Simultaneous determination of theophylline and caffeine by proton magnetic resonance spectroscopy using partial least squares regression techniques.

A 1H-NMR procedure based on an analysis of its data by a multivariate calibration method was conducted for the simultaneous determination of theophylline and caffeine in synthetic and real samples. Partial least squares regression (PLS) was chosen as the calibration method. The methyl signals of theophilline at 3.36 and 3.54 ppm that overlapped with those of caffeine were significant characteristics which were employed in this study for their analyses. The proposed method was successfully applied to recovery studies of theophylline and caffeine from real tablet samples.     

Electrochemical Characterization of In Situ Functionalized Gold Cysteamine Self‐Assembled Monolayer with 4‐Formylphenylboronic Acid for Detection of Dopamine

Functionalization of gold cysteamine (Au? CA) self‐assembled monolayer with 4‐formylphenylboronic acid (BA) via Schiff's base formation, through in situ method to fabricate Au‐CA‐BA electrode is presented and described. The fabricated electrode was used as a novel sensor for accumulation and determination of dopamine (DA). The accumulation of DA as a diol on the topside of Au‐CA‐BA as a Lewis acid, was performed via esterification (Au? CA? BA? DA), and followed for determination of DA. Functionalization, characterization, and determination steps were probed by electrochemical methods like cyclic voltammetry and electrochemical impedance spectroscopy. The data will be presented and discussed from which a new sensor for DA is introduced.     

Band selection of hyperspectral-image based weighted indipendent component analysis

Huge amounts of data in hyperspectral images have been caused to represent approaches for the band selection of these images. In this paper, a new approach based on independent component analysis (ICA) is proposed. The idea of projection pursuit is used to order the bands on the basis of a non-gaussianity distribution. Applying a negentropy function to weight bands is a novel idea that leads to the selection of bands with minimum mutual information (MI) and besides maximum entropy, with respected to the bands selected using other methods.     

Copper(II)-selective fluorimetric bulk optode membrane based on a 1-hydroxy-9,10-anthraquinone derivative having two propenyl arms as a neutral fluorogenic ionophore

A new optical chemical sensor has been developed for the selective determination of copper(II) ions in aqueous solutions. The reversible sensing system was prepared by incorporating 1-hydrpxy-2-(prop-2'-enyl)-4-(prop-2'-enyloxy)-9,10-anthraquinone (AQ) as a neutral Cu2+-selective fluoroionophore in the plasticized PVC membrane with potassium tetrakis(p-chlorophenyl borate) as an anionic additive. The response of the sensor is based on the fluorescence quenching of AQ by Cu2+ ions. At a pH 5.5, the proposed sensor displays a calibration response for Cu2+ over a wide concentration rang of 1.0 x 10(-2) to 1.0 x 10(-6) M, with a relatively fast response of less than 40 s. In addition to high stability and reproducibility, the sensor shows a unique selectivity towards Cu2+ ion with respect to common co-existing cations. The proposed fluorescence optode was applied successfully to the determination of copper(II) in black tea samples.     

Peroxyoxalate-chemiluminescence of Tinopal CBS as a commercially important optical brightener: Mechanistic study and quantification

The peroxyoxalate-chemiluminescence arising from reaction of bis(2,4,6-trichlorophenyl)oxalate with hydrogen peroxide in the presence of a brightener Tinopal CBS (2,2′-((1,1′-biphenyl)-4,4′-diyldi-2.1-ethenediyl)bisbenzene sulfonic acid, disodium salt) has been studied. The relationship between the chemiluminescence intensity and concentrations of bis(2,4,6-trichlorophenyl)oxalate, sodium salicylate (as catalyst), hydrogen peroxide and Tinopal CBS is reported. The chemiluminescence parameters including intensity at maximum chemiluminescence, time at maximum intensity, total light yield, theoretical maximum level of intensity and pseudo-first-order rate constants for the rise and fall of the chemiluminescence burst (k_r and k_f) were evaluated from computer fitting of the resulting intensity-time plots. The activation parameters E_a, ΔH^‡, ΔS^‡ and ΔG^‡ for the rise and fall steps were evaluated from the temperature dependence of k_r and k_f values. The results were discussed in terms of chemically initiated electron transfer between a reactive intermediate and Tinopal CBS as fluorescence activator. A possible mechanism involving dioxetanone derivatives as intermediates is proposed. Since there is a linear relationship between reciprocal of chemiluminescence intensity and reciprocal of fluorescer concentration, an analytical method based on partial least squares (PLS) regression was proposed for quantitative determination of Tinopal CBS. Satisfactory results were obtained with percent relative prediction error (RPE%) of 2.52 and detection limit of 2.7×10⁻⁵ M.     

