Electrochemical Derivatization of Acetaminophen for Indirect Determination of Eflornithine Using β‐CD Modified Glassy Carbon Electrode

In the present work, the oxidation of acetaminophen in the absence and presence of eflornithine was electrochemically investigated by means of cyclic voltammetry at a glassy carbon electrode (GCE). Our results indicate that N‐acetyl‐p‐benzoquinone imine (NAPQI) produced from two‐electron electrochemical oxidation of acetaminophen participates in a Michael addition reaction with eflornithine via an ECE mechanism. This fact was used for the determination of eflornithine using differential pulse voltammetry (DPV) technique on the surface of β‐Cyclodextrin modified glassy carbon (β‐CD/GC) electrode. β‐CD/GC electrode was prepared through an electrodeposition procedure and characterized by Fourier‐transform infrared spectroscopy (FT‐IR), Cyclic Voltammetry (CV), Field Emission Scanning Electron Microscopy (FESEM) and Energy‐dispersive X‐ray spectroscopy (EDS) techniques. Under optimum conditions, the β‐CD/GC electrode showed a good linearity as a function of the eflornithine concentration over the range from 5 to 100 μM with detection limit and quantification limit of 1.94 and 5.8 μM, respectively. Finally, the proposed protocol was confirmed to be successful in determination of eflornithine in human urine samples with good recovery, ranging from 97.2 % to 104.8 %.     

Study of the chemical structure and their nematicidal activity of N2O2 tetradentate Schiff base metal complexes

Coordination compounds of Cu (II), Y (III), Zr (IV) and La (III) with the tetradentate Schiff base (H₂L) obtained through the condensation of p‐phenylenediamine with salicylaldehyde under reflux conditions. The complexes were characterized by elemental analysis, magnetic susceptibility, molar conductance and also, with various spectroscopic techniques such as ¹H NMR, UV–Vis., IR and XRD techniques. Electrolytic nature of complexes was ascertained by molar conductance values. In these four complexes, the ligand chelates act in a tetradentate manner via azomethine nitrogen and oxygen atoms of phenolic groups. Electronic spectroscopic data are in agreement with an octahedral geometrical structure. Thermal degradation analyses in nitrogen gas were used to investigate the number and location of water molecules. The chemical formulae of metal complexes were confirmed by microanalytical data. The activation thermodynamic parameters, such as, E^*, ΔH^*, ΔS^* and ΔG^* were calculated from the DTG curves using Coats Redfern (CR) and Horowitz–Metzeger (HM) methods at n = 1 or n ≠ 1. Nematicidal activities indicate that the ligand exhibit greater activity when compared to its complexes. In addition metal complexes displayed good moderate nematicidal activities.     

Fast and Efficient Nitration of Salicylic Acid and Some Other Aromatic Compounds over H_3PO_4/TiO_2-ZrO_2 Using Nitric Acid

TiO₂‐ZrO₂ (1/1)‐surf with Ti and Zr molar ratio of 1/1 was prepared with surfactant through a sol‐gel method. The optimum experimental condition was investigated for nitration of salicylic acid. Then, a number of nitration reactions were carried out with a variety of aromatic compounds in the optimum condition. The 25 wt% H₃PO₄/TiO₂‐ZrO₂ (1/1)‐surf catalyst showed good selectivity and yield in a short time for the nitration of salicylic acid and some other aromatic compounds.     

Polymeric membrane coated graphite cesium selective electrode based on 4′,4″(5′) di–tert-butyl di-benzo-18-crown-6

A new PVC membrane coated graphite electrode for cesium ion based on 4′,4″(5′)di–tert-butyl di-benzo-18-crown-6 (DTBDB18C6) as ionophore was prepared. The electrode shows a near Nernstian response of 57.0 ± 1.8 mV decade^?1 over a wide activity range of 6.0 × 10^?6–1.0 × 10^?1 mol L^?1 with a limit of detection 4.0 × 10^?6 mol L^?1. The proposed electrode is suitable for use in aqueous solution in the pH range of 3.0–9.5. It has a fast response time of 10 s and can be used for at least 1 month without any considerable divergence in potential. The selectivity coefficients for Cs⁺ ion with respect to ammonium, alkali, alkaline earth and some selected transition metal ions were determined and showed a superior selectivity over Li⁺, Na⁺ and alkaline earth metal ions. The new electrode was applied for determination of Cs⁺ in spiked tap water. The electrode was also used as indicator electrode in potentiometric titration of Cs⁺ with sodium tetraphenyl borate.     

