Salicylate-selective membrane electrode based on tin(IV) tetraphenylporphyrin

The response properties of a new solvent/polymeric membrane electrode with unique selectivity toward anionic salicylate are reported. The electrode is prepared by incorporating 5, 10, 15, 20-tetraphenyl(porphyrinato)tin(IV) dichloride (Sn[TPP]Cl2) into a plasticized poly(vinyl chloride) membrane. The resulting sensor exhibits an anti-Hofmeister selectivity pattern, with high specificity for salicylate over lipophilic inorganic anions (perchlorate, periodate, thiocyanate, iodide, etc.) and biological organic anions (citrate, lactate, acetate). Moderate selectivity over structural analogues of salicylate (3- and 4-hydroxybenzoate, benzoate) is also observed. Radiotracer uptake experiments using [14C]salicylate clearly show that the metal center of the metalloporphyrin is critical for selective salicylate transport in the membrane phase. Minimal response to chloride ions makes the new electrode potentially useful for estimating salicylate levels in biological samples.     

Characterization of Fe(III)-Zr(IV) mixed and Sn(III)-doped hydrous oxides

Surface and structural properties of iron-zirconium mixed and Sn(II)-doped hydrous oxide gels have been compared with ferric oxide hydrate gel using thermal analysis, infrared spectroscopy, X-ray diffraction, electron microscopy and magnetic measurements. The mixed and doped oxide gels were found to consist of a hexagonal close packed arrangement of oxygen sublattices similar to those present in -FeOOH and -Fe₂O₃, with the iron ion quite randomly distributed in the gels. The gels were found to be composed of hexagonal to rounded and thin rod-like particles and their agglomerates. The particles in the superparamagnetic state have an incompletely compensated antiferromagnetic character.     

Electrical properties of Ga(III), In(III), Zr(IV) and Sn(IV) complexes with Schiff bases derived from 2-hydroxynaphthaldehyde and phenylenediamines

Electrical conductivity measurements were carried out for some Schiff bases derived from 2-hydroxy-1-naphthaldehyde with o-, m- and p-phenylenediamines and their metal complexes with some tri- and tetravalent ions. It has been concluded that the complexes have slight semiconducting properties. The conductivity and the activation energy were found to depend on the molecular structure of the complex as well as the ionic potential of the metal ion. The current-voltage dependence was studied for some complexes which indicated an ohmic conduction.     

Salicylate-selective electrode based on a biomimetic guanidinium ionophore

A biomimetic strategy was employed in the development of oxoanion-selective ionophores containing the guanidinium functional group. These ionophores mimic the selective interaction observed between arginine residues of proteins and oxoanions. In previous work, it was demonstrated that a structurally rigid guanidinium ionophore exhibited excellent hydrogen sulfite selectivity (Anal. Chem. 1994, 66, 3188-3192). Herein, we describe guanidinium-containing ionophores that are selective for the oxoanion salicylate. The ability to rationally design anion-selective electrodes through this biomimetic strategy, and to both alter selectivity and improve response characteristics through structural changes to the ionophore, has been demonstrated. (1)H-NMR complexation and modeling studies were used to examine and correlate the selectivity observed with the structure of the guanidinium compounds.     

Development of nano indium tin oxide (ITO) grains by alkaline hydrolysis of In(III) and Sn(IV) salts

Indium tin oxide (ITO) nano powders of different compositions (In: Sn = 90: 10, 70: 30 and 50: 50) were prepared by heat treatment (300-450°C) of mixed hydroxides of In(III) and Sn(IV). The hydroxides were obtained by the reaction of aq. NH₃ with mixed aq. solutions of In(NO₃)₃ and SnCl₄. FTIR and TG/DTA studies revealed that powders existed as In(OH)₃H₂O—SnO₃H₂H₂O in the solid state and then they transformed to In₂O₃—SnO₂ via some metastable intermediates after 300°C. Cubic phase of In₂O₃ was identified by XRD for the oxides up to 30% of Sn. Particle size measurements of the solid dispersed in acetone and SEM study for microstructure showed that the oxides were in the nano range (55-75 nm) whereas the size range determined from Debye-Scherrer equation were 11–24 nm.     