The Σ1-provability logic of HA

In this paper we introduce a modal theory ${\mathsf{iH}}_{\sigma }$ which is sound and complete for arithmetical ${\mathrm{\Sigma }}_1$-interpretations in $\mathsf{HA}$, in other words, we will show that ${\mathsf{iH}}_{\sigma }$ is the ${\mathrm{\Sigma }}_1$-provability logic of $\mathsf{HA}$. Moreover we will show that ${\mathsf{iH}}_{\sigma }$ is decidable. As a by-product of these results, we show that $\mathsf{HA}+\square \perp$ has de Jongh property.     

Efficiency analysis in two-stage structures using fuzzy data envelopment analysis

Two-stage data envelopment analysis (TsDEA) models evaluate the performance of a set of production systems in which each system includes two operational stages. Taking into account the internal structures is commonly found in many situations such as seller-buyer supply chain, health care provision and environmental management. Contrary to conventional DEA models as a black-box structure, TsDEA provides further insight into sources of inefficiencies and a more informative basis for performance evaluation. In addition, ignoring the qualitative and imprecise data leads to distorted evaluations, both for the subunits and the system efficiency. We present the fuzzy input and output-oriented TsDEA models to calculate the global and pure technical efficiencies of a system and sub-processes when some data are fuzzy. To this end, we propose a possibilistic programming problem and then convert it into a deterministic interval programming problem using the α-level based method. The proposed method preserves the link between two stages in the sense that the total efficiency of the system is equal to the product of the efficiencies derived from two stages. In addition to the study of technical efficiency, this research includes two further contributions to the ancillary literature; firstly, we minutely discuss the efficiency decompositions to indicate the sources of inefficiency and secondly, we present a method for ranking the efficient units in a fuzzy environment. An empirical illustration is also utilised to show the applicability of the proposed technique.     

Nonlinear optical and structural properties of M@C N endohedrals (M = Li,Ca and Sc,N = 60 and 70)

We have investigated the static (ω = 0) and frequency-dependent nonlinear optical (NLO) properties of the M@C _N endohedrals (M = Li, Ca, Sc, N = 60 and 70) using the SSH (Su–Schrieffer–Heeger) approximation and sum-over-state (SOS) approach. Also, we study the effects of displacement and alkali, alkaline earth and lanthanide metal atoms and type of cage on the hyperpolarisabilities of the M@C _N endohedrals. The hyperpolarisability magnitudes and spectra are in agreement with experiment and the work of others using the SSH approximation. Our results indicate that the cage-type effect on the NLO spectra of M@C _N endohedrals is dramatic. Also, atom type has little effect on the highest peak value. These relationships between the atom and cage type and hyperpolarisability values may be beneficial to experimentalists when designing new NLO materials with large NLO responses.     

On the performance of density functional schemes for computing the static dipole polarizability of 4d transition-metal monohalides

This article presents the static dipole polarizabilities of 4d transition-metal monohalides in the framework of density functional theory. The behavior of a large number of density functionals, including various types of the local spin density approximation (LSDA), the generalized gradient approximation (GGA), meta GGA (MGGA), hybrid GGA (HGGA), and hybrid meta GGA (HMGGA), has been assessed in polarizability calculations. The highly accurate CCSD(T) methodology is used to benchmark a variety of functionals. Our results indicate that there is a large variation in performance of the various functionals of each type in the calculation of the dipole polarizability. It turned out that, in the LSDA class, SVWN5 gives better results than SVWN3 for the reference values. Of the GGA methods, BP86 and BPW91 give the best results for our data set, followed by G96LYP. The TPSS functional is the best method of the MGGA class, followed by the VSXC and BB95 functionals. Moreover, the B98 and mPW1PW91 functionals are the best methods of the HGGA lineage, predicting the most accurate static dipole polarizabilities. Finally, TPSS1KCIS and PBE1KCIS are the best methods of the HMGGA functionals for that purpose. In general, it was found that the HGGA and HMGGA functionals provide the best performance.     

On monoids over which all generators satisfy a flatness property

This paper addresses conditions under which all generators in the category of right S-acts (where S is a monoid) satisfy a flatness property. There are characterizations for monoids over which all generators satisfy a flatness property α where α can stand for freeness, projectivity, strong flatness, Condition (P), principal weak flatness and torsion freeness. To our knowledge, the problem has not been studied for other flatness properties such as weak flatness, Condition (E) and regularity. The present paper addresses this gap.