Optical and electrochemical-mediated detection of ascorbic acid using manganese porphyrin and its gold hybrids

The developments concerning new hybrids based on porphyrin derivatives and colloids destined for the detection of ascorbic acid (AA) in the relevant range for medical investigations are presented. Mn(III) tetratolylporphyrin chloride (MnTTPCl), spherical gold colloid (n-Au), and their hybrid (MnTTPCl/n-Au) were chosen to be comparatively investigated by ultraviolet–visible spectroscopy in the presence of AA. The hybrid material (MnTTPCl/n-Au) has the best capacity to detect concentrations of AA in the range of 2.6 × 10^?6–4.38 × 10^?5 M. Modified glassy carbon (GC) electrodes were obtained by thin film deposition of MnTTPCl, n-Au alone, and in successive mixed thin films, comparing their response during the electrochemical oxidation of AA. The electrocatalytic effect of the MnTTPCl on the AA oxidation is justified both by the increase in the peak current density and by the shift toward more negative potentials (0.024 V). The GC/MnTTPCl electrode has the best electrocatalytic effect for the AA oxidation and is promising for sensor applications.     

Catalyzed Vinylogous Mukaiyama Aldol Reactions with Controlled Enantio‐ and Diastereoselectivities

In control : A new catalytic vinylogous Mukaiyama aldol reaction provides products with high diastereo‐ and enantioselectivities (up to 99 % de and ee; see scheme). The relative and absolute stereochemistry of a representative product was rigorously assigned by NMR and CD spectroscopies (measured and calculated), X‐ray diffraction, and quantum‐chemical calculations.

     

Studies on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, CuO,and TiO<Subscript>2</Subscript> water-based nanofluids: A comparative approach in laminar and turbulent flow

The Prandtl number, Reynolds number and Nusselt number are functions of thermophysical properties of nanofluids, and these numbers strongly influence the convective heat transfer coefficient. The thermophysical properties vary with volumetric concentration of nanofluids. Therefore, a comprehensive analysis was performed to evaluate the effects on the performance of nanofluids due to variations of density, specific heat, thermal conductivity and viscosity, which are functions of nanoparticle volume concentration. Three metallic oxides, aluminum oxide (Al₂O₃), copper oxide (CuO), and titanium dioxide (TiO₂), dispersed in water as the base fluid were studied. A convenient figure of merit, known as the Mouromtseff number, is used as a base of comparisonfor laminar and turbulent flows. The results indicated that the considered nanofluids can successfully replace water in specific applications for a single-phase forced convection flow in a tube.     

Electrical control of spin relaxation in a quantum dot

We demonstrate electrical control of the spin relaxation time T1 between Zeeman-split spin states of a single electron in a lateral quantum dot. We find that relaxation is mediated by the spin-orbit interaction, and by manipulating the orbital states of the dot using gate voltages we vary the relaxation rate W identical withT1(-1) by over an order of magnitude. The dependence of W on orbital confinement agrees with theoretical predictions, and from these data we extract the spin-orbit length. We also measure the dependence of W on the magnetic field and demonstrate that spin-orbit mediated coupling to phonons is the dominant relaxation mechanism down to 1 T, where T1 exceeds 1 s.     

Parametrically forced pattern formation

Pattern formation in a nonlinear damped Mathieu-type partial differential equation defined on one space variable is analyzed. A bifurcation analysis of an averaged equation is performed and compared to full numerical simulations. Parametric resonance leads to periodically varying patterns whose spatial structure is determined by amplitude and detuning of the periodic forcing. At onset, patterns appear subcritically and attractor crowding is observed for large detuning. The evolution of patterns under the increase of the forcing amplitude is studied. It is found that spatially homogeneous and temporally periodic solutions occur for all detuning at a certain amplitude of the forcing. Although the system is dissipative, spatial solitons are found representing domain walls creating a phase jump of the solutions. Qualitative comparisons with experiments in vertically vibrating granular media are made. (c) 2001 American Institute of Physics.     

