Redox behavior of juglone in buffered aq.: Ethanol media

The present work reports the redox mechanism of 5-hydroxynaphthalene-1,4-dione (HND), commonly known as juglone, in buffered aqueous media having 50% of ethanol. HND followed different mechanistic routes depending upon the pH of the media and more than one pK_a were evaluated from the changes in the slope of the E_p vs. pH plot. The change of pH from acidic to neutral conditions was found to switch the mechanism from CEC to EE mechanism. Pulse techniques were utilized to determine the number of electrons involved in the oxidation and/or the reduction step and to ensure the nature of the redox process. Based upon the obtained results, an electrode reaction mechanism was proposed. Computational studies of HND supported the experimental results. UV-Visible spectroscopy was also employed for the detailed characterization of the compound in a wide range of pH and for the determination of its pK_a.     

Catalytic Chain-Transfer in Polymerization of Methyl Methacrylate. I. Chain-Length Dependence of Chain-Transfer Coefficient

Free-radical polymerization of methyl methacrylate has been conducted in the presence of a new catalytic chain-transfer agent at different temperatures. The new catalyst exhibits a strong chain transfer characteristic, and the chain-transfer coefficient varies from 2.8 × 10⁴ to 6.6 × 10⁴ and depends on chain length and temperature. The chain-transfer coefficients decrease with increasing chain length but reach a limiting value for chains more than 8 units in length. The activation energy for the chain transfer coefficient is -10.1 kJ/mol for this catalyst.     

A Convenient Synthesis of β-Amino Acid

We have reported the reductive cleavage of azlactones¹ and phenylhydrazones² of carbonyl compounds in the presence of a suitable catalyst. In this paper a general method involving a one step synthesis of β-amino acid^3,4, in good yield, through catalytic reduction of oximes of α-β-unsaturated acid is reported. This method involves the reaction of α, β-unsaturated acid with hydroxylamine hydrochloride in the presence of sodium acetate. Markovnikov's rule is followed in the synthesis of oximes of α, β-unsaturated acids.     

A technique for evaluating the oil/heavy-oil viscosity changes under ultrasound in a simulated porous medium

Theoretically, Ultrasound method is an economical and environmentally friendly or “green” technology, which has been of interest for more than six decades for the purpose of enhancement of oil/heavy-oil production. However, in spite of many studies, questions about the effective mechanisms causing increase in oil recovery still existed. In addition, the majority of the mechanisms mentioned in the previous studies are theoretical or speculative. One of the changes that could be recognized in the fluid properties is viscosity reduction due to radiation of ultrasound waves. In this study, a technique was developed to investigate directly the effect of ultrasonic waves (different frequencies of 25, 40, 68 kHz and powers of 100, 250, 500 W) on viscosity changes of three types of oil (Paraffin oil, Synthetic oil, and Kerosene) and a Brine sample. The viscosity calculations in the smooth capillary tube were based on the mathematical models developed from the Poiseuille’s equation. The experiments were carried out for uncontrolled and controlled temperature conditions. It was observed that the viscosity of all the liquids was decreased under ultrasound in all the experiments. This reduction was more significant for uncontrolled temperature condition cases. However, the reduction in viscosity under ultrasound was higher for lighter liquids compare to heavier ones. Pressure difference was diminished by decreasing in the fluid viscosity in all the cases which increases fluid flow ability, which in turn aids to higher oil recovery in enhanced oil recovery (EOR) operations. Higher ultrasound power showed higher liquid viscosity reduction in all the cases. Higher ultrasound frequency revealed higher and lower viscosity reduction for uncontrolled and controlled temperature condition experiments, respectively. In other words, the reduction in viscosity was inversely proportional to increasing the frequency in temperature controlled experiments. It was concluded that cavitation, heat generation, and viscosity reduction are three of the promising mechanisms causing increase in oil recovery under ultrasound.     

Hysteresis of two interacting magnetic pairs with inequivalent perpendicular anisotropy

We consider a model for magnetic memory that consists of strongly coupled dipolar or antiferromagnetic (AF) pairs with inequivalent perpendicular anisotropy _K1$K_1$ and _K2$K_2$. For appropriate parameter values, determined in this work, they have two inequivalent storage states with zero net magnetic moment. Both analytical and numerical calculations are performed, in some cases yielding different results because of relaxation effects (i.e., a dependence on the damping parameter α$\alpha$). Hysteresis loops for a wide variety of parameter values are obtained, both for the AF case and the dipole case. An Appendix gives analytic results for slightly non-collinear spins in an applied field, which were used to test the numerical results.     

