Development and Validation of a Densitometric HPTLC Method for Quantitative Analysis of Levofloxacin in Human Plasma

JPC – Journal of Planar Chromatography – Modern TLC -     

Stability of Indices in the KKT Conditions and Metric Regularity in Convex Semi-Infinite Optimization

This paper deals with a parametric family of convex semi-infinite optimization problems for which linear perturbations of the objective function and continuous perturbations of the right-hand side of the constraint system are allowed. In this context, Cánovas et al. (SIAM J. Optim. 18:717–732, [2007]) introduced a sufficient condition (called ENC in the present paper) for the strong Lipschitz stability of the optimal set mapping. Now, we show that ENC also entails high stability for the minimal subsets of indices involved in the KKT conditions, yielding a nice behavior not only for the optimal set mapping, but also for its inverse. Roughly speaking, points near optimal solutions are optimal for proximal parameters. In particular, this fact leads us to a remarkable simplification of a certain expression for the (metric) regularity modulus given in Cánovas et al. (J. Glob. Optim. 41:1–13, [2008]) (and based on Ioffe (Usp. Mat. Nauk 55(3):103–162, [2000]; Control Cybern. 32:543–554, [2003])), which provides a key step in further research oriented to find more computable expressions of this regularity modulus. This research was partially supported by Grants MTM2005-08572-C03 (01-02) and MTM2006-27491-E (MEC, Spain, and FEDER, E.U.), ACOMP06/117-203 and ACOMP/2007/247-292 (Generalitat Valenciana, Spain), and CIO (UMH, Spain).     

Effects of activated carbon properties on the adsorption of naphthalene from aqueous solutions

The aim of this work was to investigate the role of porous and chemical heterogeneities of activated carbons in the adsorption of naphthalene from aqueous media. A commercially available activated carbon was used as the adsorbent, and its surface heterogeneity was systematically altered by heat treatment at 450 and 850 °C, obtaining a series of carbons with various oxygen contents and similar surface functionalities. The results confirmed that the adsorption of naphthalene depends strongly on the pore size distribution of the adsorbent, particularly narrow microporosity. Moreover, oxygen functionalities reduced the accessibility and affinity of naphthalene to the inner pore structure via formation of hydration clusters. Consequently, the hydrophobic/hydrophilic character of the adsorbent is important, since it dominates the competitive adsorption of water. Adsorbents with a high non-polar character (i.e., low oxygen content) have proven to be more efficient for naphthalene adsorption.     

On the Lipschitz Modulus of the Argmin Mapping in Linear Semi-Infinite Optimization

This paper is devoted to quantify the Lipschitzian behavior of the optimal solutions set in linear optimization under perturbations of the objective function and the right hand side of the constraints (inequalities). In our model, the set indexing the constraints is assumed to be a compact metric space and all coefficients depend continuously on the index. The paper provides a lower bound on the Lipschitz modulus of the optimal set mapping (also called argmin mapping), which, under our assumptions, is single-valued and Lipschitz continuous near the nominal parameter. This lower bound turns out to be the exact modulus in ordinary linear programming, as well as in the semi-infinite case under some additional hypothesis which always holds for dimensions n ? 3. The expression for the lower bound (or exact modulus) only depends on the nominal problem’s coefficients, providing an operative formula from the practical side, specially in the particular framework of ordinary linear programming, where it constitutes the sharp Lipschitz constant. In the semi-infinite case, the problem of whether or not the lower bound equals the exact modulus for n > 3 under weaker hypotheses (or none) remains as an open problem.     

New supramolecular liquid crystals induced by hydrogen bonding between pyridyl-1,2,4-oxadiazole derivatives and 2,5-thiophene dicarboxylic acid

Supramolecular liquid crystalline complexes were obtained from binary mixtures of 3-(4-pyridyl)-5-(4-n-alkoxy)phenyl-1,2,4-oxadiazoles and 2,5-thiophene dicarboxylic acid. Although the oxadiazole derivatives and the dicarboxylic acid are non-mesomorphic, the H-bonded complexes exhibit mesomorphism. Their liquid crystalline properties were investigated by differential scanning calorimetry and polarizing optical microscopy. The complexes exhibit enantiotropic nematic phases. A structural study involving AM1 semi-empirical calculations is also described.     

Pump–probe studies of EUV and X-ray emission dynamics of laser-irradiated noble gas droplets

The interaction of high intensity 100-ps laser pulses with micron-sized noble gas (argon and krypton) droplets is experimentally investigated via a series of pump–probe experiments monitoring the delay-dependent X-ray and extreme ultraviolet (EUV) emission, and by imaging frequency-doubled probe light scattered from the interaction region. An understanding of the time scales for this interaction is important for optimization of EUV sources for next-generation lithography that utilizes laser-produced plasmas (LPP). Depending on the spectral region of interest, the type of emission, and the droplet characteristics, the effective emission lifetime was found to extend from a few hundred picoseconds to as long as several nanoseconds, in agreement with the expected plasma expansion, EUV excitation, and recombination emission time scales. Received: 22 August 2002 / Accepted: 8 February 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-301/3149-363, E-mail: riq@wam.umd.edu     

Laser-polarized 129Xe NMR at 1.88 T and 8.5 mT: a signal-to-noise ratio comparison

