A theoretical plate model accounting for slow kinetics in chromatographic elution

The chromatographic elution has been studied from different perspectives. However, in spite of the simplicity and evident deficiencies of the plate model proposed by Martin and Synge, it has served as a basis for the characterization of columns up-to-date. This approach envisions the chromatographic column as an arbitrary number of theoretical plates, each of them consisting of identical repeating portions of mobile phase and stationary phase. Solutes partition between both phases, reaching the equilibrium. Mobile phase transference between the theoretical plates is assumed to be infinitesimally stepwise (or continuous), giving rise to the mixing of the solutions in adjacent plates. This yields an additional peak broadening, which is added to the dispersion associated to the equilibrium conditions. It is commonly assumed that when the solute concentration is sufficiently small, chromatographic elution is carried out under linear conditions, which is the case in almost all analytical applications. When the solute concentration increases above a value where the stationary phase approximates saturation (i.e. becomes overloaded), non-linear elution is obtained. In addition to overloading, another source of non-linearity can be a slow mass transfer. An extended Martin and Synge model is here proposed to include slow mass-transfer kinetics (with respect to flow rate) between the mobile phase and stationary phase. We show that there is a linear relationship between the variance and the ratio of the kinetic constants for the mass transfer in the flow direction (τ) and the mass transfer between the mobile phase and stationary phase (ν), which has been called the kinetic ratio (κ=τ/ν). The proposed model was validated with data obtained according to an approach that simulates the solute migration through the theoretical plates. An experimental approach to measure the deviation from the equilibrium conditions using the experimental peak variances and retention times at several flow rates is also proposed.     

An HPLC method for determination of azadirachtin residues in bovine muscle

A high-performance liquid chromatography (HPLC) method for the determination of azadirachtin (A and B) residues in bovine muscle has been developed. Azadirachtin is a neutral triterpene and chemotherapeutic agent effective in controlling some pest flies in horses, stables, horns and fruit. The actual HPLC method uses an isocratic elution and UV detection. Liquid-liquid extraction and solid-phase purification was used for the clean-up of the biological matrix. The chromatographic determination of these components is achieved using a C18 analytical column with water-acetonitrile mixture (27.5:72.5, v/v) as mobile phase, 1 mL/min as flow rate, 45 °C column temperature and UV detector at 215 nm. The azadirachtin peaks are well resolved and free of interference from matrix components. The extraction and analytical method developed in this work allows the quantitation of azadirachtin with precision and accuracy, establishing a lower limit of quantitation of azadirachtin, extracted from the biological matrix.     

Statistical mechanics of hydrated electron recombination in liquid and supercritical water

The photochemical yield of hydrated electrons as a function of temperature in liquid and supercritical water is treated in terms of energy fluctuations of the medium. The geminate pair, consisting of a positive ion and a hydrated electron, is regarded as a H-like atom embedded in a completely relaxed dielectric continuum. If the local medium energy is larger than the ionization energy of this atom, the electron escapes its geminate partner. By making use of the classical theory of energy fluctuations, escape probability is described by a simple explicit function, the variable of which is a combination of temperature, relative permittivity, and specific heat. First our earlier calculations on the recombination of solvated electrons, produced by ionizing radiation in a number of polar liquids, are improved and then the theory is compared with the experimental results on temperature dependent electron survival by Kratz et al. [S. Kratz, J. Torres-Alcan, J. Urbanek, J. Lindner, and P. Vo?hringer, Phys. Chem. Chem. Phys. 12, 12169 (2010)]. Two adjustable parameters are needed to achieve reasonable quantitative agreement.     

Ab initio characterization of the Ne-I2 van der Waals complex: intermolecular potentials and vibrational bound states

A theoretical study of the potential energy surface and bound states is performed for the ground state of the NeI(2) van der Waals (vdW) complex. The three-dimensional interaction energies are obtained from ab initio coupled-cluster, coupled-cluster single double (triple)/complete basis set, calculations using large basis sets, of quadruple- through quintuple-zeta quality, in conjunction with relativistic effective core potentials for the heavy iodine atoms. For the analytical representation of the surface two different schemes, based on fitting and interpolation surface generation techniques, are employed. The surface shows a double-minimum topology for linear and T-shaped configurations. Full variational quantum mechanical calculations are carried out using the model surfaces, and the vibrationally averaged structures and energetics for the NeI(2) isomers are determined. The accuracy of the potential energy surfaces is validated by a comparison between the present results and the corresponding experimental data available. In lieu of more experimental measurements, we also report our results/predictions on higher bound vibrational vdW levels, and the influence of the employed surface on them is discussed.     

Computational study of the interaction of indole-like molecules with water and hydrogen sulfide

The characteristics of the interaction between water and hydrogen sulfide with indole and a series of analogs obtained by substituting the NH group of indole by different heteroatoms have been studied by means of ab initio calculations. In all cases, minima were found corresponding to structures where water and hydrogen sulfide interact by means of X-H···π contacts. The interaction energies for all these π complexes are quite similar, spanning from -13.5 to -18.8 kJ/mol, and exhibiting the stability sequence NH > CH(2) ≈ PH > Se ≈ S > O, for both water and hydrogen sulfide. Though interaction energies are similar, hydrogen sulfide complexes are slightly favored over their water counterparts when interacting with the π cloud. σ-Type complexes were also considered for the systems studied, but only in the case of water complexes this kind of complexes is relevant. Only for complexes formed by water and indole, a significantly more stable σ-type complex was found with an interaction energy amounting to -23.6 kJ/mol. Oxygen and phosphorous derivatives also form σ-type complexes of similar stability as that observed for π ones. Despite the similar interaction energies exhibited by complexes with water and hydrogen sulfide, the nature of the interaction is very different. For π complexes with water the main contributions to the interaction energy are electrostatic and dispersive contributing with similar amounts, though slightly more from electrostatics. On the contrary, in hydrogen sulfide complexes dispersion is by far the main stabilizing contribution. For the σ-type complexes, the interaction is clearly dominated by the electrostatic contribution, especially in the indole-water complex.     

