New evidence of appropriate fruit juice redox conditions for citric acid acting as a proton-carrier on Pt electrode: the effect on evaluating antioxidant properties

Journal of Solid State Electrochemistry - Recent scientific data in respect of the different effect of citric acid on antioxidant activity of plant polyphenols in pure solutions (no polyphenol...     

Determination of 1-hydroxypyrene in human urine by HPLC with electrochemical detection at a boron-doped diamond film electrode

A high-performance liquid chromatographic method with electrochemical detection (HPLC-ED) at a boron-doped diamond film electrode with preliminary separation and preconcentration by solid-phase extraction (SPE) has been developed for the determination of 1-hydroxypyrene (1-HP) in human urine. 1-HP is among the most widely used biomarkers of exposure to polycyclic aromatic hydrocarbons. Optimal HPLC-ED conditions have been found: mobile phase methanol-0.05 mol L(-1) phosphate buffer pH 5.0 (80:20, v/v), detection potential +1,000 mV versus Ag/AgCl (3 mol L(-1) KCl), and flow rate 0.8 mL min(-1). For SPE, LiChrolut(?) RP-18 E cartridges were used. The extraction yield was (87.0 ± 5.8)% (n = 5). The concentration dependence of 1-HP was measured in the concentration range from 0.01 to 10 μmol L(-1) (2.18-2,180 μg L(-1)) using methanolic solutions resulting from the SPE pretreatment of spiked human urine samples. The limit of detection (signal-to-noise ratio 3) and the limit of quantification (signal-to-noise ratio 10) of the biomarker were 0.013 μmol L(-1) (2.84 μg L(-1)) and 0.043 μmol L(-1) (9.39 μg L(-1)), respectively, which is sufficient for its determination in the urine of persons exposed to polycyclic aromatic hydrocarbons.     

Monolayers of an amphiphilic para-carboxy-calix[4]arene act as templates for the crystallization of acetaminophen

The title compound, 5,11,17,23-tetra-carboxy-25,26,27,28-tetradodecyloxy-calix[4]arene, 1, has been studied at the air–water interface, self-assembled as Langmuir monolayers, for its ability to interact with an active pharmaceutical ingredient (API), acetaminophen (APAP), and to initiate its crystallization. The Π/A isotherm study shows that there is a clear interaction between 1 and APAP causing an expansion of the monolayer. In addition to the known phase transition occurring at a surface tension of 38 mN m^?1, an additional kink is observed in the compression isotherm for concentrations of APAP above 40 mM suggesting that this API is causing an additional phase transition of the monolayer. Interface-initiated crystallization studies show that the presence of a monolayer spread on a supersaturated solution of APAP (26 g L^?1) triggers this API crystal growth from the interface. The transfer of 1-based monolayers on glass surfaces has been carried out using the Langmuir–Blodgett technique. The so-produced monolayers have been shown to template the crystallization of APAP. LB films of 1 have characterized using imaging and spectroscopic ellipsometry. The results suggest that each monolayer has an average thickness of 18 Å, which is consistent with the molecular structure of 1 self-organized parallel to the interface with the alkyl chains pointing out parallel to the axis of the macrocycle and without interdigitation of the alkyl chains. The presence of APAP in the subphase during the LB transfer causes a limited but relevant increase in the layer thickness. The study of the capabilities of the LB films to initiate crystallization of APAP is also demonstrated showing the influence of the monolayer packing on the quantity of formed crystals.     

Photoelectron spectra and structures of three cyclic dipeptides: PhePhe, TyrPro, and HisGly

We have investigated the electronic structure of three cyclic dipeptides: cyclo(Histidyl-Glycyl) (cHisGly), cyclo(Tyrosyl-Prolyl) (cTyrPro), and cyclo(Phenylalanyl-Phenylalanyl) (cPhePhe) in the vapor phase, by means of photoemission spectroscopy and theoretical modeling. The last compound was evaporated from the solid linear dipeptide, but cyclised, losing water to form cPhePhe in the gas phase. The results are compared with our previous studies of three other cyclopeptides. Experimental valence and core level spectra have been interpreted in the light of calculations to identify the basic chemical properties associated with the central diketopiperazine ring, and with the additional functional groups. The valence spectra are generally characterized by a restricted set of outer valence orbitals separated by a gap from most other valence orbitals. The theoretically simulated core and valence spectra of all three cyclic dipeptides agree reasonably well with the experimental spectra. The central ring and the side chains act as independent chromophores whose spectra do not influence one another, except for prolyl dipeptides, where the pyrrole ring is fused with the central ring. In this case, significant changes in the valence and core level spectra were observed, and explained by stronger hybridization of the valence orbitals.     

