Kinetics and mechanism of the reaction oftrans-cyclohexane-1,2-diamine-N N N' N'-tetra-acetatomanganate(III) with substituted thioureas in aqueous medium

Summary The kinetics of reduction of [Mn^III(cydta)]^– (where H₄cydta=trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5–4.5 and 9.2–10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the Mn^III complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects.     

Surfactant-promoted enhancement in bioremediation of hexavalent chromium to trivalent chromium by naturally occurring wall algae

Research on Chemical Intermediates - The discharge of hexavalent chromium [Cr(VI)] has resulted in significant pollution because of the presence of Cr(VI) oxyanions. They are highly water-soluble,...     

Recent advances in ZnO nanostructures and thin films for biosensor applications: Review

Biosensors have shown great potential for health care and environmental monitoring. The performance of biosensors depends on their components, among which the matrix material, i.e., the layer between the recognition layer of biomolecule and transducer, plays a crucial role in defining the stability, sensitivity and shelf-life of a biosensor. Recently, zinc oxide (ZnO) nanostructures and thin films have attracted much interest as materials for biosensors due to their biocompatibility, chemical stability, high isoelectric point, electrochemical activity, high electron mobility, ease of synthesis by diverse methods and high surface-to-volume ratio. ZnO nanostructures have shown the binding of biomolecules in desired orientations with improved conformation and high biological activity, resulting in enhanced sensing characteristics. Furthermore, compatibility with complementary metal oxide semiconductor technology for constructing integrated circuits makes ZnO nanostructures suitable candidate for future small integrated biosensor devices. This review highlights recent advances in various approaches towards synthesis of ZnO nanostructures and thin films and their applications in biosensor technology.     

A complete set of self‐consistent charge density‐functional tight‐binding parametrization of zinc chalcogenides (ZnX; X=O,S, Se,and Te)

We have developed a complete set of self‐consistent charge density‐functional tight‐binding parameters for Zn? X (X = Zn, O, S, Se, Te, Cd, H, C, and N). The transferability of the derived parameters has been tested against Pseudo Potential‐Perdew, Burke and Ernzerhof (PP‐PBE) calculations and experimental values (whenever available) for corresponding bulk systems (e.g., hexagonal close packing, zinc‐blende, and wurtzite(wz)), various kinds of nanostructures (such as nanowires, surfaces, and nanoclusters), and also some small molecular systems. Our results show that the derived parameters reproduce the structural and energetic properties of the above‐mentioned systems very well. With the derived parameter set, one can study zinc‐chalcogenide nanostructures of relatively large size which was otherwise prohibited by other methods. The Zn‐Cd parametrization developed in this article will help in studying large semiconductor hetero‐nanostructures of Zn and Cd chalcogenides such as ZnX/CdX core/shell nanoparticles, nanotubes, nanowires, and nanoalloys. © 2012 Wiley Periodicals, Inc.     

Optical and dielectric properties of isothermally crystallized nano-KNbO3 in Er3+-doped K2O–Nb2O5–SiO2 glasses

Precursor glass of composition 25K₂O–25Nb₂O₅–50SiO₂ (mol%) doped with Er₂O₃ (0.5 wt% in excess) was isothermally crystallized at 800 °C for 0–100 h to obtain transparent KNbO₃ nanostructured glass–ceramics. XRD, FESEM, TEM, FTIRRS, dielectric constant, refractive index, absorption and fluorescence measurements were carried out to analyze the morphology, dielectric, structure and optical properties of the glass–ceramics. The crystallite size of KNbO₃ estimated from XRD and TEM is found to vary in the range 7–23 nm. A steep rise in the dielectric constant of glass–ceramics with heat-treatment time reveals the formation of ferroelectric nanocrystalline KNbO₃ phase. The measured visible photoluminescence spectra have exhibited green emission transitions of ²H_11/2, ⁴S_3/2 → ⁴I_15/2 upon excitation at 377 nm (⁴I_15/2 → ⁴G_11/2) absorption band of Er³⁺ ions. The near infrared (NIR) emission transition ⁴I_13/2 → ⁴I_15/2 is detected around 1550 nm on excitation at 980 nm (⁴I_15/2 → ⁴I_11/2) of absorption bands of Er³⁺ ions. It is observed that photoluminescent intensity at 526 nm (²H_11/2 → ⁴I_15/2), 550 nm (⁴S_3/2 → ⁴I_15/2) and 1550 nm (⁴I_13/2 → ⁴I_15/2) initially decrease and then gradually increase with increase in heat-treatment time. The measured lifetime (τ_f) of the ⁴I_13/2 → ⁴I_15/2 transition also possesses a similar trend. The measured absorption and fluorescence spectra reveal that the Er³⁺ ions gradually enter into the KNbO₃ nanocrystals.     

