Electrochemical Oxidation of the Antiretroviral Drug Nelfinavir on Modified Screen‐printed Electrodes

This paper describes the voltammetric study of the electrochemical oxidation of the antiretroviral drug Nelfinavir using a screen‐printed sensor modified with carbon nanotubes. The performance of the sensor in the determination of the drug was characterized in terms of precision (RSD 5.05 %, n=5) and capability of detection (10.99±0.87 μM for α=β=0.05, n=5) under optimized voltammetric conditions of pH, accumulation time and potential, in the calibration range from 10 to 150 μM of NFV. In order to check the viability of the device, the determination of the analyte in pharmaceutical and biological samples was carried out and its performance was also validated comparing it with HPLC.     

Universal properties of Ising clusters and droplets near criticality

Clusters and droplets of positive spins in the two-dimensional Ising model percolate at the Curie temperature in absence of external field. The percolative exponents coincide with the magnetic ones for droplets but not for clusters. We use integrable field theory to determine amplitude ratios which characterize the approach to criticality within these two universality classes of percolative critical behavior.     

Conformational analysis of 1,2,3,4-tetrahydroisoquinolines

Ring and nitrogen inversion account for the conformational equilibria of 3-phenyl-1, 2,3, 4-tetrahydroiso-quinolines. In order to quantitate the relative contribution of each conformer to the equilibrium, we undertook a molecular mechanics study on several substituted 3-phenyl-1, 2, 3, 4-tetrahydroisoquinolines. Predictions from calculations were checked against cmr chemical shift data. No boat conformation contributed significantly to the equilibrium. A general result of our calculations is that in all cases the 3-phenyl group in the equatorial position is strongly favored (by at least 2.50 kcal/mole). For 3-phenyl-1, 2, 3, 4-tetrahydroisoquinolines without substitution at nitrogen, N-H in equatorial position is preferred over the axial conformer, although the energy difference between both is always small (0.30–1.10 kcal/mole). For the cis-1,3-disubstituted compounds the le'3e conformers are the only species present (at least 99.8%). The calculated energy differences between the la′3a conformer and the le′3e conformer are always large (3.80–6.10 kcal/mole for the NHe conformers and 3.60–3.80 kcal/mole for the NHa conformers). The lack of a γ_1a upfield shift at C3 also points to the preference for the pseudoequatorial-equatorial conformer. For N-methyl-3-phenyl-1,2,3,4-tetrahydroisoquinoline a preference for the NMe group in the equatorial position is predicted (0.60–2.00 kcal/mole). The small downfield shift at C4 (γ_Na = 0.5 ppm) is consistent with the equatorial NMe preference. For the cis-1,2,3-trisubstituted compounds no significant γ_1a effect at C3 (γ_1a = -0.2 and 1.0 ppm) or γ_Na effect at C4 (γ_Na = 0.1 and 0.4 ppm) is observed. For these compounds, deformations due to steric congestion are evidenced by the deviation from the values of the C4a-C8a-Cl-N and C4a-C4-C3-N torsional angles, as compared to less crowded 3-phenyl-1,2,3,4-tetrahydroisoquinolines. Here the heterocyclic ring adopts a distorted half-chair conformation.     

Solid-state study of hydrazonium tartrate and deuterated hydrazonium tartrate enantiomers

A study of the crystallographic, optical, and thermochemical properties of hydrazonium tartrate and deuterated hydrazonium tartrate enantiomers is described. Crystals of the enantiomers are orthorhombic with a tetramolecular cell. The space group is P2₁2₁2₁ with the lattice parameters a₀ = 7.640 ± 0.002 Å, b₀ = 13.441 ± 0.003 Å, and c₀ = 7.029 ± 0.002 Å. No change in lattice parameters is observed on deuteration. Optical second harmonic powder analysis shows the crystals to be phase matchable at 1.06 μm with d^2ω = 11 d^2ωα-SiO₂. The optical nonlinearity being unaffected by deuterium substitution is attributed to the nonlinear electronic polarizability of the hydrogen bonds. Crystals are transparent from 239 nm to 1.61 μm. Deuteration shifts the long wavelength cutoff to 2.07 μm, without affecting the band edge.     

Low-Energy Universality in Three-Body Models

 We study the low-energy universality observed in three-body models through a scale-independent approach. From the already estimated infinite number of three-body excited energy states, which happen in the limit when the energy of the subsystem goes to zero, we are able to identify the lower energies of the helium trimers as possible examples of Thomas-Efimov states. By considering this example, we illustrate the usefulness of a scaling function, which we have defined. The approach is applied to bosonic systems of three identical particles, and also to the case where two kinds of particles are present. Received June 30, 1999; revised July 27, 1999; accepted for publication August 29, 1999     

Evaluation of forces in magnetic materials by means of energy and co-energy methods

The evaluation of the total force of magnetic origin acting upon a body in a stationary magnetic field is often carried out using the so-called magnetic energy (or co-energy) method, which is based on the derivation of the magnetic energy (or co-energy) with respect to a virtual rigid displacement of the considered body. The application of this method is usually justified by resorting to the energy conservation principle, written in terms both of electrical and of mechanical quantities. In this paper we shall re-examine the whole matter in the context of classical thermodynamics, in order to obtain a more comprehensive and general proof of the validity of the energy (or co-energy) approach and to point out its limitations. Two typical configurations will be discussed; in the first one, the field sources are represented by conducting bodies carrying free currents, whereas in the second one a permanent magnet creates the driving field. All magnetic materials are assumed to be non-hysteretic and permanent magnets are represented by means of the well-known linear model in the second quadrant of the (B,H) plane. Received 25 July 2001 and Received in final form 5 November 2001     

Binding Three-Particles at the Edge of Stability

 The stability threshold for an Efimov state is determined as a function of the physical scales of the system. Light exotic nuclei and triatomic molecules are investigated. Scaling, universality, and renormalization-group invariance properties are discussed in this context. Received October 25, 2001; accepted for publication November 12, 2001     

Thermal and dielectric properties of LiKSO4 and LiCsSO4

Measurements of the thermal and dielectric properties of single crystals of the double sulfates LiKSO₄ and LiCsSO₄ are reported. Uncertainty in the determination of the space group of LiCsSO₄ is resolved on the basis of optical second harmonic generation and pyroelectric measurements; the correct space group is Pcmn. Measurements of the pyroelectric coefficient, dielectric constant, and specific heat of LiKSO₄ permit an assessment of the suitability of this material for use in pyroelectric detectors.