Separation and preconcentration of131I− and131IO 3 − in a liquid-liquid system

The application of isotope exchange in a liquid-liquid system for the separation and preconcentration of¹³¹I^– and¹³¹IO^3/– from water is described. For this purpose a solution of elemental iodine in tri-n-butyl phosphate diluted with toluene was used. The influence of various factors on the separation efficiency of¹³¹I was investigated. These are: time of the exchange, concentration of a carrier in the aqueous phase, concentration of I₂ in the organic phase, volume ratio of the phases, pH, foreign ions, storage of the organic phase, etc. The method is quite rapid and the selective preconcentration of these chemical forms of radioiodine from water can be accomplished even in the presence of the most important fission products. This method makes also possible to separate these chemical forms from each other under controlled pH conditions. The activity of the separated radioiodine can be measured advantageously, e.g., by homogeneous liquid scintillation counting after decolourization of the organic phase.     

Determination of trace calcium by solid substrate-room temperature phosphorimetry

A new method for the determination of trace calcium by solid substrate-room temperature phosphorimetry is established. It is based on the fact that chromeazurols azurol S-phenanthroline-NaCMC (CAS-phen-NaCMC) system can emit strong and stable room temperature phosphorescence (RTF) on the solid substrate in the filter paper. Ca2 and phenanthroline can form complex ion Ca(phen)32 , which will form complex [Ca(phen)3(CAS)2] with CAS. In the result, the number of CAS molecules in each spot increased, causing sharp increase of the RTP signal of the CAS-phen-NaCMC system.     

Determination of trace arsenic(V) by catalytic solid substrate-room temperature phosphorescence quenching method

In the H2SO4 medium and in the presence of dodecylbenzene sulfonic acid sodiumsalt (DBS), dimethyl yellow (R) could emit strong and stable solid substrate room temperature phosphorescence (RTP) on filter paper. And NaIO4 could oxidize R to cause the RTP quenching. Arsenic(V) could catalyze the reaction of NaIO4 oxidizing R, which caused the RTP sharply quenching. The reducing value of phosphorescence intensity (△Ip) for the system with DBS is 3.3 times higher than that without DBS. Moreover, the△Ip is proportional to the concentration of As(V). Based on the facts above, a new RTP quenching method for the determination of trace As(V) has been established.     

Determination of trace PAHs in seawater and sediment pore-water by solid-phase microextraction (SPME) coupled with GC/MS

A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. The SPME operational parameters have been optimized, and the effects of salinity and dissolved organic matter (DOM) on PAHs recoveries have been investigated. SPME measures only the portion of PAHs which are water soluble, and can be used to quantify PAH partition coefficient between water and DOM phases. The detection limits of the overall method for the measurement of sixteen PAHs range from 0.1 to 3.5 ng/g, and the precisions of individual PAH measurements range from 4% to 23% RSD. The average recovery for PAHs is 88.2±20.4%. The method has been applied to the determination of PAHs in seawater and sediment porewater samples collected in Jiaozhou Bay and Laizhou Bay in Shandong Peninsula, China. The overall levels of PAHs in these samples reflect moderate pollution compared to seawater samples reported elsewhere. The PAH distribution pattern shows that the soluble PAHs in seawater and porewater samples are dominated by naphthalenes and 3 ring PAHs. This is in direct contrast to those of the sediment samples reported earlier, in which both light and heavy PAHs are present at comparable concentrations. The absence of heavy PAHs in soluble forms (<0.1-3.5 ng/L) is indicative of the strong binding of these PAHs to the dissolved or solid matters and their low seawater solubility.     

Bi2(IO3)(IO6): First combination of [IO3]− and [IO6]5− anions in three-dimensional framework

A new bismuth (III) iodate periodate, Bi₂(IO₃)(IO₆) was obtained from hydrothermal reactions using Bi(NO₃)₃·5H₂O, and H₅IO₆ as starting materials. Bi₂(IO₃)(IO₆) crystallizes in the monoclinic space group P2₁/c (No. 14) with lattice parameters ɑ = 8.1119(6), b = 5.4746(4), c = 16.357(1) Å, β = 99.187(2)°, V = 717.07(9) ų, Z = 4. The structure of Bi₂(IO₃)(IO₆) features a three-dimensional framework which is a combination of [Bi(1)O₅] tetragonal pyramids, [Bi(2)O₈] bicapped trigonal prisms and [IO₃]⁻ and [IO₆]⁵⁻ anions. Thermal analysis shows that the compound is thermally stable up to about 350 °C. The solid state UV-vis-NIR diffuse reflectance spectrum indicates that Bi₂(IO₃)(IO₆) is a semiconductor with a band gap of 2.76 eV.     

