A New Sensitive Fluorescence Sensor and Photocatalyst for Determination and Degradation of Sodium Valproate Using g-C3N4@Fe3O4@CuWO4 Nanocomposite and FCCD Optimization.

In this research, carbon nitride nanocomposite coupled with Fe3O4 and CuWO4 was thermally synthesized and characterized by different techniques, including SEM, TEM, XRD, EDX, and FTIR. Due to sodium valproate's luminescence quenching of this nanocomposite, a reliable, accurate, sensitive, selective, and fast-acting sodium valproate assay was proposed. Optimization of this fluorescent sensor was carried out by the FCCD approach. In the optimum conditions, the plot of sodium valproate concentration versus nanocomposite fluorescence emission showed a linear response (R2 = 0.9918), with a range of 0-0.55 µM, the limit of detection (S/N = 3) equal to 0.85 nM and limit of qualification equal to 2.82 nM. Photocatalytic activity of g-C3N4@Fe3O4@CuWO4 (40%) nanocomposite exhibited a good potency to sodium valproate degradation. Active species of degradation including superoxide radicals, holes, and hydroxyl radicals were investigated using ammonium oxalate, benzoquinone, and 2-propanol to identify the mechanism of photodegradation action. The activity of benzoquinone in the photocatalytic process led to a reduction in the rate of analyte degradation, which indicates the prominent role of superoxide radicals compared to other species in the degradation process. The degradation rate of the analyte using the Fenton reagent was found to be around two times more than in the Fenton reagent-free process. The possible mechanism for the fluorescence sensor and photocatalytic degradation reaction was also discussed.

Global and local QSPR models to predict supercooled vapour pressure for organic compounds.

In this study, a quantitative structure-property relationship (QSPR) approach was used for estimation of logarithmic values of supercooled liquid vapour pressure (log PL) of a large set of structurally diverse organic compounds. This set includes 12 local sets of aromatic and aliphatic hydrocarbons, polychlorinated biphenyls, ethers, polychlorinated and brominated diphenylethers, polychlorinated naphthalenes and alcohols. Some simple models based on the linear relationship between log PL and VolSurf descriptors were developed as global models, and a general equation as a simple way to calculate the supercooled liquid vapour pressure of organic chemicals was provided. A descriptor representing the hydrophilic regions (WO1) of organic chemicals showed the highest correlation with log PL and resulted in a one-parameter global model characterized by satisfactory statistical performance; calibration (r2c) and prediction (r2p) correlation coefficient of 0.84 and 0.85, respectively. Moreover, local QSPR models were also developed for each subset of organic compounds and, as expected, the statistical results obtained from these models were better than the global one. From the descriptors involved in the models, it is concluded that the hydrophilic and hydrophobic regions at different energy levels and polarizability usually determine the variation of supercooled liquid vapour pressure of organic compounds.

3D-QSAR studies on the toxicity of substituted benzenes to Tetrahymena pyriformis: CoMFA, CoMSIA and VolSurf approaches.

Three-dimensional quantitative structure-activity relationship (3D-QSAR) analysis were performed on the toxicity of a large set of substituted benzenes toward ciliate Tetrahymena pyriformis. The 3D-QSAR studies were carried out using comparative molecular field analysis (CoMFA), comparative molecular similarity indices analysis (CoMSIA) and VolSurf techniques. The optimal CoMFA and CoMSIA models obtained from the training set were all statistically significant with correlation coefficients (R(2)) greater than 0.79 and absolute error less than 0.33 in log units. The predictive ability of the models was externally evaluated through the prediction of a test set (20 percent of the whole data set) that were not included in the training set. A simple and fairly good predictive linear model based on VolSurf descriptors was also developed that showed an adequate prediction power of the toxicity (pIGC50) of substituted benzenes. Validation, reliability and robustness of models were also evaluated by leave-one-out, leave-four-out, bootstrapping and progressive scrambling approaches. The results confirmed that in addition to hydrophobic effects, electrostatic and H-bonding interactions also play important roles in the toxicity of substituted benzenes. The information obtained from CoMFA and CoMSIA 3-D contour maps could be useful to explain the toxicity mechanism of substituted benzenes.

