Deamination and decarboxylation in the chromium(III)-catalysed oxidation of L-valine by alkaline permanganate and analysis of chromium(III) in microscopic amounts by a kinetic method

The kinetics of Cr^III-catalysed oxidation of L-valine by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction between permanganate and L-valine in alkaline medium exhibits 2:1 stoichiometry (KMnO₄:l-valine). The reaction shows first order dependence on [permanganate] and [chromium(III)], and less than unit order dependence each in [L-valine] and alkali concentrations under the experimental conditions. However the order in [L-valine] and [alkali] changes from first order to zero order as the concentrations change from lower to higher respectively. The results suggest the formation of a complex between L-valine and the hydroxylated species of Cr^III. The complex reacts further with 1 mol of alkaline permanganate species in a rate-determining step, resulting in the formation of a free radical, which again reacts with 1 mol of alkaline permanganate species in a subsequent fast step to yield the products. The reaction constants involved in the mechanism were evaluated. The activation parameters with respect to the slow step of the mechanism were obtained and discussed. The title reaction has been utilised to analyse chromium(III) in the 26.0 ng cm^–3–1.0 g cm^–3 range.     

Experimental and theoretical studies of Mn(II) and Co(II) metal complexes of a tridentate Schiff's base ligand and their biological activities

We have used the condensation method to synthesize 2-acetyl-5-methylsemicarbazone ligand. Manganese(II) and Cobalt(II) complexes having formula [ML₂]X₂ were synthesized where M = Mn(II) and Co(II), L = ligand, X = Cl⁻, CH₃COO⁻, NO₃⁻, ½SO₄²⁻. The characterization data suggests the octahedral geometry for all the synthesized complexes. Tridentate nature of the 2-acetyl-5-methylsemicarbazone ligand was revealed by IR studies. Molar conductance analysis suggested the electrolytic nature of the complexes. The theoretical study includes geometrical optimization, HOMO-LUMO energy gap, energetic parameters and dipole moment. These results also confirmed the tridentate nature of the ligand and the octahedral geometry of complexes. The molecular electrostatic potential (MEP) study suggested the reactive sites for an electrophilic or nucleophilic attack in the ligand. We tested the synthesized compounds for their antifungal and antibacterial action via well diffusion method and found that parent ligand after the coordination with the metal ion showed more effective inhibition against bacteria and fungi.     

Role of graphene in structural transformation of zirconium oxide

Fine powders of zirconium oxide (ZrO₂) were prepared using zirconium oxychloride by combustion method. The crystalline size of pure ZrO₂ was in range of 14–45 nm. Graphene was incorporated in ZrO₂ using graphene oxide as precursor and reducing it with hydrazine hydrate. X-Ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analysis and Raman spectroscopy methods were used to characterize the samples. The role of graphene in structural transformation of ZrO₂ to monoclinic phase was clearly observed.     

An efficient method for the synthesis of quinoxaline derivatives catalyzed by titanium silicate-1

Research on Chemical Intermediates - A series of quinoxaline derivatives were efficiently synthesized by convenient and simple procedure in excellent yields using 1 wt.% of titanium silicate (TS-1)...     

Importance of micellar kinetics in relation to technological processes

The association of many classes of surface-active molecules into micellar aggregates is a well-known phenomenon. Micelles are in dynamic equilibrium, constantly disintegrating and reforming. This relaxation process is characterized by the slow micellar relaxation time constant, tau(2), which is directly related to the micellar stability. Theories of the kinetics of micelle formation and disintegration have been discussed to identify the gaps in our complete understanding of this kinetic process. The micellar stability of sodium dodecyl sulfate micelles has been shown to significantly influence technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification, solubilization, and detergency. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the breakup of micelles. Especially when the free monomer concentration is low, which is the case for many nonionic surfactant solutions, the micellar breakup time is a rate-limiting step in the supply of monomers. The Center for Surface Science & Engineering at the University of Florida has developed methods using stopped flow and pressure jump with optical detection to determine the slow relaxation time of micelles of nonionic surfactants. The results showed that the ionic surfactants such as SDS exhibit slow relaxation times in the range from milliseconds to seconds, whereas nonionic surfactants exhibit slow relaxation times in the range from seconds (for Triton X-100) to minutes (for polyoxyethylene alkyl ethers). The slow relaxation times are much longer for nonionic surfactants than for ionic surfactants, because of the absence of ionic repulsion between the head groups. The observed relaxation times showed a direct correlation with dynamic surface tension and foaming experiments. In conclusion, relaxation time data of surfactant solutions correlate with the dynamic properties of the micellar solutions. Moreover, the results suggest that appropriate micelles with specific stability or tau(2) can be designed by controlling the surfactant structure, concentration, and physicochemical conditions (e.g., salt concentration, temperature, and pressure). One can also tailor micelles by mixing anionic/cationic or ionic/nonionic surfactants for a desired stability to control various technological processes.     