Determination of trace uranium (VI) using its self-assembly with a tetradentate–monodentate ditopic ligand by resonance light scattering

We describe here a resonance light scattering (RLS) method for uranium (VI) detection by using phosphorylethanol-amido-salophen (PAS) as optical probe. PAS is a tetradentate–monodentate ditopic ligand in which the tetradentate and monodentate ligands are salophen moiety and phosphate group, respectively. PAS can chelate uranyl with its salophen moiety. The chelated uranyl can connect phosphate group in another PAS through coordination reaction. This causes the self-assembly of PAS with uranyl to form a metallo-supramolecular polymer, resulting in a production of strong RLS signal. The RLS method was established based on the self-assemble. The RLS intensity is linearly related to the concentration of uranium (VI) in the 0.8–32 ng mL^?1 range, with a detection limit of 0.24 ng mL^?1 detection limit under optimal conditions. The method was successfully applied to determine uranium (VI) in environmental water samples with the recoveries between 97.1% and 102.6%.     

Enhanced chemiluminescence of the luminol–KIO4 system by ZnS nanoparticles

The chemiluminescence (CL) intensity of the luminol–KIO₄ system is strongly enhanced by addition of zinc sulfide nanoparticles (ZnS-NPs) capped with 3-mercaptopropionic acid. On injection of fluoroquinolones into the luminol–KIO₄–ZnS–NP system, CL intensity is substantially increased. The CL emission peaks at 430 nm, thus indicating that the luminophore is 3-aminophthalate. The enhancement effect is attributed to a catalytic effect of the ZnS-NPs, which is assumed to accelerate the electron transfer process and to facilitate radical generation. Based on theses findings, a sensitive CL assay was developed for several fluoroquinolones.     

Determination of thorium with DBF-arsenaz by flow-injection analysis

A sensitive,selective,rapid,simple,and convenient method for the determination of thoriumwas developed.The method was based on the color reaction of thorium with DBF-arsenazo in astrong acidic medium (4 mol/L HCI).The flow-injection technique was used with an automated flow-injection analyzer.Beer's law was obeyed in the range of 0—1.4 μg/mL.The relative standarddeviations were less than 1%.     

Determination of Sugars by LC with On-Line Electrogenerated Cu(HIO6)2]5−–Luminol Chemiluminescence Detection

A novel method was developed for the determination of sugars such as glucose, fructose and lactose by column liquid chromatography coupled with chemiluminescence detection. The LC separation used a Kromasil NH₂ column (250 × 4.6 mm, i.d.: 5 μm, pore size, 100 Å) with a mobile phase consisting of acetonitrile and water. The chemiluminescence detection was based on the enhancement effect of the selected sugars on the chemiluminescence intensity between luminol and [Cu(HIO₆)₂]^5?, which was on-line electrogenerated by constant current electrolysis. The limits of detection for determination of glucose, fructose and lactose were 4, 3 and 20 μg mL^?1, respectively. The proposed method has been successfully applied to the determination of glucose and fructose in grape samples and lactose in milk samples.     

A novel combined electrochemical oscillator from cathode and anode in IO3−/Fe(CN)64− system

Experimental studies have been performed for the simultaneous potential or current oscillations occurring both on cathode and anode in the IO₃⁻/Fe(CN)₆⁴⁻ system. The combined oscillator exhibits very different behavior from that of the individual oscillators on each electrode owing to the different waveforms and incommensurate oscillating frequencies of the individual oscillators. The potential oscillation of the combined oscillator is essentially a sum of those of the individual oscillators for the mixed system, whereas the sum coming from the single systems is slightly different, mainly due to the difference in ionic strength between the single system and the mixed system. The separate current oscillators also seem to interfere with each other, probably through the restricted distribution of the applied voltage in both electrodes and the ohmic drop in addition to the effect of ionic strength.     

