Preconcentration and Determination of Toxic Metals by A New Calix[4]arene Bonded HPLC Column

The present study deals with the preconcentration and determination of toxic metal ions using p-tetranitrocalix[4]arene (3) appended silica-based new HPLC column. The synthesized material was characterized using Fourier transform infrared and scanning electron microscopy techniques. The sorption characteristics of the HPLC column were investigated for three toxic metals (Cd²⁺, Hg²⁺ and Pb²⁺) in column agreement. The experiments were performed in five steps that were monitored using a UV–visible diode-array detector. However, all the HPLC experimental results were reconfirmed by using atomic absorption spectrophotometer. The effect of concentration on the sorption efficiency of the column was evaluated for all the three metals and the data obtained were investigated using Langmuir, Freundlich and Dubinin–Redushkevich (D–R) sorption isotherms. The value of coefficient of determination (R ²), i.e. 0.99, suggested that the Freundlich sorption isotherm was found to be the best-fit model for all the three toxic metal ions, whereas, mean free energy was calculated from the D–R isotherm as 5.3, 5.7, and 5.8 kJ/mol for Pb²⁺, Cd²⁺, and Hg²⁺, respectively; suggesting that physical electrostatic force is involved in the sorption process. The developed method was validated for system efficiency, accuracy, and precision.

     

Synthesis, characterization and antioxidant activity copper-quercetin complex

Quercetin (3,3',4',5,7-pentahydroxyflavone) one of the most abundant dietary flavonoids, has been investigated in the presence of Cu(II) in methanol. The spectroscopic studies (UV-vis, (1)H NMR and IR) were useful to assess the relevant interaction of Quercetin with Cu(II) ions, the chelation sites and dependence of the complex structure from the metal/ligand ratio. A 1:2 (L:M) complex was indicated by Job's method of continuous variation, which was applied to ascertain the stoichiometric composition of the complex. The antioxidant activities of the compounds were evaluated by using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method. The complexed flavonoid was much more effective free radical scavengers than the free flavonoids.     

The N-alkyldithiocarbamato complexes [M(S2CNHR)2] (M=Cd(II) Zn(II); R=C2H5, C4H9, C6H13, C12H25); their synthesis, thermal decomposition and use to prepare of nanoparticles and nanorods of CdS

A series of N-alkyldithiocarbamato complexes [M(S2CNHR)2] (M=Cd(II), Zn(II); R=C2H5, C4H9, C6H13, C12H25) have been synthesised and characterized. The decomposition of these complexes to sulfates has been investigated, and a mechanism proposed. The structures of [Zn(S2CNHHex)2], [Cd(SO4)2(NC5H5)4)]n and [Cd(SO4)2(NC5H5)2(H2O)2)]n have been determined by X-ray single crystal method. The cadmium complex [Cd(S2CNHC12H25)2] and zinc complex [Zn(S2CNHC6H13)2] were used as single-source precursors to synthesize CdS and ZnS nanoparticles, respectively. The synthesis of CdS nanoparticles was carried under various thermolysis conditions and changes in the shape of derived nanoparticles were studied by transmission electron microscope (TEM).     

A critical point analysis of two phonon structure in the far infrared dielectric response of GaAs

The technique of asymmetric Fourier transform spectroscopy has been used to determine the complex relative permittivities of undoped GaAs at frequencies near the transverse optic mode. It is demonstrated that the anharmonic damping function calculated from these results is sensitive to two phonon processes excited by the anharmonic decay of the qO transverse optic phonon. Critical-point phonon frequencies are assigned from the structure revealed in damping function.     

The efficacy of nitrosonaphthol functionalized XAD-16 resin for the preconcentration/sorption of Ni(II) and Cu(II) ions

Amberlite XAD-16 resin has been functionalized using nitrosonaphthol as a ligand and characterized employing elemental, thermogravimetric analysis and FT-IR spectroscopy. The sorption of Ni(II) and Cu(II) ions onto this functionalized resin is investigated and optimized with respect to the sorptive medium (pH), shaking speed and equilibration time between liquid and solid phases. The monitoring of the influence of diverse ions on the sorption of metal ions has revealed that phosphate, bicarbonate and citrate reduce the sorption up to 10–14%. The sorption data followed Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherms. The Freundlich parameters computed are 1/n = 0.56 ± 0.03 and 0.49 ± 0.05, A = 9.54 ± 1.5 and 6.0 ± 0.5 mmol g⁻¹ for Ni(II) and Cu(II) ions, respectively. D–R isotherm yields the values of X_m = 0.87 ± 0.07 and 0.35 ± 0.05 mmol g⁻¹ and of E = 9.5 ± 0.23 and 12.3 ± 0.6 kJ mol⁻¹ for Ni(II) and Cu(II) ions, respectively. Langmuir characteristic constants estimated are Q = 0.082 ± 0.005 and 0.063 ± 0.003 mmol g⁻¹, b = (4.7 ± 0.2) × 10⁴ and (7.31 ± 0.11) × 10⁴ l mol⁻¹ for Ni(II) and Cu(II) ions, respectively. The variation of sorption with temperature gives thermodynamic quantities of ΔH = −58.9 ± 0.12 and −40.38 ± 0.11 kJ mol⁻¹, ΔS = −183 ± 10 and −130 ± 8 J mol⁻¹ K⁻¹ and ΔG = −4.4 ± 0.09 and −2.06 ± 0.08 kJ mol⁻¹ at 298 K for Ni(II) and Cu(II) ions, respectively. Using kinetic equations, values of intraparticle transport and of first order rate constant have been computed for both the metal ions. The sorption procedure is utilized to preconcentrate these ions prior to their determination in tea, vegetable oil, hydrogenated oil (ghee) and palm oil by atomic absorption spectrometry using direct and standard addition methods.     