Intermetallic compound formation between lead-free solders (Sn) and Cu or Ni electrodes

A kinetic model based on the principle of maximum degradation rate of the total system free energy, MDR law using thermodynamic data, is proposed and successfully applied to the selection of the first intermetallic compound (IMC) phase in Cu/Sn and Ni/Sn diffusion couples. The first phases predicted with this model for Cu/Sn and Ni/Sn are Cu₆Sn₅ and Ni₃Sn₄, respectively, resulting in good agreement with experimental observations.     

Coprecipitation of neptunium(IV) and plutonium(IV) with hydrolyzed iron(III) in carbonate solutions

In regeneration of Np(IV)-and Pu(IV)-containing recycled solvent by treatment with aqueous sodium carbonate contaminated with iron, some portion of Np(IV) and Pu(IV) coprecipitates with hydrolyzed iron. The degree of coprecipitation of Np and Pu depends on both the iron and sodium carbonate concentrations. The presence of n-dibutyl hydrogen phosphate in the recycled solvent before its regeneration does not noticeably affect the coprecipitation of Np and Pu. The possible mechanisms of coprecipitation of actinides with hydrolyzed iron in carbonate solutions are discussed.     

Synthesis and photocatalytic properties of nanomaterials based on titanium(IV) and cerium(IV) oxides

We have studied the phase transitions, morphology, and photocatalytic activity of titanium(IV) oxide–cerium(IV) oxide materials at Ce doping levels from 1 to 20 wt % and heat-treatment temperatures from 80 to 1150°C. The highest photocatalytic activity under illumination in the spectral range λ ≥ 670 nm is offered by mesoporous X-ray amorphous and multiphase (X-ray amorphous phase + anatase + rutile + CeO₂) nanomaterials, whereas the two-phase materials (rutile + CeO₂) have the lowest photocatalytic activity.     

Bismuth (III) PVC membrane ion selective electrodes based on two compounds: Acylhydrazone and thiosemicarbazone with 1,3,4-thiadiazole

Two Bi^3 + selective electrodes based on L1 and L2 incorporated into a polyvinylchloride (PVC) membrane have been developed. The ionophores L1 and L2 are 2-(5-amino-1,3,4-thiadiazol-2-ylthio)-N′-benzylidene acetohydrazone and 1-(2-(5-amino-1,3,4-thiadiazol-2-ylthio) acetyl)-4-benzoylthiosemicarbazone, respectively. These electrodes are composed of dioctylphtalate (DOP) as a plasticizer and sodium tetraphenylborate (NaTPB) as the lipophilic additive. The best performance was obtained with the membrane compositions of L1 (0.30): PVC (33.22): DOP (66.36): NaTPB (0.12) (%, w/w) and L2 (1.00): PVC (33.00): DOP (65.91): NaTPB (0.09) (%, w/w). Two membrane electrodes show Nernstian response slopes towards Bi^3 + (20.2 and 19.7 mV/decade, respectively) over the concentration range of 10^? 7–10^? 3 and 10^? 7–10^? 2 M, respectively. The effects of the pH and the possible interfering cations were investigated. Both electrodes have a response time of about 10 s, and they can work in a certain concentration aqueous ethanol solution. The prepared electrodes were used as an indicator electrode in potentiometric titration of Bi^3 + ions with EDTA. The membrane sensors were also applied to the determination of Bi^3 + content in compound bismuth aluminate tablets.     