Comparative molecular field analysis and comparative molecular similarity index analysis studies on 1H NMR chemical shift of NH group of diaryl triazene derivatives.

Comparative molecular field analysis (CoMFA), comparative molecular field analysis region focusing (CoMFA-RF) for optimizing the region for the final partial least square analysis, and comparative molecular similarity indices analysis (CoMSIA) methods were employed to develop three-dimensional quantitative structure-activity relationship (3D-QSAR) models of (1)H NMR chemical shift of NH proton of diaryl triazene derivatives. The best orientation was searched by all-orientation search (AOS) strategy to minimize the effect of the initial orientation of the structures. The predictive abilities of CoMFA-RF and CoMSIA models were determined using a test set of ten compounds affording predictive correlation coefficients of 0.721 and 0.754, respectively, indicating good predictive power. For further model validation, cross validation (leave one out), progressive scrambling, and bootstrapping were also applied. The accuracy and speed of obtained 3D-QSAR models for the prediction of (1)H NMR chemical shifts of NH group of diaryl triazene derivatives were greater compared to some computational well-known procedures.

Indoleamine 2,3-dioxygenase is expressed in the endometrium of cycling mice throughout the oestrous cycle.

Indoleamine 2,3-dioxygenase (IDO), an enzyme responsible for tryptophan catabolism, is thought to be required to prevent the rejection of the allogenic fetus by maternal T cells and to protect against intra- and extra-cellular pathogens. Consequently, we studied the expression of IDO in the endometrium of female Balb/c mice during the oestrous cycle. At each phase, the endometrium was peeled away and the relative expression of IDO mRNA was detected by semi-quantitative RT-PCR. The presence of IDO protein was confirmed in each phase by Western blotting and immunohistochemistry. Our results showed that IDO is expressed in the endometrium of cycling mice during all the phases of oestrous cycle. The expression of IDO was highest at the oestrus and lowest at the dioestrus. By means of Western blotting and immunohistochemistry, we obtained evidence that IDO protein is synthesised in the endometrium of cycling mice throughout the oestrous cycle. In accordance with RT-PCR results, IDO protein was predominant at the oestrus phase. IDO protein was mainly localised in the glandular and luminal epithelial cells. Our results support the concept of IDO providing a mechanism of innate immunity to protect from ascending infections of the female reproductive tract. In addition, considering the fact that mating only occurs during the oestrus phase, the high expression of IDO in this phase is likely to be a mechanism that induces immunological tolerance of the fetus.

Spectroscopic characterization of thiazole orange-3 DNA interaction.

The interaction of a new derivative of thiazole orange (TO-3) with calf thymus DNA (ctDNA) has been investigated by fluorescence and absorption spectroscopy. When TO-3 binds to ctDNA, absorption bands exhibit significant hypochromicity at low base pair/dye ratio (BP/D ratio), and high BP/D show hyperchromicity with red shift. The spectral changes are attributed to the different species formed between TO-3 and ctDNA in the titration course of the dye molecule with DNA. Multivariate curve resolutions-alternating least squares (MCR-ALS) is applied to the absorption measurements recorded to recover the concentration profiles and the pure spectra of the DNA/TO-3 complexes involved in the process. The binding constant and size of the binding site have been determined spectrophotometrically using the McGhee von Hippel equation. MCR-ALS has been used to reveal the precise concentration profiles of all detectable species formed between ctDNA and TO-3 and their pure spectral profiles.

Simultaneous square wave voltammetric determination of 2-mercaptobenzothiazole and 2-mercaptobenzoxazole by partial least squares method in water samples.

