A Facile Strategy for Construction of Sensor for Detection of Ondansetron and Investigation of its Redox Behavior and Thermodynamic Parameters

A sodium dodecylsulfate‐doped polypyrrole (SDS‐PPy) film was elaborated on glassy carbon electrode (GCE) by an electrodeposition method in phosphate buffer solution (pH 2.0) containing pyrrole (Py) and sodium dodecyl sulfate (SDS). SDS‐PPy/GCE was used for the construction of sensor, which showed excellent electrochemical response for the detection of ondansetron (OND) compared to conventional PPy. The application of the square wave (SW), with the adsorptive accumulation, indicates a maximum response at 1.33 V in H₂SO₄ (0.5 M). The influence of experimental parameters on determination of OND is discussed. The adsorptive stripping technique showed to be more sensitive, giving responses twice as big as those of non‐accumulated OND. The substantial improvement of response permits the development of an electroanalytical technique with a linear concentration in the range (1.0–80 μM), low detection (0.09 μM), and quantification limits (0.3 μM), and acceptable relative standard deviations of repeatability (0.59 %), and reproducibility (1.51 %). Consequently, this electrode is promising candidate for an accurate electroanalytical determination of OND in pharmaceutical samples with high sensitivity and selectivity, good accuracy and precision. The electrooxidation of OND at SDS‐PPy/GCE at various temperatures were studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔG*, ΔH* and ΔS*) parameters.     

Oxidative polymerization of diphenylamine-2-carboxylic acid: Synthesis, structure, and properties of polymers

Polymers of diphenylamine-2-carboxylic acid are synthesized for the first time via chemical oxidative polymerization. The effects of the concentration of reagents, their ratio, and the temperature and time of reaction on the yield and chemical structure of poly(diphenylamine-2-carboxylic acid) are studied by IR and UV spectroscopy. It is shown that the growth of polymer chains proceeds through the C-C addition in the para position of phenyl rings relative to nitrogen. During the thermal oxidation of poly(diphenylamine-2-carboxylic acid), COOH groups and dopant molecules are successively eliminated; with a further increase in temperature, the polymer behaves as polydiphenylamine. The main processes of thermooxidative degradation of poly(diphenylamine-2-carboxylic acid) begin at 570°C. This value is 120°C higher than the corresponding parameter in the case of polydiphenylamine.     

Determination of the critical surface tension of wetting of minerals treated with surfactants by shear flocculation approach

This paper contributes the shear flocculation method as a new approach to determine the critical surface tension of wetting of minerals treated with surfactants. This newly developed approach is based on the decrease of the shear flocculation of the mineral suspension, with decreasing of the surface tension of the liquids used. The solution surface tension value at which shear flocculation does not occur can be defined as the critical surface tension of wetting (gamma c) of the mineral. By using the shear flocculation method, the critical surface tensions of wetting (gamma c) for calcite and barite minerals, treated with surfactants, were obtained as 30.9 and 35.0 mN/m, respectively. These values are in good agreement with data reported previously on the same minerals obtained by the contact angle measurement and flotation methods. The chemical agents used for the treatment of calcite and barite particles were sodium oleate and sodium dodecyl sulfate, respectively.     

New Methacrylate Copolymers Based on the Benzofurane Ring: Synthesis,Characterization, Monomer Reactivity Ratios and Biological Activity

The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, ¹H-NMR, ¹³C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi.     

A Ready‐to‐Use Electrochemical Kit Design for the Diagnosis of Single Nucleotide Polymorphisms

In this study, for the first time a model electrochemical kit was constructed for the detection of a functional polymorphism in catechol‐O‐methyl transferase (COMT) gene which is important for diagnosis of neuropsychiatric disorders as Alzheimer disease. The disposable pencil graphite electrode (PGE) is designed as a “kit” and the probe DNA covered PGE can detect single nucleotide polymorphisms (SNPs) from real samples based on the guanine oxidation signal even after 5 months of kit preparation (150 days durability).The detection limit (S/N=3) of the biosensor was calculated as 1.18 pmol of synthetic target sequence and 6.09×10⁵ molecules of real samples in 30 min detection time.     