Hydrophobicity of ionisable compounds studied by countercurrent chromatography

Countercurrent chromatography (CCC) is a liquid chromatography technique in which the stationary phase is also a liquid. The main chemical process involved in solute separation is partitioning between the two immiscible liquid phases: the mobile phase and the support-free liquid stationary phase. The octanol-water partition coefficients (P(o/w)) is the accepted parameter measuring the hydrophobicity of molecules. It is considered to estimate active principle partitioning over a biomembrane. It was related to the substance biological activity. CCC is able to work with an octanol stationary phase and an aqueous mobile phase. In this configuration, CCC is a useful and easy alternative to measure directly the P(o/w) of the molecules compared to other methods including the classical and tedious shake-flask method. Three ketones are used as model compounds to illustrate the CCC protocol of P(o/w) measurement. The focus of this work is put on ionisable molecules whose apparent P(o/w) is completely changed by ionization. β-Blockers, diuretics and sulfonamides are compound classes that were studied. Some of the experimentally determined P(o/w) coefficients of the molecular forms disagreed with calculated and experimental values available in the literature. The P(o/w) coefficients of the ionic forms and the acidity constants were also calculated using a theoretical model. Relationships between biological properties and hydrophobicity are also discussed.     

Low-level laser therapy improves skeletal muscle performance, decreases skeletal muscle damage and modulates mRNA expression of COX-1 and COX-2 in a dose-dependent manner

We tested if modulation in mRNA expression of cyclooxygenase isoforms (COX-1 and COX-2) can be related to protective effects of phototherapy in skeletal muscle. Thirty male Wistar rats were divided into five groups receiving either one of four laser doses (0.1, 0.3, 1.0 and 3.0 J) or a no-treatment control group. Laser irradiation (904 nm, 15 mW average power) was performed immediately before the first contraction for treated groups. Electrical stimulation was used to induce six tetanic tibial anterior muscle contractions. Immediately after sixth contraction, blood samples were collected to evaluate creatine kinase activity and muscles were dissected and frozen in liquid nitrogen to evaluate mRNA expression of COX-1 and COX-2. The 1.0 and 3.0 J groups showed significant enhancement (P < 0.01) in total work performed in six tetanic contractions compared with control group. All laser groups, except the 3.0 J group, presented significantly lower post-exercise CK activity than control group. Additionally, 1.0 J group showed increased COX-1 and decreased COX-2 mRNA expression compared with control group and 0.1, 0.3 and 3.0 J laser groups (P < 0.01). We conclude that pre-exercise infrared laser irradiation with dose of 1.0 J enhances skeletal muscle performance and decreases post-exercise skeletal muscle damage and inflammation.     

A Study of Resonances in a One-Dimensional Model with Singular Hamiltonian and Mass Jumps

We study the resonances produced in a one dimensional quantum system with an infinite potential on the negative real line plus two Dirac delta barriers centered at the points a,b>0. The system mass is not constant but undergoes jumps at the singular points a and b of the potential. We study the behavior of the resonances under the change of parameters such that the weight of the deltas or the heights of mass jumps. Possible degeneration of these resonances is also considered.     

OPTIMAL HARVESTING TIME OF FARMED AQUATIC POPULATIONS WITH NONLINEAR SIZE‐HETEROGENEOUS GROWTH

Abstract This paper examines the question of optimal harvesting time in a size‐heterogeneous farmed aquatic population, using a model reflecting the effect of population density on both overall mortality rate and individual growth. This analysis enables an optimal harvesting rule to be deduced. The results obtained are applied to shrimp culture in recirculation systems in Mexico. Numerical solutions are derived for different production scenarios. Assuming identical culture conditions, results are also obtained under the hypothesis of homogeneous population growth, the view traditionally taken in the relevant economic literature. The optimal harvesting times calculated tend to decrease with higher densities, although this rule fails under the size‐heterogeneous population model. In general, optimal harvesting times are overestimated when size‐homogeneity in the culture is assumed. Our analysis reveals that management predictions are significantly mistaken if the size‐heterogeneity phenomenon is not taken into account.     

Spectral deformation and Bäcklund transformation of constrained Willmore surfaces

The class of constrained Willmore surfaces in space-forms forms a Möbius invariant class of surfaces with strong links to the theory of integrable systems. This paper is dedicated to an overview on the topic. We define a spectral deformation, by the action of a loop of flat metric connections, and Bäcklund transformations, by applying a dressing action. We establish a permutability between spectral deformation and Bäcklund transformation and verify that all these transformations corresponding to the zero multiplier preserve the class of Willmore surfaces. We show that, for special choices of parameters, both spectral deformation and Bäcklund transformation preserve the class of constrained Willmore surfaces admitting a conserved quantity, and, in particular, the class of constant mean curvature surfaces in 3-dimensional space-forms.