A rapid sensitive and versatile method for simultaneous determination of 2-mercaptobenzothiazole (MBT) and 2-mercaptobezoxazole (MBO) based on the square wave voltammetric (SWV) using mercury drop electrode (SMDE) has been presented. A three-electrode system containing SMDE working electrode, Pt auxiliary electrode and Ag/AgCl reference electrode was used throughout. The linear calibration graphs are in the concentration range of 7-40 microg mL(-1) and the equations are: (Deltai)=1.372CMBT-9.112 (r=0.9982) and (Deltai)=0.246CMBO-1.736 (r=0.9985) for MBT and MBO, respectively. Partial least squares regression (PLS) was applied to resolve the seriously overlapped voltammograms without any pre-separation step. The five level partial factorial design was used as calibration design method and the cross-validation method was used to select the number of significant factor for PLS model building. Five significant PLS components are used for MBT and MBO. A set of synthetic sample mixtures were used to validate the propose method. The root-mean-square errors of predictions (RMSEPs) and percent of relative prediction errors (RPEs) are 0.841 and 0.777 microg mL(-1) and +/-3.58 and +/-3.74% for MBT and MBO, respectively. The developed method was then applied to the analysis of these two compounds in different water samples with satisfactory results.

Conductometric simultaneous determination of acetic acid, monochloroacetic acid and trichloroacetic acid using orthogonal signal correction-partial least squares.

A simultaneous conductometric titration method for determination of mixtures of acetic acid, monochloroacetic acid and trichloroacetic acid based on the multivariate calibration partial least squares is proposed. It is possible to obtain an adjustable model to relate squared concentration values of the mixtures used in the calibration range by conductance. The effect of orthogonal signal correction (OSC) as a preprocessing technique used to remove the information unrelated to the target variables is studied. The calibration model was build using conductometric titrations data of 16 mixtures of three acids. The concentration matrix was designed by a orthogonal design. The root mean squares error of prediction (RMSEP) for acetic acid, monochloroacetic acid and trichloroacetic acid with and without OSC were 0.08, 0.30 and 0.08, and 0.15, 0.40 and 0.18, respectively. The results obtained by OSC-PLS are better than the PLS and this indicate the successful application of the OSC filter as a good preprocessing method in multivariate calibration methods. The proposed procedure allows the simultaneous determination of these acids, in the synthetic mixtures.

A new algorithm for the determination of protolytic constants from spectrophotometric data in multiwavelength mode: Calculations of acidity constants of 4-(2-pyridylazo)resorcinol (PAR) in mixed nonaqueous-water solvents.

A new efficient, simple and versatile algorithm is presented for determination of the protolytic constants from spectrophotmetric data in multiwavelength mode based on the combining of hard and soft modeling. The algorithm was checked by determining the acidity constants of a triprotic acid from theoretical and real absorption-pH data. The real spectral data are obtained from photometric titration of different solutions of 4-(2-pyridylazo)resorcinol (PAR) by a standard base solution under an inert atmosphere. The algorithm starts the minimization process using an user supplied number of components and initial guesses of the unknown parameters and refined in a least squares manner. New algorithm is implemented in the new version of DATAN package (version 3.1). The validity of the obtained results was checked by some well known programs such as DATAN 2.1, SPECFIT/32, SQUAD, a modified version of difference spectra and a A-pH curve method. The comparison of the outputs of the DATAN 3.1 with the other programs reveals that there is a very good agreement between the obtained results and mentioned programs.

Multiwavelength spectrophotometric determination of protolytic constants of 4-(2-pyridylazo) resorcinol (PAR) in binary DMF-water mixtures.

A multiwavelength spectrophotometric titration method was applied to study the protolytic constants of 4-(2-pyridylazo) resorcinol(PAR), in binary DMF+water mixtures. UV-vis absorption spectra of PAR solution were recorded in the course of pH-metric titration of acidic solutions of PAR with standard base solution. The protolytic equilibrium constants, spectral profiles, concentration diagrams and also the number of components have been calculated from the fitting of the pH-spectral titration data with appropriate mass balance equations by a home written program according to an established target factor analysis. To precise determination of number of absorptive components a recently developed statistical indicator function (IND function) was used. A glass electrode calibration procedure based on a four-parameter equation [Formula: see text] based on the Gran's plots was used to obtain pH readings in the concentration scale (p(c)H). It has been observed that there is an inverse relationship between second and third protolytic constants and mole fraction of DMF. The effect of the solvent on the protolytic constants was discussed.

Thermodynamic characterization of the dimerization equilibrium of an asymmetric dye by spectral titration and chemometric analysis.