Determination of trace europium by use of the new fluorescence system europium–sparfloxacin–1,10-phenanthroline–sodium dodecyl sulfate

A new lanthanide-sensitized luminescence system: europium–sparfloxacin–1,10-phenanthroline–sodium dodecyl sulfate has been discovered. The spectrofluorimetric properties of the system were studied. The effect of experimental conditions on the fluorescence intensity was defined. Under the optimum conditions, the fluorescence intensity of the system is a linear function of the concentration of europium in the range 5.0×10^–9–1.0×10^–6 mol L^–1 and the detection limit is 1.0×10^–10 mol L^–1. The system was used for the determination of trace amounts of europium in rare earth samples with satisfactory results.     

In situ monitoring of potential oscillations in the reduction of IO3− by electrochemical quartz crystal microbalance

Electrochemical quartz crystal microbalance (EQCM) has been employed to study the potential oscillatory mechanism for the IO₃⁻ reduction accompanying periodic hydrogen evolution. The new experimental results that were obtained by in situ EQCM monitoring clearly demonstrate the all key steps involved in the oscillation: the diffusion-limited depletion of IO₃⁻ by reduction, the formation, growth and departure of hydrogen bubbles on the surface, and the convection-induced replenishment of IO₃⁻ by the hydrogen evolution. In addition to the frequency response to the surface mass change as reported in the literature, our study first shows that simultaneous frequency responses to the changes of density and viscosity in the diffusion layer during the oscillation can also provide meaningful and even decisive information on the oscillatory mechanism for the oscillators involving the coupling of electrochemical reactions with diffusion and convection mass transfer.     

I−/IO3 − Assemblies as Promoters of Iodohydrin Formation

Abstract

The direct conversion of olefins to their corresponding iodohydrins is efficient with I^?/IO₃ ^? assemblies in an aqueous acidic medium. Iodohydrins were obtained in moderately good yields at ambient reaction conditions without employing any metal catalysts. The addition of IOH across the olefin follows the Morkovnikov's rule.     

Study of the copper(II)-Aztreonam™ system by potentiometry and spectrophotometry,and structural characterization by 13C NMR relaxation

Potentiometric and spectrophotometric results obtained for the Cu(II)-Aztreonam system give a clear indication of the cheating properties of this antibiotic toward the Cu²⁺ ion, coordinated already at pH ≌ 2. Only one single complex of 1:1 stoichiometry is formed. Measurements of ¹³C relaxation rates allow us to attribute a coordination scheme via the carboxylic and aminic groups.     

Transport parameters of I− and IO3 − determined in crushed granitic rock columns and groundwater system under dynamic flow conditions

Transport of two principal inorganic iodine anions separately in two crushed crystalline granitic rocks, gabbro and tonalite, have been investigated. The rocks were crushed and sieved, and finally a fraction between 0.25 and 0.80 mm was filled in 5 cm³ PET columns (medical syringes) of 5.40 cm length and 1.24 cm in inner diameter. NaI and NaIO₃ were dissolved in synthetic groundwater (SGW) in a concentration as low as 10^?4 mol/dm³. The SGW was pumped into the columns at a seepage velocity of 0.031 ± 0.001 cm/min using a multi-head peristaltic pump. Iodine concentration in the outflow SGW from the columns was determined by UV–Vis spectrophotometry at 510 nm absorption maximum in CHCl₃ using redox reactions. By the use of a dependence of concentration on the number of pore volumes from the outflow and the linear isotherm model, based on erfc-function, breakthrough curves were constructed and the principal transport parameters were calculated. The values of sorption and desorption retardation coefficients of about 1 for both iodide and iodate have been obtained, which show evidence of practically non-sorption behavior of these chemical forms of iodine in the tested granitic rocks. The values of hydrodynamic dispersion coefficients and corresponding Peclet numbers were about 0.0077 ± 0.0006 and 21.6 ± 1.8 cm²/min, respectively, for both anions and rocks under given conditions.     