Regioselective Acceptorless Dehydrogenative Coupling of N‐Heterocycles toward Functionalized Quinolines,Phenanthrolines, and Indoles

A new strategy has been developed for the oxidant‐ and base‐free dehydrogenative coupling of N‐heterocycles at mild conditions. Under the action of an iridium catalyst, N‐heterocycles undergo multiple sp³ C? H activation steps, generating a nucleophilic enamine that reacts in situ with various electrophiles to give highly functionalized products. The dehydrogenative coupling can be cascaded with Friedel–Crafts addition, resulting in a double functionalization of the N‐heterocycles.     

Surfactant mediated oxygen reuptake in water for green aerobic oxidation: mass-spectrometric determination of discrete intermediates to correlate oxygen uptake with oxidation efficiency

A novel strategy of catalytic green aerobic oxidation by surfactant-mediated oxygen reuptake in water offers a new dimension to the applications of surfactants to look beyond as solubility aids and a conceptual advancement in understanding the role of surfactants in aquatic organic reactions through mass spectrometry guided identification of discrete intermediates.     

Adsorbents based on carbon microfibers and carbon nanofibers for the removal of phenol and lead from water

This paper describes the production, characteristics, and efficacy of carbon microfibers and carbon nanofibers for the removal of phenol and Pb(2+) from water by adsorption. The first adsorbent produced in the current investigation contained the ammonia (NH(3)) functionalized micron-sized activated carbon fibers (ACF). Alternatively, the second adsorbent consisted of a multiscale web of ACF/CNF, which was prepared by growing carbon nanofibers (CNFs) on activated ACFs via catalytic chemical vapor deposition (CVD) and sonication, which was conducted to remove catalytic particles from the CNF tips and open the pores of the CNFs. The two adsorbents prepared in the present study, ACF and ACF/CNF, were characterized by several analytical techniques, including SEM-EDX and FT-IR. Moreover, the chemical composition, BET surface area, and pore-size distribution of the materials were determined. The hierarchal web of carbon microfibers and nanofibers displayed a greater adsorption capacity for Pb(2+) than ACF. Interestingly, the adsorption capacity of ammonia (NH(3)) functionalized ACFs for phenol was somewhat larger than that of the multiscale ACF/CNF web. Difference in the adsorption capacity of the adsorbents was attributed to differences in the size of the solutes and their reactivity towards ACF and ACF/CNF. The results indicated that ACF-based materials were efficient adsorbents for the removal of inorganic and organic solutes from wastewater.     

Microgels for the encapsulation and stimulus-responsive release of molecules with distinct polarities

A microfluidic strategy for the encapsulation and stimulus-responsive release of molecules with distinct polarities from the interior of microgels is reported. The approach relies on (i) the generation of a primary O/W emulsion by the ultrasonication method, (ii) MF emulsification of the primary emulsion, and (iii) photopolymerization of the monomer present in the aqueous phase of the droplets, thereby transforming them into microgels. Non-polar molecules are dissolved in oil droplets embedded in the microgels. Polar molecules are physically associated with the hydrogel network. Upon heating, the microgels contract and release polar and non-polar cargo molecules. The approach paves the way for stimuli-responsive vehicles for multiple drug delivery.