Electrooxidation of dextromethorphan on a carbon nanotube–carbon microparticle–ionic liquid composite: applied to determination in pharmaceutical forms

The electrooxidation of dextromethorphan on a composite constructed with carbon nanotube–ionic liquid–carbon microparticles was investigated by cyclic voltammetry in a 100 mM phosphate buffer solution, pH 7.40. In the voltammograms, an irreversible diffusion-controlled anodic peak appeared. The diffusion coefficient of dextromethorphan, the electron-transfer coefficient, and the standard rate constant of the electrooxidation process were found to be 3.45?×?10^?6 cm² s^?1, 0.65, and 1.67?×?10^?3 cm s^?1, respectively. A sensitive and timesaving determination procedure was developed for the analysis of dextromethorphan, and the corresponding analytical parameters were reported. Using this method, dextromethorphan was determined with an LOD and LOQ of 8.81 and 29.36 μM in a linear range of 2.5?×?10^?4 to 3.3?×?10^?3 M, respectively. The proposed amperometric method was successfully applied to the analysis of commercial pharmaceutical products (syrup and oral drop), and the results were in good agreement with the declared values.     

<Emphasis Type="Italic">o</Emphasis>-Phenylenediamine as a New Catalyst in the Highly Regioselective Conversion of Epoxides to Halohydrins with Elemental Halogens

Summary. The regioselective ring opening of epoxides using elemental iodine and bromine in the presence of o-phenylenediamine as a new catalyst affords vicinal iodo alcohols and bromo alcohols in high yields. The major advantages of this method are versatility, high regioselectivity, a cheap and commercially available catalyst, mild and neutral reaction conditions, and short reaction times. Fourier transform Raman spectroscopy was used to study the reaction of iodine with o-phenylenediamine. The results indicate that the complex [(Diamine)I]⁺·I₅^– is formed, and we suggest that the major nucleophile is the pentaiodide ion. This bulky nucleophile has a fundamental role in the high regioselectivity observed attacking the less sterically hindered epoxide carbon.     

Photoinduced carbene generation from diazirine modified task specific phosphonium salts to prepare robust hydrophobic coatings

3-Aryl-3-(trifluormethyl)diazirine functionalized highly fluorinated phosphonium salts (HFPS) were synthesized, characterized, and utilized as photoinduced carbene precursors for covalent attachment of the HFPS onto cotton/paper to impart hydrophobicity to these surfaces. Irradiation of cotton and paper, as proof of concept substrates, treated with the diazirine-HFPS leads to robust hydrophobic cotton and paper surfaces with antiwetting properties, whereas the corresponding control samples absorb water readily. The contact angles of water were determined to be 139° and 137° for cotton and paper, respectively. In contrast, water placed on the untreated or the control samples (those treated with the diazirine-HFPS but not irradiated) is simply absorbed into the surface. Additionaly, the chemically grafted hydrophobic coating showed high durability toward wash cycles and sonication in organic solvents. Because of the mode of activation to covalently tether the hydrophobic coating, it is amenable to photopatterning, which was demonstrated macroscopically.     

Oxidation and determination of Gabapentin on nanotubes of nickel oxide-modified carbon paste electrode

The electrooxidation of Gabapentin was studied on nanotubes of nickel oxide-modified carbon paste electrode for the first time. Cyclic voltammetry was employed to investigate the electrooxidation process. A simple, sensitive, and efficient amperometric method was developed for the analysis of the drug, and the corresponding analytical parameters were reported. For Gabapentin, a detection limit of 0.3 μM was obtained in a linear range of 2.4–50 μM. The proposed amperometric method was also applied to the analysis of commercial capsules, and the results were in good agreement with the declared values. Also, the applicability of the method to the direct assay of the drug in human serum and urine was described.     

The quantum chemical calculation of NMR two-bond spin–spin coupling constants in the N?···H–OH?→?N–H···OH? switching

A quantum chemical study has been carried out to investigate the effects of the size of H₂O cluster and substituents (X = H, Me, OMe, CHO, NO, and NO₂) in the para position of the anilide ion on the two-bond spin–spin coupling constants (SSCCs) ^2h J _N···O across in the N–H–O switching at B3LYP/6-311 ++G(2d,2p) level of theory. The changes in ^2h J _N···O SSCCs due to variation of substituent and H₂O cluster size were well monitored by changes in binding energy, structural parameter, electron density topography, natural charge, charge transfer, and percentage of p-character of N atom in the C–N bond. Linear correlations were found between ^2h J _N···O and above-mentioned properties.     

The Different,but Interesting Behaviors of Benzyl Systems in the Willgerodt-Kindler Reaction under Solvent-Free Conditions

On the benzyl system, bearing various functional groups, have been carried out the Willgerodt-Kindler reaction to obtain thiobenzmorpholide ( 1 ). The reactions, under solvent-free conditions, were performed in both classical (reflux, room temperature) and nonclassical (microwave) conditions to attempt our elucidation of the reactions pathways. Unlike benzylamine and benzyl mercaptan, benzyl halides give poor result due to the type of amine. The experimental results suggest that the proposed reaction pathway involves the oxidation coupling of benzylic substrates, followed by a thiolation step and an attack of the amine on the thiolated product to give ( 1 ).     

Microwave Thermolysis: A Rapid and Selective Method for the Cleavage of THP Ethers Using CrO 3 Supported onto Zeolite in Solventless System

Oxidative deprotection of tetrahydropyranyl ethers (THP ethers) using chromium trioxide supported onto zeolite under microwave irradiation in solvent free condition is described.     

FACILE REDUCTION OF AROMATIC NITRO COMPOUNDS WITH HYDROIODIC ACID UNDER MICROWAVE IRRADIATION ON SOLID SUPPORT

Reduction of aromatic nitro compounds to amine with hydroiodic acid was revisited. Under microwave irradiation on solid support the reduction proceeded efficiently and rapidly.