Solvent effect on the kinetics of oxidation of [Co(en)2amS]2+ by IO4−

The dependence of the rate constants for the oxidation of [Co(en)2amS]2+ (amS=–SCH2CH2NH2 2– by IO4– on solvent composition has been established for aqueous mixtures of MeOH, i-PrOH, t-BuOH, urea (U), ethylene carbonate (EC), acetonitrile (AN), dimethyl formamide (DMF) and acetone (Me2CO). Addition of aprotic cosolvents leads to marked decrease in the reaction rate in comparison to monohydroxylic alcohols. Alcohols inhibit the reaction rate in order MeOH < i-PrOH < t-BuOH. The change in solvation on going from the initial to the transition state are discussed in terms of the Gibbs transfer function, Gt0.     

Ru3(CO)12-Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Hemilabile ligands have been applied extensively in transition metal catalysis, but preparations of these molecules typically require multistep synthesis. Here, modular assembly of diverse phosphine-amide ligands, including related axially chiral compounds, is first reported through ruthenium-catalyzed C−H activation of phosphines with isocyanate directed by phosphorus(III) atoms. High reactivity and regioselectivity can be obtained by using a Ru₃(CO)₁₂ catalyst with a mono-N-protected amino acid ligand. This transformation significantly expands the pool of phosphine-amide ligands, some of which have shown excellent efficiency for asymmetric catalysis. More broadly, the discovery constitutes a proof of principle for facile construction of hemilabile ligands directly from the parent monodentate phosphines by C−H activation with ideal atom, step and redox economy. Several dinuclear ruthenium complexes were characterized by single-crystal X-ray diffraction analysis revealing the key mechanistic features of this transformation.     

Determination of trace platinum by supramolecular catalytic kinetic spectrofluorimetry of β–cyclodextrin–platinum–KBrO3–salicylaldehyde furfuralhydrazone

A supramolecular catalytic kinetic spectrofluorimetric method was developed for the determination of platinum(IV) and the possible mechanism of catalytic reaction was discussed. The method was based on the fluorescence-enhancing reaction of salicylaldehyde furfuralhydrazone (SAFH) with potassium bromate, which was catalysed by platinum(IV) in a water–ethanol medium. β–Cyclodextrin (β-CD) obviously sensitized the determination at pH 5.20 and 25°C. Under optimum conditions, the β-CD–platinum–KBrO₃–SAFH supramolecular kinetic catalytic reaction system had excitation and emission maxima at 372 and 461 nm, respectively. The linear range of this method was 0.60–180 ng ml⁻¹ with a relative standard deviation of 1.2%, and the detection limit was 0.18 ng ml⁻¹. Investigation of the mechanism and the effects of interferences is presented. The proposed method was applied successfully to determine trace platinum(IV) in the chemotherapeutic drug cisplatin and serum from patients with satisfactory results.      

Low-voltage thin-layer electrophoresis of inorganic anions on silica gel-G and titanium (IV) tungstate layers: separation of coexisting F−, Cl−, Br− and I−, I−, IO3− and IO4−, Fe(CN)64− and Fe(CN)63−

The electrophoretic behavior of twenty anions has been studied on silica gel-G, titanium (IV) tungstate and silica gel-G- titanium (IV) tungstate admixture layers using 0.1 M solutions of oxalic acid, citric acid, tartaric acid, succinic acid and acetic acid as background electrolyte. The mechanism of migration is explained in terms of adsorption and the solubility of various sodium or potassium salts of the anions in water. Titanium (IV) tungstate behaves only as an adsorbent and not as an ion exchanger. Being a cation exchanger, there is no exchange phenomenon occurring with anions. The migration of halides increase linearly with an increase in the bare ion radii of these ions. Differential migration of the anions on silica gel-G layers led to binary, ternary and quaternary separations of similar anions such as F⁻ – Cl⁻ – Br⁻ – I⁻, I⁻ – IO₃⁻ – IO₄⁻, BrO₃⁻ – IO₃⁻ and Fe(CN)₆³⁻ – Fe(CN)₆⁴⁻. The two cyanoferrate ions are separated from industrial waste water and from fixer and bleach solutions. The migration of anions has also been found to be in accordance with their lyotropic numbers.

     

Determination partition coefficients of volatile organic substances in the system liquid–air for the creation of calibration gas-phase samples with trace concentrations of substances

The results of determination of Henry’s coefficients for an equilibrium vapor containing trace concentrations of acetone, benzene, toluene, and xylenes over their aqueous solutions are presented. Continuous gas extraction is used.