Free amino acids analysis by liquid chromatography with tandem mass spectrometry in several botanicals with antioxidant character

A novel method based on liquid chromatography with tandem mass spectrometry for the analysis of 19 amino acids in plant materials is described. For the analysis, the plant material is extracted with 0.1 N hydrochloric acid with internal standards present in the extraction solution. The filtered extracts are injected using no clean‐up into the liquid chromatographic system coupled with a triple‐quadrupole tandem mass spectrometer with an electrospray ionization source. The analytes are separated using ion pair chromatography on a reversed‐phase column. The detection is performed in multiple‐reaction monitoring positive‐ion mode. Quantitation is obtained using calibrations. The validated procedure has been applied for the analysis of amino acids in 18 samples of plant material including botanicals with antioxidant character. The analysis requires 16 min separation time, has excellent precision and accuracy allowing amino acid analysis in a wide range of concentrations.     

Energy-dependent tunneling in a quantum dot

We present measurements of the rates for an electron to tunnel on and off a quantum dot, obtained using a quantum point contact charge sensor. The tunnel rates show exponential dependence on drain-source bias and plunger gate voltages. The tunneling process is shown to be elastic, and a model describing tunneling in terms of the dot energy relative to the height of the tunnel barrier quantitatively describes the measurements.     

Validated ion pair liquid chromatography/fluorescence detection method for assessing the variability of the loratadine metabolism occurring in bioequivalence studies

Inter- and intra-individual variability of the loratadine (LOR) metabolism in Caucasian subjects was assessed during a bioequivalence study for two pharmaceutical formulations (solid oral dosage forms) containing 10 mg of the active substance. The analytical data were obtained by applying a reliable, low-cost and sensitive ion pair liquid chromatography/fluorescence (IPLC/FLD) method for determination of both loratadine and descarboethoxyloratadine (DCL) in human plasma samples. The sample preparation procedure is based on liquid-liquid extraction of the target analytes from alkalinized plasma using diethyl-ether. The separation of the analytes and 8-chloroazatadine as internal standard (IS) was achieved through an isocratic ion pair (IP) elution on a Purospher((R)) STAR RP-18 column. The mobile phase containing sodium dodecyl sulfate (SDS) as ion pairing agent was pumped at a flow rate of 1 mL/min. Fluorescence detection (FLD) was achieved at 280 nm (excitation) and 440 nm (emission) wavelengths. The increased sensitivity of the method is also based on a large sample injected volume (250 microL). Linear response was found over the 0.5-20 ng/mL concentration interval for both target compounds. Low limits of quantification (LLOQ) around 0.3 ng/mL were found for LOR and DCL. Method validation is presented.     

Tsallis Entropy for Loss Models and Survival Models Involving Truncated and Censored Random Variables

The aim of this paper consists in developing an entropy-based approach to risk assessment for actuarial models involving truncated and censored random variables by using the Tsallis entropy measure. The effect of some partial insurance models, such as inflation, truncation and censoring from above and truncation and censoring from below upon the entropy of losses is investigated in this framework. Analytic expressions for the per-payment and per-loss entropies are obtained, and the relationship between these entropies are studied. The Tsallis entropy of losses of the right-truncated loss random variable corresponding to the per-loss risk model with a deductible d and a policy limit u is computed for the exponential, Weibull, χ2 or Gamma distribution. In this context, the properties of the resulting entropies, such as the residual loss entropy and the past loss entropy, are studied as a result of using a deductible and a policy limit, respectively. Relationships between these entropy measures are derived, and the combined effect of a deductible and a policy limit is also analyzed. By investigating residual and past entropies for survival models, the entropies of losses corresponding to the proportional hazard and proportional reversed hazard models are derived. The Tsallis entropy approach for actuarial models involving truncated and censored random variables is new and more realistic, since it allows a greater degree of flexibility and improves the modeling accuracy.