Ultrasensitive determination of cobalt in single hair by capillary electrophoresis using chemiluminescence detector

By use of the high separation capability of capillary electrophoresis (CE) and ultrasensitive chemiluminescence (CL) detection, a CE-CL method was proposed for the ultrasensitive determination of trace cobalt in a single hair, which is potentially useful in construction of the fingerprint of trace elements in the hair collected from crime scenes. In this work, the CE experimental conditions, CL experimental conditions and the digestion methods for the analysis of a single hair sample for cobalt were investigated in detail. The relative limit of detection (LOD, 3σ) was 0.01 ng/mL, and the absolute LOD was 2.4 × 10^− 16 g considering the sampling volume of 24 nL. Using a dry digestion method, the analytical results for certified reference hair samples by the proposed method were in good agreement with the certified values. Finally, this method was successfully used to detect trace cobalt in a single hair from three adults. It has potential applications in forensic analysis.     

A Mercury-Free Thick-Film Graphite Electrode for Determining Cobalt in Natural and Potable Waters by Stripping Voltammetry

A mercury-free thick-film graphite electrode is proposed for determining cobalt(II) by stripping voltammetry. It was found that nitroso-R-salt ensures the highest efficiency of the preconcentration and determination of cobalt(II), as compared to the other organic reagents. The effects of different parameters (the pH of the solution, the concentration of organic reagents, the potential and duration of preconcentration, potential sweep rate, and interfering elements) were studied to select the optimum conditions for determining cobalt(II) at a mercury-free thick-film graphite electrode. The detection limit for cobalt(II) was 7.3 × 10^–12 M (or 0.4 ng/L) for a preconcentration time of 30 s. A procedure for determining cobalt(II) in potable and natural waters was developed and certified (certificate no. 224.01.10.002/2004, Ural Scientific Research Institute of Metrology).     

Emulsion membrane extraction of cobalt using aromatic beta-hydroxyoxime

A batch pertraction (liquid membrane extraction, MX) of cobalt has been studied, with industrial reagent LIX 64N and ABF (USSR) as a carrier. The influence of cobalt, reagents and acid concentration has been searched. The kinetic and hydrodynamic characteristics of the emulsion were optimized. In one batch pertraction process it is possible to reach 100-fold cobalt preconcentration with 93–98% yield from 1 dm³ sample volume.     

Novel two-ply composite membranes of chitosan and sodium alginate for the pervaporation dehydration of isopropanol and ethanol

Novel two-ply dense composite membranes were prepared using successive castings of sodium alginate and chitosan solutions for the pervaporation dehydration of isopropanol and ethanol. Preparation and operating parameters namely polymer types facing to the feed stream, NaOH treatment for the regeneration of chitosan, and crosslinking system types were investigated using the factorial design method. It was shown that these parameters were all critical to the performance of the membrane in the form of the main and interaction effects. The pervaporation performance of the two-ply membrane with its sodium alginate layer facing the feed side and crosslinked or insolubilized in sulfuric acid solution was compared with the pure sodium alginate and the chitosan membranes in terms of the flux and separation factors. It was shown that although its flux was lower than that of the pure sodium alginate and chitosan membranes, the separation factors at various alcohol concentrations were in between values for the two pure membranes. For the dehydration of 90 wt% isopropanol–water mixtures the performance of the two-ply membrane which was moderately crosslinked in formaldehyde was found to match the high performance of the pure sodium alginate membrane. This two-ply membrane had fluxes of 70 g/m² h at 95% EtOH, 554 g/m² h at 90% PrOH and separation factors of 1110 at 95% EtOH, 2010 at 90% PrOH and its mechanical properties were better than that of the pure sodium alginate membrane.     

Pyridylazo-diaminobenzenes as reagents for cobalt: Spectrophotometric determination of cobalt in silicates and meteorites

Six pyridylazo-diaminobenzenes have been synthesized and assessed as chromogens for the spectrophotometric determination of traces of cobalt. Five of the reagents having chloro-, bromo- and iodo-substitutions on the heterocyclic ring show high colour stabilities and extreme sensitivities in their reactions in strongly acidic medium. The effective molar absorptivities range between 1.00 and 1.23·10⁵ 1 mole^-1 cm^-1. Only iron and chromium(VI) interfere; the presence of fluoride and hydroxylamine makes the reactions specific. 4-(5-Bromo-2-pyridylazo)-1,3-diamino-benzene has been applied to the determination of cobalt in silicate rocks and meteorites with good precision and accuracy.     

