corresponding to the H- and the D-abstraction, respectively. The calculated KIE at 263 K turns out to be 1.126. Analogously, a H/T KIE of 1.17 at the same temperature has been found for the reaction of (1)O(2) with the tritiated derivative of tetramethylethylene.     

Thermodynamic equilibrium of the solute distribution in size-exclusion chromatography

Our understanding of the nature of solute retention in size-exclusion chromatography (SEC) is predicated upon an equilibrium, entropy-controlled, size-exclusion mechanism. The entropic nature of the separation depends, in turn, upon the solute distribution coefficient (K(SEC) being at (or close to) thermodynamic equilibrium. Classic experiments to confirm this assumption were performed over thirty years ago. Here, we combine information obtained from both flow and static mixing SEC experiments to show that the solute distribution in SEC is in thermodynamic equilibrium over a molar mass range extending one order of magnitude higher than previously measured (from 2 x 10(3) to 1.1 x 10(6) Da) using crosslinked polystyrene packing material of identical pore size (10(4) A). The differences between our observations and previous ones conducted over three decades ago are ascribed, principally, to advances in stationary phase synthesis and column technology for SEC in particular and, secondarily, to improvements in the performance of the various instrumental components of liquid chromatographic systems in general.     

Formation of trinuclear palladium orthometalated complexes with unprecedented asymmetrical (mu 3-S)(mu 3-X) bridges (X = OH, SR, O2CR) from mu 2-hydroxo dimeric complexes and CS2

Complexes [Pd(3)(mu(3)-S)(mu(3)-X)(L)(3)] (L = orthometalated imine), obtained by an unusual reaction of mu(2)-OH dimeric complexes and CS(2), are an unprecedented type of asymmetrical bridges between metallatriangles, which force an all-cis arrangement of the three orthometalated ligands relative to the metallatriangle.     

A chiral molecular conductor: synthesis, structure, and physical properties of [ET]3[Sb2(L-tart)2].CH3CN (ET = bis(ethylendithio)tetrathiafulvalene; L-tart = (2R,3R)-(+)-tartrate)

The salt [ET](3)[Sb(2)(L-tart)(2)].CH(3)CN (1) has been obtained by electrocrystallization of the organic donor bis(ethylendithio)tetrathiafulvalene (ET or BEDT-TTF) in the presence of the chiral anionic complex [Sb(2)(L-tart)(2)](2-) (L-tart = (2R,3R)-(+)-tartrate). This salt crystallizes in the chiral space group P2(1)2(1)2(1) (a = 11.145(2) angstroms, b = 12.848(2) angstroms, c = 40.159(14) angstroms, V = 5750.4(14) angstroms(3), Z = 4) and is formed by alternating layers of the anions and of the organic radicals in a noncentrosymmetric alpha-type packing. This compound shows a room temperature electrical conductivity of approximately 1 S.cm(-1) and semiconducting behavior with an activation energy of approximately 85 meV. Analysis of the magnetic susceptibility and band structure, however, suggests that this compound should be a narrow band gap semiconductor.     

Study of the stabilization energies of halide-water clusters: an application of first-principles interaction potentials based on a polarizable and flexible model

The aim of this work is to compute the stabilization energy E(stab)(n) of [X(H(2)O)(n)](-) (X identical with F, Br, and I for n=1-60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of [X(H(2)O)(n)](-) clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E(stab)(n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: (1) the Koopmans' theorem and (2) calculation of the difference between the interaction energy of [X(H(2)O)(n)](-) and [X(H(2)O)(n)] clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E(stab)(n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E(stab)(n) and the structure of clusters has been found. The diversity of E(stab)(n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of the E(stab)(n) is not significant as long as it was high enough to avoid cluster trapping into local equilibrium configurations which guarantees an appropriate sampling of the configurational space. Parallel tempering method was applied in particular cases to guarantee satisfactory sampling of clusters at low temperature.     

Development of a Sequential Injection Analysis Device for the Determination of Total Polyphenol Index in Wine

A sequential injection analysis method is developed for the determination of the total polyphenol index in wines. The determination is based on the Folin-Ciocalteu reaction, which is monitored spectrophotometrically. Interactions between experimental variables and their optimal levels were investigated using factorial designs. The proposed system is fully computerised and is able to monitor polyphenol index in real samples of white, sweet and red wines. The calibration graph is linear from 5 to 200mg·L^–1 using Tannic acid as standard, with a detection limit of 3.2mg·L^–1. Interferences are studied. For validation purposes the proposed methodology was applied to the determination of the total polyphenol index in different types of wines and compared with earlier alternatives in order to assess their performance.