Effect of cationic gemini surfactants on the hydrolysis of carboxylate and phosphate esters using hydroxamate ions

The kinetics of the hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyl diphenyl phosphate (PNPDPP) by hydroxamate ions mediated by gemini surfactants with quaternary ammonium bromide (16-n-16,2Br⁻, n = 3, 4, 6, 12) and pyridinium chloride (12py-n-py12,2Cl⁻, n = 3, 4) head group have been investigated at 27 °C. The gemini surfactant with the pyridinium head group, 12-py-4-py12,2Cl⁻ (tetramethylene-1,4 bis dodecylpyridinium chloride) shows a large rate acceleration effect than that with an ammonium head group, 16-12-16,2Br⁻, relative to those in water. The apparent pK _a of the hydroxamic acids have been determined in the presence of gemini surfactants. Catalytic system N-phenylbenzohydroxamate/12py-4-py12,2Cl⁻ demonstrated over ~1,590-fold and ~255-fold rate enhancement in the hydrolysis of PNPA and PNPDPP, respectively, for the identical reaction performed in buffer aqueous media at 27 °C. The second order rate constant and binding constants for reactions were determined employing pseudophase model for micellar catalysis.     

Pulse Radiolysis Study of Initiation,Dimerization, and Propagation Steps of 3,3-Dimethylacrylic Acid in Aqueous Medium

Rates of initiation, dimerization, and first propagation steps originating from the hydrated electron and hydroxyl radical reactions with 3,3-dimethylacrylic acid monomer have been investigated using the technique of pulse radiolysis. The initiation step for the protonated monomer is found to be faster than that of the deprotonated form. The dimerization step is about two orders of magnitude faster than the first propagation step. Radical species are more reactive than the corresponding radical-anionic species, and the β-protonated electron adduct to the monomer is found to propagate faster than other electron adduct species. The different transient species have been characterized by their absorption spectra, λ_max, extinction coefficient, pK, and redox behavior. Based on these observations, the most probable structures are suggested.     

Extraction studies of plutonium from acidic solution using γ-ray induced PC-88A/TBP modified polymers

2-Ethylhexyl-2-ethylhexyl phosphonic acid (PC-88A) and Tributylphosphate (TBP) extractants have been attached to polypropylene (PP) in granular, film and non-woven fabric forms, by a simultaneous γ-ray irradiation method. The extraction of plutonium from the acidic radioactive liquid waste by modified polymers was studied by varying the γ-ray dose. The uptake of plutonium was also studied by polyethylene (PE) in film form. This modified polymer also showed extraction capability for plutonium from nitric acid medium. The uptake of plutonium depends upon the γ-ray dose as well as the nature and source of the polymer. Liquid–solid extraction studies showed that the equivalent amount of uptake of plutonium on TBP–polyethylene film requires twice the γ-ray dose as compare to TBP–polypropylene film. It was observed that at given γ-ray dose polypropylene fabric is not sturdy, compare to the granules and films, and material leach out in aqueous phase. The presence of other solvents like di-methyl formamide (DMF) and cyclohexane during γ-ray irradiation were able to enhance the extraction capabilities. The optimum conditions established during this study was successfully applied for the separation of plutonium, uranium and thorium from the fission products in acidic waste solution.     

Application of synthesized mesoporous titania microspheres for arsenic [(III) and (V)] uptake studies

The present work describes the application of radiotracer technique for studying uptake of arsenic on titanium hydroxide, commercial titanium dioxide (TiO₂) powder (anatase) and synthesized mesoporous titania beads in acidic, neutral, and alkaline conditions. Sol–gel templating method was used to prepare titania–polysaccharide composites, with different polymer contents. Mesoporous titania was obtained by heat treatment of the composite beads in a controlled environment. The synthesis process was optimized, using thermogravimetry analysis. X-ray diffraction patterns confirmed the formation of anatase pure phase titania (TiO₂) at 700 °C in different environments, and scanning electron microscopy studies confirmed uniform pore size distribution. The effect of surface area, polymer content and pH on uptake of arsenic(III) and (V) on the synthesized titania beads was also investigated. Arsenic(V) was found to be retained quantitatively on the titania beads synthesized from 0.8% polymer content titania–polymer composite precursor in neutral to alkaline conditions. Details of the results obtained are discussed.     

The α‐effect in micelles: Nucleophilic substitution reaction of p‐nitrophenyl acetate with N‐phenylbenzohydroxamate ion

Pseudo‐first‐order rate constants have been determined for the nucleophilic substitution reactions of p‐nitrophenyl acetate with p‐chlorophenoxide (4‐ClC₆H₄O^?) and N‐phenylbenzohydroxamate (C₆H₅CON(C₆H₅)O^?) ions in phosphate buffer (pH 7.7) at 27°C. The effect of cationic, (CTAB, TTAB, DTAB), anionic (SDS), and nonionic (Brij‐35) surfactants has been studied. The k_obs value increases upon addition of CTAB and TTAB. The effect of DTAB and other surfactants on the reaction is not very significant. The micellar catalysis and α‐effect shown by hydroxamate ion have been explained. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 26–31, 2006     