Chemiluminescent Determination of Vitamin B12 Using Charge Coupled Device (CCD)

A method was developed for the determination of vitamin B₁₂ based on the enhancement of cobalt (II) on the chemiluminescence (CL) reaction between luminol and percarbonate (powerful source of hydrogen peroxide). The release of cobalt (II) from the vitamin B₁₂ was reached by a simple and fast microwave digestion (20 s microwave digestion time and a mix of nitric acid and hydrogen peroxide). A charge coupled device (CCD) photodetector, directly connected to the cell, coupled with a simple continuous flow system was used to obtain the full spectral characteristics of cobalt (II) catalyzed luminol-percarbonate reaction.

The optima experimental conditions were established: 8.0 m mol L^?1 luminol in a 0.075 mol L^?1 carbonate buffer (pH 10.0) and 0.15 mol L^?1 sodium percarbonate, in addition to others experimental parameters as 0.33 mL s^?1 flow rate and 2 s integration time, were the experimental conditions which proportionate the optimum CL emission intensity. The emission data were best fitted with a second-order calibration graph over the cobalt (II) concentration range from 4.00 to 300 µ g L^?1 (r² = 0.9990), with a detection limit of 0.42 µ g L^?1. The proposed method was successfully applied to the determination of vitamin B₁₂ in pharmaceuticals.     

Pervaporation properties of novel alginate composite membranes for dehydration of organic solvents

A novel organic dehydration membrane consisting of aminated polyacrylontrile (PAN) microporous membrane as sublayer, alginate coating as top layer has been prepared and characterized by pervaporation experiment. The influence of hydrolysis and amination of the microporous support layer on selectivity and flux was studied and it was shown that amination of the sublayer improved pervaporation performance of the composite membrane greatly. The counter cation of alginate coatings as dense separating layer also influenced separation properties of the membrane, which was better for K⁺ than for Na⁺. This novel composite membrane with K⁺ as counter ion has a high separation factor of 1116 and a good permeation rate of 350 g/m² h for pervaporation of 90 wt.% ethanol aqueous solution at 70°C, higher separation factors and fluxes for n-PrOH/water, i-PrOH/water, acetone/water and dioxane/water systems. The results show that the separation factor and flux of this membrane increase with raising the operating temperature. At the same time, SEM micrographs show that the hydrolysis and amination of PAN microporous membrane change its pore structure. From the results it can be concluded that pore structure of the sublayer in addition to its chemical structure also make influence of separation properties of the composite membrane.     

Cloud point formation based on mixed micelles in the presence of electrolytes for cobalt extraction and preconcentration

A new micelle-mediated phase separation of metal ions, applied for preconcentrating trace levels of cobalt as a prior step to its determination by flame atomic spectroscopy, has been developed. Two methods were proposed employing both Triton X-100 and sodium dodecyl sulfate (SDS) as a mixed micellar system while the phase separation was induced by HCl or NaCl addition. Cobalt was complexed with pyridylazo compounds (PAN, PAR, 5-Br-PADAP) in an aqueous surfactant medium and it was concentrated in the surfactant rich phase after phase separation. The chemical variables affecting the cloud point extraction were evaluated, optimized and successfully applied to cobalt determination in pharmaceutical samples. Under the optimized conditions, the preconcentration system permitted limits of detection as 1.1 and 1.6 μg l⁻¹ cobalt, respectively, when HCl and NaCl were used. Both proposed methods showed linear calibration within a 25-200 μg l⁻¹ cobalt range. The extraction efficiency was investigated at different cobalt concentrations (40-185 μg l⁻¹) and good recoveries (98-102%) were obtained by using NaCl as electrolyte. The results obtained were compared with those observed with ET AAS.     

Characteristics of sodium alginate membranes for the pervaporation dehydration of ethanol–water and isopropanol–water mixtures

Alginate membranes for the pervaporation dehydration of ethanol–water and isopropanol–water mixtures were prepared and tested. The sodium alginate membrane was water soluble and mechanically weak but it showed promising performance for the pervaporation dehydration. To control the water solubility the sodium alginate membrane was crosslinked ionically using various divalent and trivalent ions. Among them the alginate membrane crosslinked with Ca²⁺ ion showed the highest pervaporation performance in terms of the flux and separation factors.     