Potentiometric determination of mefenamic acid in pharmaceutical formulation by membrane sensor based on ion-pair with basic dye

The characteristics,performance and application of membrane sensors based on ion-pair Brilliant Green mefenamate are described.The sensor’s response to the mefenamate ion has the sensitivity of （86.0±2.0） mV/pC over the range of 9×10^-5-1×10^-2moI/Land the detection limit of 4.5×10^-5mol/L at pH 8.5-12.The sensor is easily assembled at a relatively low cost and has fast response time（5-10 s）.The proposed sensor displayed good selectivity for mefenamate ion in the presence of different substances.It was used to determine mefenamic acid in pharmaceuticals.     

Structural Study of C-undecylcalix[4]resorcinarene Solvate with Dioxane

The crystal structure of the molecular complex of C-undecylcalix[4]resorcinarene with dioxane has been determined by X-ray analysis. The asymmetric unit contains one host and four guest molecules. The calix[4]resorcinarene moiety adopts a bowl conformation with C_4v symmetry. Four undecyl chains are axially oriented. Calix molecules are packed in a bowl-to-bowl fashion with alternating hydrophilic and hydrophobic layers. One of the hydrophilic dioxane molecules is located at the rim of the calix moiety and is hydrogen bonded to the other one. There is no interaction to attract, or direct the dioxane molecule into the interior of the cavity. There is an exo complex formed. The dioxane molecules – located in the hydrophobic part – are highly disordered.     

A BEM for transient thermoelastic analysis of a functionally graded layer on a homogeneous substrate under thermal shock

Transient thermoelastic analysis of isotropic and linear thermoelastic bimaterials, which are constituted by a functionally graded (FG) layer attached to a homogeneous substrate, subjected to thermal shock is presented in this paper. For this purpose, a boundary element method for transient linear coupled thermoelasticity is developed. The material properties of the FG layer are assumed to be continuous functions of the spatial coordinates. The boundary-domain integral equations are derived by using the fundamental solutions of linear coupled thermoelasticity for the corresponding isotropic, homogeneous and linear thermoelastic solids in the Laplace-transformed domain. For the numerical solution, a collocation method with piecewise quadratic approximation is implemented. Numerical results for the dynamic stress intensity factors are presented and discussed. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nilpotent Gelfand pairs and spherical transforms of Schwartz functions I: rank-one actions on the centre

The spectrum of a Gelfand pair of the form ${(K\ltimes N,K)}$ , where N is a nilpotent group, can be embedded in a Euclidean space ${{\mathbb R}^d}$ . The identification of the spherical transforms of K-invariant Schwartz functions on N with the restrictions to the spectrum of Schwartz functions on ${{\mathbb R}^d}$ has been proved already when N is a Heisenberg group and in the case where N?=?N _3,2 is the free two-step nilpotent Lie group with three generators, with K?=?SO₃ (Astengo et?al. in J Funct Anal 251:772–791, 2007; Astengo et?al. in J Funct Anal 256:1565–1587, 2009; Fischer and Ricci in Ann Inst Fourier Gren 59:2143–2168, 2009). We prove that the same identification holds for all pairs in which the K-orbits in the centre of N are spheres. In the appendix, we produce bases of K-invariant polynomials on the Lie algebra ${{\mathfrak n}}$ of N for all Gelfand pairs ${(K\ltimes N,K)}$ in Vinberg’s list (Vinberg in Trans Moscow Math Soc 64:47–80, 2003; Yakimova in Transform Groups 11:305–335, 2006).     

Saturated Commutative Spaces of Heisenberg Type

In this paper, we give a partial classification of commutative spaces of Heisenberg type. Several classification results were known previously. In order to avoid complicated technical details, we restrict ourselves to saturated commutative spaces. Our results are presented in Table II.     

Large Deviation Probabilities for Square-Gaussian Stochastic Processes

We investigate properties of square-Gaussian stochastic processes. These processes are formed by quadratic forms of Gaussian processes or by limits in the mean square of quadratic forms of Gaussian processes. Special classes of these processes are determined and investigated. For processes from these classes estimates of large deviation probability are obtained. These estimates we use to estimate the probability that Gaussian vector-valued process leave some region on some interval of time. We construct asymptotic confidence regions for estimates of covariance functions of vector-valued Gaussian processes. Criterion of hypothesis testing on covariance functions of these processes is constructed.