Effective removal of 4-Aminophenol from aqueous environment by pea (Pisum sativum) shells activated with sulfuric acid: Characterization,isotherm, kinetics and thermodynamics

The threat of phenol contamination in aquatic ecosystems is significant for the health of the earth's water systems as well as all humans on it. The present study was conducted to synthesize a cost-effective adsorbent (pea shells activated with sulfuric acid, PSASA) from agriculture waste (pea shells) and its use for effective removal of toxic 4-Aminophenol (4-AP). Newly designed PSASA exhibited significant adsorption of 4-AP which was confirmed by SEM, FT-IR, and XRD analysis. Surface topography confirmed high unevenness of the PSASA surface and the macroporous feature of the PSASA was confirmed by BET analysis. . Multiple testing was done to see how various factors affected adsorption such as adsorbent dose, temperature, pH, PZC, the effect of KCl and urea addition and the effect of the initial concentration of 4-AP. A drop in adsorption uptake of 4-AP was observed as the temperature increases from 25 °C to 45 °C. Maximum adsorption uptake (q_m) was found to be 106.11 mg/g at an optimum pH of 7.0 and 25 °C. Among various adsorption isotherm models tested, Langmuir Isotherm gave the best explanation with high R² values of experimental data. The pseudo-first-order model was found to explain the kinetics of adsorption well. The thermodynamic finding confirms the adsorption process was physical and exothermic. The adsorption of 4-AP was primarily governed by electrostatic interaction, hydrogen-bonding and π-π exchange mechanism. Because of the positive outcomes of the present research, we can use the PSASA as a cost-effective adsorbent for removing phenolic compounds.     

Synthesis and characterization of dimeric μ-oxidovanadium complexes as the functional model of vanadium bromoperoxidase

Two vanadium (IV) complexes [V^IVO(Haeae-sal)(MeOH)]⁺ ( 1 ) and [V^IVO(Haeae-hyap)(MeOH)]⁺ ( 2 ) were prepared by reacting [VO(acac)₂] with ligands [H₂aeae-sal] ( I ) and [H₂aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 10² h⁻¹) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 10² h⁻¹) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 10⁴ h⁻¹ whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 10³ h⁻¹ for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.     

The ABC of Insulin: The Organic Chemistry of a Small Protein

Insulin is a small protein crucial for regulating the blood glucose level in all animals. Since 1922 it has been used for the treatment of patients with diabetes. Despite consisting of just 51 amino acids, insulin contains 17 of the proteinogenic amino acids, A- and B-chains, three disulfide bridges, and it folds with 3 α-helices and a short β-sheet segment. Insulin associates into dimers and further into hexamers with stabilization by Zn²⁺ and phenolic ligands. Selective chemical modification of proteins is at the forefront of developments in chemical biology and biopharmaceuticals. Insulin's structure has made it amenable to organic and inorganic chemical reactions. This Review provides a synthetic organic chemistry perspective on this small protein. It gives an overview of key chemical and physico-chemical aspects of the insulin molecule, with a focus on chemoselective reactions. This includes N-acylations at the N-termini or at Lys^B29 by pH control, introduction of protecting groups on insulin, binding of metal ions, ligands to control the nano-scale assembly of insulin, and more.     

Quantitative estimations of bivariate summation‐integral–type operators

In this paper, we study the approximation properties of bivariate summation‐integral–type operators with two parameters . The present work deals within the polynomial weight space. The rate of convergence is obtained while the function belonging to the set of all continuous and bounded function defined on ([0],∞)(×[0],∞) and function belonging to the polynomial weight space with two parameters, also convergence properties, are studied. To know the asymptotic behavior of the proposed bivariate operators, we prove the Voronovskaya type theorem and show the graphical representation for the convergence of the bivariate operators, which is illustrated by graphics using Mathematica. Also with the help of Mathematica, we discuss the comparison by means of the convergence of the proposed bivariate summation‐integral–type operators and Szász‐Mirakjan‐Kantorovich operators for function of two variables with two parameters to the function. In the same direction, we compute the absolute numerical error for the bivariate operators by using Mathematica and is illustrated by tables and also the comparison takes place of the proposed bivariate operators with the bivariate Szász‐Mirakjan operators in the sense of absolute error, which is represented by table. At last, we study the simultaneous approximation for the first‐order partial derivative of the function.     

A Robust numerical approach for singularly perturbed time delayed parabolic partial differential equations

We consider the numerical solution of a initial boundary value problem with a time delay. The problem under consideration is singularly perturbed from the mathematical perspective. Assuming that the coefficients of the differential equation are smooth, we construct and analyze the finite difference method whose solutions converge pointwise at all points of the domain independently of the singular perturbation parameter. The method permits its extension to the case of adaptive meshes, which may be used to improve the solution. Numerical examples are presented to demonstrate the effectiveness of the method. The convergence obtained in practice satisfies the theoretical predictions.     

Long distance atomic teleportation with as good success as desired

Long distance atomic teleportation (LDAT) is of prime importance in long distance quantum communication. Scheme proposed by Bose et al. (1999) in principle enables us to have LDAT using cavity decay. However it gives message state dependent fidelity and success rate. Here, using interaction of entangled coherent states with atom–cavity systems and a two-step measurement, we show how, LDAT can be achieved with unit fidelity and as good success as desired under ideal conditions. The scheme is unique in that, the first measurement predicts success or failure. If success is predicted then second measurement gives perfect teleportation. If failure is predicted the message-qubit remains conserved therefore a second attempt may be started. We found that even in presence of decoherence due to dissipation of energy our scheme gives message state independent success rate and almost perfect teleportation in single attempt with mean fidelity of teleportation equal to 0.9 at long distances. However if first attempt fails, unlike ideal case where message-qubit remains conserved with unit fidelity, in presence of decoherence the message-qubit remains conserved to some degree, therefore mean fidelity of teleportation can be increased beyond 0.9 by repeating the process.     

An Efficient,Basic Resin-Mediated,One-Pot Synthesis of Dithiocarbazates Through Alcoholic Tosylates

A quick and efficient, one-pot synthesis of dithiocarbazates was accomplished in high yields by the reaction of various alcoholic tosylates of primary, secondary, and tertiary alcohols, with substituted hydrazines using an Amberlite IRA 400 (basic resin)/CS ₂ system. The reaction conditions are mild with simpler work-up procedures than previously reported methods.     

Kinetics of Polymerization of Methyl Methacrylate initiated by AIBN in the Presence of Acetophenone

The present investigation aims at estimating the retarding effect of acetophenone in the polymerization of methyl methacrylate initiated by α,α' -azobisisobutyronitrile in the temperature range of 50 to 80°C. The results are interpreted in terms of Tüdös kinetic parameter (β). The effects of varying concentrations of substrate, monomer, initiator, and salts have been investigated. A suitable reaction scheme and rate expression have been suggested on the basis of the experimental findings, and another kinetic parameter (K) to represent the reactivity of acetophenones toward the polymer radical has been obtained graphically.