Visible-Light-Driven Intermolecular Reductive Ene–Yne Coupling by Iridium/Cobalt Dual Catalysis for C(sp3)−C(sp2) Bond Formation

A new methodology to form C(sp³)−C(sp²) bonds by visible-light-driven intermolecular reductive ene–yne coupling has been successfully developed. The process relies on the ability of the Hantzsch ester to contribute in both SET and HAT processes through a unified cobalt and iridium catalytic system. This procedure avoids the use of stoichiometric amounts of reducing metallic reagents, which is translated into high functional-group tolerance and atom economy.     

Separation and concentration of cobalt from ammoniacal solutions containing cobalt and nickel by emulsion liquid membranes using 5,7-dibromo-8-hydroxyquinoline (DBHQ)

The separation and concentration of cobalt from ammoniacal solutions containing nickel and cobalt by an emulsion liquid membranes (ELMs) using 5,7-dibromo-8-hydroxyquinoline as extractant has been presented. Membrane solution consists of a diluent (kerosene), a surfactant (Span 80), a modifier (tributylphosphate), and an extractant (DBHQ). Very dilute sulphuric solution containing EDTA as complexing agent, buffered at pH 5.0, has been used as a stripping solution. pH of ammoniacal feed solution containing cobalt and nickel was adjusted to 9.0 with hydrochloric acid. The important variables governing the permeation of cobalt have been studied. These variables are membrane composition, pH of the feed solution, cobalt and nickel concentrations of the feed solution, mixing speed, surfactant concentration, extractant concentration, EDTA concentration and pH of the stripping solution, and phase ratio. After the optimum conditions had been determined, it was possible to selectively extract 99.0% of cobalt from ammoniacal feed solution containing Co²⁺ and Ni²⁺ ions. The separation factors of cobalt with respect to nickel, based on initial feed concentration, have experimentally found to be of as high as 247.5 for about equimolar Co–Ni feed solutions.     

Determination of five trace elements in sea water after separation by anion-exchange chromatography

Summary A preconcentration technique involving anion-exchange in a thiocyanate medium has been developed for the determination of traces of vanadium, cobalt, copper, zinc, and cadmium in sea water. A conventional, small column containing a strongly basic anionexchange resin Amberlite CG 400 in the thiocyanate form allows the five trace metals to be concentrated from a 11 of sea water sample adjusted to 0.1M in thiocyanate and 0.1M in hydrochloric acid. Sorbed metals can be recovered simultaneously by elution with 140 ml of 2M perchloric acid. A stepwise elution technique is also developed, which permits removal of vanadium-copper-cobalt as a group, zinc, and cadmium to improve the selectivity of the separation. A simple scheme of separation for vanadium, copper, and cobalt is given, so that spectrophotometric determinations of these metals even with nonselective reagents may be feasible. Results are quoted on the preconcentration and subsequent spectrophotometric determination of the five metals in brine and sea waters.     

Spectrophotometry Determination of Cobalt after Extraction of its Ternary Complex with 3-(4-Phenyl-2-Pyridyl)-5,6-Diphenyl-1,2,4-Triazine and Tetraphenylborate into Molten Naphthalene

The reaction of 3-(4-phenyl-2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PPDT) and tetraphenylborate (TPB) with cobalt (II) has been studied to determine the optimum conditions for the extraction and quantitative spectrophotometry determination of this metal. The ternary complex is extracted into molten naphthalene at pH 3.6–7.4. The solid naphthalene containing the cobalt associated complex is separated by filtration and dissolved in acetonitrile. Beer's law is obeyed in the concentration range 8–140 μg cobalt in 10 ml of acetonitrile solution. The molar absorptivity and sensitivity are 4.2×10³ l·mol^?1·cm^?1 and 0.01408 μg/cm², respectively. The other factors such as pH, amounts of reagents and naphthalene, shaking and standing times, and the effect of diverse ions are studied. The method has been applied to the determination of cobalt in iron steel alloys.     