Synthesis and DFT calculations of oxido and phenylimido-rhenium(V) complexes incorporating the N,O donor ligand 2-[(2-hydroxyethylimino)methyl]phenol

The reactions of equimolar amounts of trans-[ReOC1₃(PPh₃)₂] or trans-[Re(NPh)(PPh₃)₂Cl₃] with a Schiff base formed by condensation of 2-hydroxy-4-methoxybenzaldehyde and ethanolamine (H₂L) result in the formation of cis-[ReO(HL)PPh₃Cl₂] (1a) and trans-[Re(NPh)(HL)(PPh₃)Cl₂] (2b), respectively, in good yields. 1a and 2b have been characterized by a range of spectroscopic and analytical techniques. The X-ray crystal structures of 1a and 2b reveal that 1a is an octahedral cis-Cl,Cl oxorhenium(V) complex, while 2b is a trans-Cl,Cl phenylimidorhenium(V) complex. The complexes are weakly emissive at room temperature with quantum yields of 10^?4. Density functional theory calculations of the electronic properties of the complexes were performed and are in agreement with the experimental results. The complexes display quasi-reversible Re(V)/Re(VI) redox couples in acetonitrile. There is reasonable agreement between the experimental and calculated redox potentials of 1a and 2b.     

Surface Plasmon Resonance (SPR) Based Optimization of Biosynthesis of Silver Nanoparticles from Rhizome Extract of <Emphasis Type="Italic">Curculigo orchioides</Emphasis> Gaertn. and Its Antioxidant Potential

The present study for the first time explores the use of Central composite design (CCD) of RSM to optimize the process parameters of biosynthesis of AgNPs from rhizome extract of Curculigo orchioides based on the absorbance of surface plasmon resonance (SPR) band at 430 nm that corresponds to the synthesis of mono-disperse, spherical AgNPs. A polynomial model was established as a functional relationship between the synthesis of AgNPs and four independent variables such as concentration of AgNO₃, % rhizome extract, pH and temperature. The optimum conditions for maximum AgNPs synthesis were 2 mM concentration of AgNO₃, 20 % rhizome extract, pH 8, and temperature of 60 °C. A significant correlation (R ² = 0.8947) was observed between the experimental data and the predicted values indicating the adequacy of the model. Transmission electron microscopy (TEM) revealed spherical particles with size range of 5–28 nm. Selected area electron diffraction pattern and X-ray diffraction analysis confirmed the face-centered cubic structure of metallic silver. The plausible mechanism for the reduction of AgNO₃ to AgNPs was proposed following the identification of functional groups by FTIR. The antioxidative activity of AgNPs was demonstrated with scavenging of hydrogen peroxide (H₂O₂), 1,1-Diphenyl-2-picrylhydrazyl (DPPH) and superoxide radicals.     

Defect-Free Synthesis of a Fully π-Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders**

Fully π-conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect-free synthesis and resolution of a fully π-conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid-promoted alkyne benzannulations of a rationally designed, random-coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix-inversion barrier, the isolated excess one-handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10⁻² and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well-supported by molecular dynamics simulation.     

Kinetic studies of nonaqueous polymerization of methyl methacrylate initiated by ferric laurate–n-hexyl amine system

The polymerization of methyl methacrylate was studied in carbon tetrachloride medium with ferric laurate, a metal soap, in combination with n-hexyl amine as the initiator system at 60°C. The rate of polymerization was found to be linear with the monomer concentration and proportional to the square root of both ferric ion and amine concentration. A reaction scheme involving initial complex formation between ferric ion and amine and subsequent reaction of the complex with the solvent molecule to produce free radicals responsible for initiation of polymerization has been postulated to account for the observed results.