Dilution induced thickening in hydrotrope-rich rod-like micelles

Dilution induced changes in the microstructure and rheological behavior of micelles formed by a cationic surfactant-anionic hydrotrope mixture has been investigated in the hydrotrope-rich region. The surfactant used is cetyltrimethylammonium bromide (CTAB) and the hydrotropic salt is sodium 3-hydroxy naphthalene 2-carboxylate (SHNC). The concentration of the mixture is varied from 0.5% to 10.0% w/w (φ=0.005-0.100) at a fixed weight ratio of hydrotrope to surfactant (85:15). Rheological studies indicate Newtonian flow behavior at low and high volume fractions (0.005 and 0.100) while a shear thinning behavior is observed at intermediate volume fractions. The zero-shear viscosity η(0) also passes through a maximum upon changes in the concentration. The most striking feature in our study is that a low viscosity Newtonian fluid transforms to a viscoelastic fluid, upon dilution, and then again to a Newtonain fluid. Small angle neutron scattering studies of 10.0% micellar solution show the presence of rod-like aggregates. Upon dilution, the scattering intensity per unit concentration shows an increase in the low q-region. The nature of pair distance distribution function and subsequent model fitting indicates a transition from rod-like micelles to unilamellar vesicles upon dilution. This behavior is explained in terms of the volume fraction dependant solubilization of hydrotropes in the rod-like micelles and consequent changes in the composition of the mixed micelles.     

Interaction of Folic Acid with Mn2+ Doped CdTe/ZnS Quantum Dots: In Situ Detection of Folic Acid

To utilize the nanomaterials as an effective carrier for the drug delivery applications, it is important to study the interaction between nanomaterials and drug or biomolecules. In this study GSH functionalized Mn²⁺-doped CdTe/ZnS QDs has been utilized as a model nanomaterial due to its high luminescence property. Folic acid (FA) gradually quenches the FL of GSH functionalized Mn²⁺???doped CdTe/ZnS QDs. The Stern-Volmer quenching constant (K_sv), binding constant (K_s) and effective quenching constant (Ka) for the FA-QDs system is calculated to be 1.32?×?10⁵ M^?1, 1.92?×?10⁵ and 0.27?×?10⁵ M^?1, respectively under optimized condition (Temp. 300 K, pH 8.0, incubation time 40 min.). The effects of temperature, pH, and incubation time on FA-QDs system have also been studied. Statistical analysis of the quenched FL intensity versus FA concentration revealed a linear range from 1?×?10^?7 to 5.0?×?10^?5 for FA detection. The LOD of the current nano-sensor for FA was calculated to be 0.2 μM. The effect of common interfering metal ions and other relevant biomolecules on the detection of FA (12.0 μM) have also been investigated. L-cysteine and glutathione displayed moderate effect on FA detection. Similarly, the common metal ions (Na⁺, K⁺, Ca²⁺ and Mg²⁺) produced minute interference while Zn²⁺ Cu²⁺ and Fe³⁺ exert moderate interference. Toxic metal ions (Hg²⁺ and Pb²⁺) produced severe interferences in FA detection.

Graphical abstract

GSH-Mn²⁺ CdTe/ZnS QDs based Fluorescence Nanosensor for Folic acid

     

Catalyst Control in Switching the Site Selectivity of C−H Olefinations of 1,2-Dihydroquinolines: An Approach to Positional-Selective Functionalization of Quinolines

A unique approach to achieve site-selective C−H olefinations exclusively at the C-3- or C-8-positions in the quinoline framework has been developed by catalyst control. Distal C(3)−H functionalization is achieved by using palladium catalysis, whereas proximal C(8)−H functionalization is obtained by employing ruthenium catalysis. Switching the site selectivity within a single substrate directly indicates two diverse pathways, which are operating under the palladium- and ruthenium-catalyzed reaction conditions.     

Green Luminescent CdTe Quantum Dot Based Fluorescence Nano-Sensor for Sensitive Detection of Arsenic (III)

Arsenic (As³⁺) is a hazardous and ubiquitous element; hence the quantitative detection of arsenic in various kinds of environmental sample is an important issue. Herein, we reported L-cysteine capped CdTe Quantum dot based optical sensor for the fluorometric detection of arsenic (III) in real water sample. The method is based on the fluorescence quenching of QDs with the addition of arsenic solution that caused the reduction in fluorescence intensity due to strong interaction between As³⁺ and L-cysteine to form As(Cys)₃. The calibration curve was linear over 2.0 nM-0.5 μM arsenic with limit of detection (LOD) of 2.0 nM, correlation coefficient (r²) of 0.9698, and relative standard deviation (RSD %) of 5.2%. The Stern-Volmer constant for the quenching of CdTe QDs with As³⁺ at optimized condition was evaluated to be 1.17 × 10⁸ L mol^?1 s^?1. The feasibility of the sensor has been analyzed by checking the inference of common metal ions available in the water such as K⁺, Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Al³⁺, Co²⁺, Cr²⁺, Fe³⁺ and its higher oxidation state As⁵⁺.

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Graphical Abstract Schematic representation of As³⁺ detection by L-Cysteine capped CdTe QDs

     

Spectrofluorometric Determination of Mercury and Lead by Colloidal CdS Nanomaterial

Heavy metal ions such as Hg and Pb are hazardous due to very high toxicity, mobility, and ability to accumulate through the food chain or atmosphere in the environment system. Therefore, ultrasensitive determination of mercury and lead is important to provide an evaluation index of ions in aqueous environment. This paper describes the investigation of surface modified quantum dots (QDs) as a sensing receptor for Hg²⁺ and Pb²⁺ ion detection by optical approach. Water-soluble L-cysteine-capped CdS QDs have been synthesized in aqueous medium. These functionalized nanoparticles were used as a fluorescence sensor for Hg²⁺ and Pb²⁺ ions, involved in the fluorescence quenching. The effect of foreign ions on the intensity of CdS QDs showed a low interference response toward other metal ions except Cu²⁺ and Fe²⁺ ions. The limit of detection (LOD) of this system is found to be 1.0 and 3.0 nM for Hg²⁺ and Pb²⁺ ions, respectively.