Reversed phase foam chromatography : Separation of iron from copper,cobalt and nickel in the tri-n-butyl phosphate-hydrochloric acid system

The separation of iron from cobalt, copper and nickel by reversed-phase foam chromatography was investigated. The distribution of Fe, Co and Cu in TBP-HCl and TBP(polyurethane foam)-HCl systems was measured. Iron can be separated from the three other metals on polyether-type polyurethane foam columns loaded with TBP. The break-through curve of iron on TBP (polyurethane foam) columns was measured. The column was found suitable for the separation of ⁵⁸Co and ⁵⁹Fe isotopes.     

Co-crystallization of ultramicro quantities of cobalt with α-nitroso-β-naphthol

The co-crystallization of ultramicro quantities of cobalt with α-nitroso-β-naphthol, was investigated by radio-tracer techniques. More than 99% cobalt, even when carrier-free, could be recovered. The distribution was studied and appeared to follow the logarithmic distribution law. The interference of a large excess of zinc was almost negligible. The method was applied to tlie carrier-free separation of cobalt isotopes (⁵⁵Co, ⁵⁶Co, ⁵⁷Co, ⁵⁸Co) produced by deuteron bombardment of an iron target. Contamination by manganese (⁵⁴Mn, ⁵²Mn) and iron (⁵⁹Fe) was, even in the absence of manganese carrier, almost negligible.     

Polyurethane-pyridylazonaphthol foams in the preconcentration and separation of trace elements

The feasibility of using PAN—polyether and polyester polyurethane foams in batch and column operations has been examined. The effects of pH, plasticizer and various anions present in the aqueous solution on the extraction behaviour of cobalt, iron and manganese have been investigated. In dynamic systems, the effect of flow rate on the extraction efficiencies of these metal ions has been investigated. The uptake of cobalt(III) and manganese(II) on PAN—polyester foam columns is quantitative at flow rates up to 10 ml min^-1 and 2 ml min^-1, respectively. The retention of iron(III) by the foam column is not quantitative even at a flow rate of 1 ml min^-1. Preconcentration of cobalt and its separation from various concentrations of manganese are successful..     

60Co removal from aqueous solutions using charcoal

Charcoal, treated in different ways, can be used in the separation of⁶⁰Co from aqueous solutions. The cobalt species involved in the process were identified by high voltage electrophoresis. The best results were obtained using thermally and chemically treated charcoal with a maximum retention of 1.24 mmol cobalt per gram. It was also found that the cobalt was not desorbed from the chemically treated charcoal when washed with distilled water. However, it was eluted from the charcoal with 2.3N hydrochloric solution. Samples containing⁶⁰Co were analysed during the sorption process by gamma-ray spectrometry.     

Reversed-phase foam chromatography: Separation of trace amounts of cobalt from nickel in the tri-n-octvlamine-hydrochloric acid system

The separation of cobalt and nickel in hydrochloric acid media by reversed-phase chromatography on open-cell polyether-type polyurethane foam columns loaded with tri-n-octylamine hydrochloride has been studied. The results showed that good results are obtained with 11.4 and 17.7% loadings of the amine. The separation was studied in the Ni:Co range from 1 to 10⁸.     

Determination of cobalt(II), copper(II) and iron(II) by ion chromatography with chemiluminescence detection

An optimized flow-injection manifold for the chemiluminescence determination of cobalt(II), copper(II), iron(II) and chromium(III) by their catalytic effect on the luminol reaction is described. Detection limits are 0.0006, 0.08, 0.3 and 0.1 ng ml^?1, respectively. The suppression effect of several carboxylic acids on the emission intensity is discussed. A procedure for the separation of cobalt(II), copper(II) and iron(II) on a low-capacity, silica-based cation-exchange column, using 5 mM oxalic acid at pH 4.2 as the mobile phase and post-column detection via the luminol reaction, is also described. Detection limits for cobalt(II) and copper(II) are 0.01 and 5 ng ml^?1, respectively.     

Directed Electron Delivery from a Pb-Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO2 Photoreduction Coupled with Water Oxidation

The development of high-performance photocatalytic systems for CO₂ reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs₂AgBiBr₆ nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g⁻¹ h⁻¹ for visible-light-driven CO₂-to-CO conversion coupled with water oxidation to O₂, over 8 times of the unmodified Cs₂AgBiBr₆ (36±8 μmol g⁻¹ h⁻¹), also far surpassing the documented systems (<150 μmol g⁻¹ h⁻¹). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs₂AgBiBr₆ can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.