Separation of brombuterol enantiomers in capillary electrophoresis with cyclodextrin‐type chiral selectors and investigation of structure of selector‐selectand complexes using nuclear magnetic resonance spectroscopy

The major goal of this study was to determine the affinity pattern of brombuterol (BB) enantiomers toward various cyclodextrins (CD) and to evaluate the potential of NMR spectroscopy for understanding fine mechanisms of interactions between CDs and BB enantiomers. Separation of BB enantiomers was performed in a fused‐silica capillary using a phosphate buffer, pH 2.5, at the room temperature in the normal polarity mode. It was shown once again that CE in combination with NMR spectroscopy represents a very sensitive tool for studies of affinity patterns and structure of CD complexes with chiral guests. Although opposite affinity patterns of BB enantiomers were observed toward native β‐ and γ‐CDs, no significant differences between the structures of the complexes of these two CDs with BB were detected by NMR spectroscopy. In contrary to this, the opposite affinity pattern of BB enantiomers toward β‐CD and its two sulfated derivatives, heptakis (2,3‐O‐diacetyl‐6‐sulfo)‐β‐CD (HDAS‐β‐CD) and heptakis (2‐O‐methyl‐3,6‐di‐O‐sulfo)‐β‐CD (HMDS‐β‐CD) was associated with major differences in the structure of the complexes. In addition, it was shown again that HMDS‐β‐CD provides separation of enantiomers without formation of inclusion‐type complex with the chiral analyte.     

A Sensitive and Selective RP-LC Method for the Simultaneous Determination of the Antihypertensive Drugs,Enalapril, Lercanidipine,Nitrendipine and Their Validation

A RP-LC method is presented, which is sensitive and selective for the simultaneous determination of enalapril–lercanidipine and enalapril–nitrendipine binary mixtures in their pharmaceutical dosage forms. The analyte peaks were detected using the LC method with the mobile phase ratio of methanol: water (70:30 v/v, pH 3.0) and a 1.0 mL min⁻¹ flow rate. The detection wavelength was selected at 210 nm using photo diode array detector and column temperature was optimized to 30 °C. Linearity was obtained at different concentration ranges for all working pharmaceutically active compounds between 0.5 and 25 μg mL⁻¹. The proposed methods were extensively validated according to USP 27 requirements and ICH guidelines. The methods were applied to the analysis of pharmaceutical dosage forms containing binary mixtures of enalapril–lercanidipine and enalapril–nitrendipine. Moreover, the proposed methods were applied for the degradation studies of the selected compounds. Degradation studies were conducted using stress conditions such as UV light, acidic and alkaline hydrolysis, oxidation and heat in oven, to evaluate the ability of the separation of the response of standard compounds from their degradation products.

     

Reactions of 1S, 1D,and 3P carbon atoms with water. Oxygen abstraction and intermolecular formaldehyde generation mechanisms; An MCSCF study

Reactions of singlet and triplet carbon atoms with water are explored theoretically using CASSCF–MCQDPT2, CCSD, and DFT methodologies. The ¹S carbons are found to be unreactive. Depending on the carbon atom generation method and the reaction medium, gas‐phase C(³P) attacking water may generate CO and atomic hydrogen as the end products. Reaction paths of the C(¹D) + H₂O system are complicated due to the involvement of two reactive potential energy surfaces with branchings occurring along each. Modifications in product distributions for reactions taking place in condensed phases are elaborated. The decisive reaction conditions, under which the oxygen abstraction and intermolecular formaldehyde generation dominate, are suggested to clarify the discrepancy related with experimental CO observation. The findings are consistent with available experimental data on this system. Oxygen abstraction and intermolecular formaldehyde generation mechanisms suggested here are capable of serving as models for similar reactions of alcohols. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012