The signal-to-noise ratio of nuclear magnetic resonance signals from laser-polarized 129Xe gas was investigated at 8.5 mT and compared to that of signals acquired at 1.88 T. A dedicated 8.5 mT resistive magnet was constructed and used to acquire the signals. The SNR for 1 atm of xenon gas with a polarization of 1% was measured to be 1900 at a field of 1.88 T. Under identical acquisition conditions, the SNR at 8.5 mT was about 60 (or 32 times lower). After measuring and including all of the electrical factors of the detection systems at each field strength, theory indicates the SNR value measured at 8.5m T should be about 36 times lower. Considering the widely differing frequencies and completely different detection systems the agreement is quite good and indicates that extrapolating the frequency dependence of the SNR down to very low fields does work as long as the detection system parameters are carefully accounted for. This work suggests that magnetic resonance (MR) imaging is achievable on ideal gas samples at 8.5 mT using laser-polarized 129Xe gas down to the practical resolution limit of about 0.5mm, although the SNR will be very low (approximately 1.4). The feasibility of imaging small animals at 8.5 mT is discussed and it is suggested that a field of about 50 mT is required.     

Regioselective enzymatic acylations of polyhydroxylated eudesmanes: semisynthesis, theoretical calculations, and biotransformation of cyclic sulfites

Different lipase enzymes have been tested in order to perform regioselective acetylations on the eudesmane tetrol from vulgarin. High yields (95%) of 1,12-diacetoxy derivative (4) were achieved in 1 h with Candida antarctica lipase (CAL). However, only the 12-acetyl derivative (6) was obtained in similar yield with Mucor miehei (MML) or Candida cylindracea (CCL) lipases. The enzymatic protection at C-1 and C-12 has been used to form eudesmane cyclic-sulfites between C-6 and C-4 atoms. The R/S-sulfur configuration has been assigned by means of the experimental and theoretical (13)C and (1)H NMR chemical shifts. The theoretical shifts were calculated using the GIAO method, with a MM+ geometry optimization followed by a single-point calculation at the B3LYP/6-31G(*) level (B3LYP/6-31G(*)//MM+). Moreover, B3LYP/6-31G(*) geometry optimizations were carried out to test the B3LYP/6-31G(*)//MM+ results, for the deacetylated sulfites (12 and 15). In addition to the delta(C) and delta(H) shifts, the (3)J(HH) coupling constants were also calculated and compared with the experimental values when available. Finally, different reactivities have been checked in both sulfites by biotransformation with Rhizopus nigricans. While the R-sulfite gave 2 alpha- and 11 beta-hydroxylated metabolites, the S-sulfite yielded only regioselective deacetylations. Furthermore, both sulfites showed different reactivities in redox processes.     

Sounds produced by Australian Irrawaddy dolphins, Orcaella brevirostris

Sounds produced by Irrawaddy dolphins, Orcaella brevirostris, were recorded in coastal waters off northern Australia. They exhibit a varied repertoire, consisting of broadband clicks, pulsed sounds and whistles. Broad-band clicks, "creaks" and "buzz" sounds were recorded during foraging, while "squeaks" were recorded only during socializing. Both whistle types were recorded during foraging and socializing. The sounds produced by Irrawaddy dolphins do not resemble those of their nearest taxonomic relative, the killer whale, Orcinus orca. Pulsed sounds appear to resemble those produced by Sotalia and nonwhistling delphinids (e.g., Cephalorhynchus spp.). Irrawaddy dolphins exhibit a vocal repertoire that could reflect the acoustic specialization of this species to its environment.     

Synthesis, testing, and characterization of a novel Nafion membrane with superior performance in photoassisted immobilized Fenton catalysis

A new type of Nafion/Fe structured membrane ensuring faster kinetics, higher efficiency, and mechanical properties has been prepared and will be compared in its performance with the Fe-exchanged commercial Dupont 117 Nafion/Fe membrane during the abatement of model organic compounds. During the casting of the laboratory Nafion sample, the iron ions were introduced directly into the Nafion oligomer solution. This novel laboratory Nafion/Fe was tested as an immobilized catalyst in the degradation of several toxic pollutants showing a faster photoassisted degradation kinetics and a wider effective photocatalytic pH range compared to the Fe-exchanged commercial Dupont 117 Nafion/Fe membrane. When carrying out Ar ion sputtering of the 50 topmost catalyst layers, evidence is presented by X-ray photoelectron spectroscopy that Fe ions are found in the inner Nafion layers and seem to be responsible for the immobilized photoassisted Fenton processes leading to the degradation of 4-chorophenol (4-CP) taken as a model organic pollutant for the degradation process reported in this study. In the laboratory sample, the iron oxy/hydroxy Nafion moiety undergoes a transition to a more stable Nafion/Fe species during 4-CP degradation as determined by X-ray diffraction. This more stable form shows a higher iron dispersion and crystallinity compared to the fresh sample and is stabilized by the Nafion matrix avoiding the formation of separate iron phases. By infrared absorption (Fourier transform infrared), evidence is presented for the band of akaganeite-like species at 870 cm(-1) on the laboratory Nafion/Fe sample. This band disappears after 4-CP degradation because of the formation of the more highly dispersed iron species. Sputtering experiments show a decrease of F-containing groups in the laboratory Nafion/Fe samples closer to the catalyst upper layer while the amounts of Fe, C, and in particular O species increase in the topmost layer(s). In particular, the oxygenated species develop in the Nafion/Fe up to approximately 50 A below the catalyst surface. These species remain stable during the long-term Nafion/Fe degradation of 4-CP. Dynamo-mechanical analysis performed on laboratory Nafion/ Fe membrane samples revealed that these membranes possessed a greater mechanical modulus and resistance than the commercial Dupont 117 Nafion membrane.