Assessing soil pollution from a municipal waste dump in Islamabad, Pakistan: a study by INAA and AAS

INAA and AAS techniques have been employed to determine 40 elements in soil of a municipal waste dump in sector H-11, Islamabad. Background soil was also analyzed to study the extent of contamination of the dump site soil. Most of the major elements in these soils represented the geochemical composition of the soil in this area. The enrichment factors for quantified elements identified high Sb and Mg contents that could be attributed to the presence of PET and food materials in the waste. Geo-accumulation Index (I _geo), Pollution Index (PI) and the Integrated Pollution Index (IPI) have also been calculated for all elements. The values for these indices show that municipal waste has distorted the soil ambiance and the soil of waste dump site is slightly to moderately polluted as compared to the background soil. The dump soil was found to be moderately polluted by the elements Ba, Br, Ga, Rb, Zn, Ni and Pb. Significantly high Cu, Mg and Sb contamination was observed for the waste soil that is likely to pose an environmental issue if current waste disposal procedures are continuously employed.     

A new approach to the reduction of sulfoxides to sulfides with 1,3-dithiane in the presence of electrophilic bromine as catalyst

A new, mild, and novel method is described for the efficient deoxygenation of sulfoxides to their corresponding sulfides with 1,3-dithiane at room temperature in the presence of catalytic amounts of N-bromosuccinimide (NBS), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TABCO), or Br(2) as the source of electrophilic bromine.     

1H NMR Study of Hindered Internal Rotation of Tetramethylthiuram Disulfide in Binary Dimethyl Sulfoxide‐Chloroform Mixtures

Hindered internal rotation about the C‐N single bonds joining the thiuram disulfide was studied by ¹H NMR complete line‐shaped analysis in different dimethyl sulfoxide‐chloroform (DMSO‐CDCl₃) mixtures. From the temperature dependence of methyls proton spectra, activation parameters (E_a, ΔH^≠, ΔS^≠, and ΔG^≠) were obtained. The Arrhenius plots showed a distinct isokinetic temperature at about 35 °C at which the exchange rate is more or less independent of the solvent composition. The resulting ΔH^≠ against TΔS^≠ plot showed a firmly good linear correlation, indicating the existence of an enthalpy‐entropy composition in an exchange process.     

Kinetic Spectrophotometric Determination of Trace Amounts of Nitrite by Catalytic Reaction between Methylthymol Blue and Bromate

A kinetic spectrophotometric method for determination of trace nitrite in two dynamic ranges (2–100 and 100–500 ng/mL) based on its catalytic effect on the reaction between methylthymol blue and potassium bromate in acidic (sulfuric acid) media is described. The reaction was monitored spectrophotometrically by measuring the decreasing color of methylthymol blue at 437 nm by the fixed‐time method of 4.0 min at 30°C. The detection limit is 0.6 ng/mL, and the relative standard deviations for 50.0 and 250.0 ng/mL nitrite are 1.6% and 1.3%, respectively. The method was used for the determination of nitrite in water samples.     

Modified carrageenan. 5. Preparation,swelling behavior,salt‐ and pH‐sensitivity of partially hydrolyzed crosslinked carrageenan‐graft‐polymethacrylamide superabsorbent hydrogel

The polysaccharide, kappa‐carrageenan (κC) was chemically modified to achieve a novel superabsorbent hydrogel via graft copolymerization of methacrylamide (MAM) onto the substrate followed by alkaline hydrolysis. Ammonium persulfate (APS) and N,N′‐methylene bisacrylamide (MBA) were used as a free‐radical initiator and a crosslinker, respectively. The saponification reaction was carried out using sodium hydroxide aqueous solution. Either κC‐g‐PMAM or hydrolyzed κC‐g‐PMAM (PMAM: polymethacrylamide) was characterized by FT‐IR spectroscopy. The effect of grafting variables (i.e. concentration of MBA, MAM, and APS) and alkaline hydrolysis conditions (i.e. NaOH concentration, hydrolysis time and temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. The swelling capacity of these hydrogels was also measured in various salt solutions. Results indicated that the swelling ratios decreased with an increase in the ionic strength of the salt solutions. This behavior can be attributed to charge screening effect for monovalent cations, as well as ionic crosslinking for multivalent cations. Absorbency of superabsorbing hydrogels was examined in buffer solutions with pH range 1–13. Also, the pH reversibility and on–off switching behavior, at pH values 3.0 and 8.0, makes the synthesized hydrogels good candidates for controlled delivery of bioactive agents. Finally, swelling kinetics in distilled water and various salt solutions was preliminary investigated. Results showed that the swelling in water was faster than in saline solutions. Copyright © 2004 John Wiley & Sons, Ltd.