Structural,magnetic and electrical properties of Co1−xZnxFe2O4 synthesized by co-precipitation method

Nanoparticles of Co_1−xZn_xFe₂O₄ with stoichiometric proportion (x) varying from 0.0 to 0.6 were prepared by the chemical co-precipitation method. The samples were sintered at 600 °C for 2 h and were characterized by X-ray diffraction (XRD), low field AC magnetic susceptibility, DC electrical resistivity and dielectric constant measurements. From the analysis of XRD patterns, the nanocrystalline ferrite had been obtained at pH=12.5–13 and reaction time of 45 min. The particle size was calculated from the most intense peak (3 1 1) using the Scherrer formula. The size of precipitated particles lies within the range 12–16 nm, obtained at reaction temperature of 70 °C. The Curie temperature was obtained from AC magnetic susceptibility measurements in the range 77–850 K. It is observed that Curie temperature decreases with the increase of Zn concentration. DC electrical resistivity measurements were carried out by two-probe method from 370 to 580 K. Temperature-dependent DC electrical resistivity decreases with increase in temperature ensuring the semiconductor nature of the samples. DC electrical resistivity results are discussed in terms of polaron hopping model. Activation energy calculated from the DC electrical resistivity versus temperature for all the samples ranges from 0.658 to 0.849 eV. The drift mobility increases by increasing temperature due to decrease in DC electrical resisitivity. The dielectric constants are studied as a function of frequency in the range 100 Hz–1 MHz at room temperature. The dielectric constant decreases with increasing frequency for all the samples and follow the Maxwell–Wagner's interfacial polarization.     

Studies of Hindered Rotation and Magnetic Anisotropy by 1H, 13C and 19F NMR. The Diels-Alder Adduct of N- Pentafluorophenylmaleimide and Phencyclone: A Model for Drugs.

The potent Diels-Alder diene, phencyclone, 1, reacts with N-pentafluorophenylmaleimide, 2, to form an adduct, 3, characterized by ¹H, ¹³C, and ¹⁹F NMR at 300, 75 and 282 MHz, respectively. The one-dimensional (1D) and two-dimensional (2D) ¹H and ¹³C NMR spectra of 3 at ambient temperatures imply a slow exchange limit (SEL) regime with respect to rotation of the unsubstituted bridgehead phenyl groups about severely hindered C(sp²)-C(sp³) bonds. Major non-bonded interactions are expected between the ortho protons of the C₆H₅ groups and H-1, 8 of the phenanthrenoid moiety of 3. ¹⁹F 1D and 2D (COSY) NMR spectra show that the SEL regime also obtains for rotation about the N-C₆F₅ bond of 3, with five separate fluorine signals seen, consistent with a preferred conformation in which the C₆F₅ may lie roughly perpendicular to the plane of the pyrrolidinedione moiety, and may be in the mirror symmetry plane of 3. The results are considered relevant to hindered aryl rotations in numerous Pharmaceuticals. Selected spectral data for 2 and precursors are also presented.     

Physical and Rheological Characteristics of Emulsion Model Structures Containing Iranian Tragacanth Gum and Oleic Acid

The physical and rheological properties of oil in water model emulsion systems containing Iranian tragacanth gum (TG) (0.5, 1 g/100 ml emulsions), whey protein isolate (WPI) (2, 4 g/100 ml emulsions), and oleic acid (5, 10 ml/100 ml emulsions) were investigated for droplet-size distribution, creaming index, and rheological properties of emulsions. The shear-thinning behavior of all dispersions was modeled using power law, Cross, and Ellis models. The power law model described the flow behavior of dispersions for its lowest standard error (0.29) and highest determination coefficient (R²) (0.99). Rheological investigation showed that both loss (G″) and storage (G′) modules increased as gum and oil content increased. Delta degree was 0.1 and increased as frequency increased, indicating that liquid-like viscose behavior dominated solid-like elastic behavior. Droplet-size distribution was measured by light scattering and microscopic observations revealed a flocculated system. Gum, WPI, and oil contents decreased the emulsion creaming index with gum concentration having the greatest effect.     

Forward ion-exchange kinetics of heavy metal ions on the surface of carboxymethyl cellulose Sn(IV) phosphate composite nano-rod-like cation exchanger

The Nernst?CPlanck equations with some additional assumptions was used in this study to investigate the forward kinetics and ion-exchange mechanism of heavy metal ions viz. Ni²⁺?CH⁺, Cu²⁺?CH⁺, Mn²⁺?CH⁺ and Zn²⁺?CH⁺ on the surface of carboxymethyl cellulose Sn(IV) phosphate composite nano-rod-like cation-exchanger. It was observed that heavy metals' exchange processes were imparted by the particle diffusion-controlled phenomenon. Some physical parameters i.e., fractional attainment of equilibrium U(??), self-diffusion coefficients (D _o), energy of activation (E _a), and entropy of activation (??S*) were estimated. These investigations revealed that the equilibrium is attained faster at higher temperature probably because of availability of thermally enlarged matrix of carboxymethyl cellulose Sn(IV) phosphate composite nano-rod-like cation-exchange material. The physical parameters observed for this composite cation exchanger were also compared with other composite ion exchangers. The results showed that the ion-exchange phenomenon is more feasible on the surface of this composite cation exchanger as compared with the other ion exchangers which indicated the usefulness of this composite ion exchanger in various applications.