Vibrational studies of BH−4 and BD−4 isolated in alkali halides

Single crystals of alkali halides doped with BH^?₄ and BD^?₄ were grown from the melt. Previously unreported bands in the infrared spectra of BH^?₄ and BD^?₄ isolated in different alkali halides are interpreted in terms of summation bands of internal and external modes of vibration. This has allowed the torsional and translational modes of the impurity ion to be identified. The tetrahedral symmetry of the borohydride ion is retained when it is isolated within alkali halides with the NaCl structure. A reduction of symmetry towards C_3v was observed when BH^?₄ (or BD^?₄) was isolated within lattices with CsCl structure.Raman and far infrared spectra of alkali halide/BH^?₄ systems will be reported for the first time, and high pressure infrared studies of these systems will be described. The effects of pressure in the internal mode, external modes, Fermi resonance and NaCl to CsCl structural phase changes will be discussed.     

Enrichment of Pb(II) ions using phthalic acid functionalized XAD-16 resin as a sorbent

A simple and reliable method has been developed using polymeric material containing phthalic acid as a chelating agent to concentrate ultratrace amounts of lead ions in aqueous solutions. After characterization by CHN, IR, and thermal studies, the static and dynamic sorption behavior of Pb(II) ions onto new synthetic resin has been investigated. The sorption has been optimized with respect to pH, shaking speed, and contact time between the two phases. Maximum sorption is achieved from solution of pH 5-8 after 10 min agitation time. The lowest concentration for quantitative recovery is 5.8 ng cm(-3) with a preconcentration factor of approximately 850. The kinetics of sorption follows the first-order rate equation with the rate constant k=0.58+/-0.04 min(-1). The variation of the equilibrium constant K(c) with temperature between 10 and 50 degrees C yields values of DeltaH, 52.4+/-1.65 kJmol(-1), DeltaS, 186+/-5.21 Jmol(-1)K(-1), and DeltaG(303K), -4.15+/-0.002 kJmol(-1). The sorption data of Pb(II) ions in the concentration range from 2.41x10(-6) to 1.44x10(-4) molL(-1) follows the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherms at all temperatures investigated. The sorption of Pb(II) ions onto synthesized resin in the presence of common anions and cations has also been measured. The possible sorption mechanism of Pb(II) ions onto phthalic acid modified XAD-16 is also discussed. The sorption procedure is utilized to preconcentrate Pb(II) ions prior to their determination in automobile exhaust particulates by atomic absorption spectrometry using direct and standard addition methods.     

Evaluation of perchlorate sorption behavior of calix[4]arene appended resin

In the present work, perchlorate sorption ability of calix[4]arene appended resin was investigated to develop a new efficient method for the removal of perchlorate from aqueous media. The column sorption process was performed at a wide range of pH (1–7) and perchlorate content in the effluent was determined through ion chromatography. From the results, it has been concluded that maximum sorption (97 %) of perchlorate is taking place at pH 3. The breakthrough curves were obtained as a function of time to get clear picture of sorption process and the data obtained was tested by applying two kinetic sorption models, i.e. Yoon-Nelson and BDST. The data obtained through experiments were compared with the theoretically calculated values and it has been found that both have close agreement with each other.     

Facilitated kinetic transport of Cu(II) through a supported liquid membrane with calix[4]arene as a carrrier

In the present investigation, p-morpholinomethylcalix[4]arene (1) has been examined as a carrier in supported liquid membrane (SLM) for Cu(II) transport. The influence of different parameters, such as solvent, membrane dipping time, support membrane, co-anions, donor and acceptor pH, and carrier concentration on Cu(II) transport, was checked. The permeability values were calculated by using Danesi mass transfer model. Higher Cu(II) permeability was observed in diphenyl ether, with 1 h dipping time, Celgard 2500 and Cl^? as co-anion. The optimum pH for donor phase was 2 and that for acceptor phase was neutral at 10^?3 M carrier concentration. Diffusion coefficients were calculated using Reinhoudt's model, lag time measurements as well as by Wilke–Chang relation and compared. The transport was found to be diffusion-controlled in the membrane phase and the diffusion coefficient was calculated to be 1.54 × 10^?10 m/s whereas the extraction constant was calculated to be 1.19 × 10^?5 m/s.     

Cold Pad-Batch dyeing method for cotton fabric dyeing with reactive dyes using ultrasonic energy

Reactive dyes are vastly used in dyeing and printing of cotton fibre. These dyes have a distinctive reactive nature due to active groups which form covalent bonds with -OH groups of cotton through substitution and/or addition mechanism. Among many methods used for dyeing cotton with reactive dyes, the Cold Pad Batch (CPB) method is relatively more environment friendly due to high dye fixation and non requirement of thermal energy. The dyed fabric production rate is low due to requirement of at least twelve hours batching time for dye fixation. The proposed CPB method for dyeing cotton involves ultrasonic energy resulting into a one third decrease in batching time. The dyeing of cotton fibre was carried out with CI reactive red 195 and CI reactive black 5 by conventional and ultrasonic (US) method. The study showed that the use of ultrasonic energy not only shortens the batching time but the alkalis concentrations can considerably be reduced. In this case, the colour strength (K/S) and dye fixation (%F) also enhances without any adverse effect on colour fastness of the dyed fabric. The appearance of dyed fibre surface using scanning electron microscope (SEM) showed relative straightening of fibre convolutions and significant swelling of the fibre upon ultrasonic application. The total colour difference values ΔE (CMC) for the proposed method, were found within close proximity to the conventionally dyed sample.