The monomer-dimer equilibrium of an asymmetric cyanine dye has been investigated by means of UV-Vis spectroscopy. The data have been processed by a recently developed chemometric method for quantitative analysis of undefined mixtures, that is based on simultaneous resolution of the overlapping bands in the whole set of absorption. In this work the dimerization constant of 1-carboxydecyl-4-{3-[3-methyl-3H-benzothiazol-2-ylidene]-propenyl}-quinolinium (TO-3) has been determined by studying the dependence of absorption spectrum on temperature in the range 25-72.5 degrees C at different total concentrations of dye (8.5x10(-6) to 2.87x10(-5)M). Utilizing the van't Hoff relation, which describes the dependence of the equilibrium constant on temperature, as constraint we determine the spectral responses of the monomer and dimer species as well as the enthalpy and entropy of the dimerization equilibrium.

beta-Correction as a preprocessing method for partial least squares in simultaneous determination of zinc and lead.

An error analysis of predicted values using spectral correction matrix and partial least squares (PLS) modeling is applied for the determination of Zn(2+) and Pb(2+) with methylthymol blue (MTB) as a metallochromic indicator. The concentration ranges for Pb(2+) and Zn(2+) in standard solution sets are 0.5-5.2 and 0.1-2.5mugml(-1), respectively. The experimental calibration set was composed of 20 sample solutions using a random design for two component mixtures. The absorption spectra were recorded from 400 to 700nm. The two wavelengths, which exert the minimum error in prediction of two metal ion concentrations, are chosen according to an error analysis of different pairs of wavelengths. The effect of the pH on the sensitivity in determination of Zn(2+) and Pb(2+) using MTB was studied in order to choose the optimum pH (pH=6) for determination. The values of root mean square difference (RMSD) for lead and zinc using beta-correction partial least squares were 0.0977 and 0.1266, respectively. The effect of diverse ions and several experimental parameters were studied. The method was used for the determination of lead and zinc in alloy samples.

Kinetic spectrophotometric determination of thiocyanate based on its inhibitory effect on the oxidation of methyl red by bromate.

A kinetic spectrophotometric method for measuring thiocyanate is described. The proposed method is based on the inhibitory effect of thiocyanate on the oxidation of Methyl Red by bromate in the presence of nitrite, which was monitored at 520 nm. The variables affecting the rate of the reaction were investigated and the optimum conditions were established. Thiocyanate can be measured in the range of 0.05-1.1 microg ml(-1) with a detection limit of 0.025 microg ml(-1). This method has been used to determine trace thiocyanate in urine and tap water samples.

A potentiometeric study of protonation and complex formation of xylenol orange with alkaline earth and aluminum ions.

Xylenol orange (XO) is one of the complexometric indicators, that can bind to metal cations at both their amino and acidic groups. In this study the protonation constants and distribution diagrams of XO were studied pH-metrically, and the corresponding six protonation constants were calculated. The complex formation between XO (L) and alkaline earth ions (M) was investigated and the formation constants of the resulting complexes ML, MHL, M(2)L and M(2)HL were determined. The stabilities of both ML and M(2)L complexes were found to vary in the order Mg(2+)> Ca(2+)> Sr(2+)> Ba(2+). Studying the complex formation between Al(3+) ion (M) and XO (L), it was observed that four complexed species with stoichiometries ML, ML(2), MHL and MH(2)L could be formed in solution. It was also found that the Al L(2) complex can act as a chelating agent for further complexation with two cations other than Al(3+) ion (i.e. Ba, L, Al, L, Ba, Mg, L, Al, L, Mg, and Mg, L, Al, L, Ba). The formation constants of the resulting mixed complexes were determined and their distribution diagrams were investigated.

Spectrophotometric determination of acidity constants of some anthraquinones and anthrones in methanol-water mixtures.

The acidity constants of some synthetic derivatives of 9,10-anthraquinone and 9-anthrone in methanol-water mixtures at 25 degrees have been determined spectrophotometrically. A linear reverse relationship is observed between pK(a1) of all acids and the mole fraction of methanol. The influence of substituents in the molecular structure on the ionization constants is discussed.