Adsorption characteristics and separation of Cr(III) and Cr(VI) on hydrous titanium(IV) oxide

A hydrous titanium(IV) oxide was prepared to study the adsorption characteristics and the separation of chromium species. Batch sorption studies have been carried out to determine the effect of pH on the sorption of Cr(III) and Cr(VI) on hydrous TiO2. An excellent separation efficiency of Cr(III) and Cr(VI) was obtained at pH 2. The adsorption percentage of Cr(VI) was above 99%, whereas that of the Cr(III) was less than 1% at this pH. The adsorption isotherm of Cr(VI) on hydrous TiO2 at pH 2 was in good agreement with the Langmuir isotherm. The maximum adsorption capacity of Cr(VI) on TiO2 was 5 mg g(-1). The rate of adsorption of Cr(VI) by hydrous TiO2 with average particle diameter 250 and 500 microm has been studied under particle diffusion controlled conditions. The diffusion coefficients of Cr(VI) for both hydrous TiO2 having average particle diameter of 250 and 500 microm was calculated at pH 2 as 3.84 x 10(-10) m2 s(-1) and 8.86 x 10(-10) m2 s(-1), respectively.     

Lanthanum(IlI) PVC membrane electrodes based on 1,3,5-trithiacyclohexane

Novel plasticized polymeric membrane (PPME) and membrane-coated graphite (MCGE) electrodes based on 1,3,5-trithiacyclohexane for highly selective determination of La3+ ion have been developed. The electrodes exhibit Nernstian responses over very wide concentration ranges (8.0 x 10(-6)-5.0 x 10(-2) M for PPME and 4.0 x 10(-8)-1.0 x 10(-2) M for MCGE). The limit of detections were 5.0 x 10(-6) and 2.0 x 10(-8) M for PPME and MCGE, respectively. The electrodes possess a fast response time of approximately 10 s and can be used for at least 6 months without observing any deviation. The proposed electrodes revealed excellent selectivities for La3+ over a wide variety of alkali, alkaline earth, transition, and heavy metal ions and could be used in a pH range of 5.0-8.0. The practical utility of the electrodes has been demonstrated by their use as indicator electrodes in the potentiometric titration of La3+ ions with EDTA and in determination of F- in some mouthwash preparations.     

Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes

A novel method for the detection of arsenic(III) in 1 M HCl at a gold nanoparticle-modified glassy carbon electrode has been developed. The gold nanoparticles were electrodeposited onto the glassy carbon electrode via a potential step from +1.055 to -0.045 V vs SCE for 15 s from 0.5 M H2SO4 containing 0.1 mM HAuCl4. The resulting electrode surfaces were characterized with both AFM and cyclic voltammetry. Anodic stripping voltammetry of arsenic(III) on the modified electrode was performed. After optimization, a LOD of 0.0096 ppb was obtained with LSV.     

Electrochemical detection of arsenic(III) using iridium-implanted boron-doped diamond electrodes

Iridium-modified, boron-doped diamond electrodes fabricated by an ion implantation method have been developed for electrochemical detection of arsenite (As(III)). Ir+ ions were implanted with an energy of 800 keV and a dose of 10(15) ion cm(-2). An annealing treatment at 850 degrees C for 45 min in H2 plasma (80 Torr) was required to rearrange metastable diamond produced by an implantation process. Characterization was investigated by SEM, AFM, Raman, and X-ray photoelectron spectroscopy. Cyclic voltammetry and flow injection analysis with amperometric detection were used to study the electrochemical reaction. The electrodes exhibited high catalytic activity toward As(III) oxidation with the detection limit (S/N = 3), sensitivity, and linearity of 20 nM (1.5 ppb), 93 nA microM(-1) cm(-2), and 0.999, respectively. The precision for 10 replicate determinations of 50 microM As(III) was 4.56% relative standard deviation. The advantageous properties of the electrodes were its inherent stability with a very low background current. The electrode was applicable for analysis of spiked arsenic in tap water containing a significant amount of various ion elements. The results indicate that the metal-implanted method could be promising for controlling the electrochemical properties of diamond electrodes.     

Ultraviolet absorption of cerium(III) and cerium(IV) in some simple glasses

The optical absorption spectra of cerium (III) and cerium (IV) in Na₂O-B₂O₃, Na₂O-SiO₂, Na₂O-P₂O₅ glasses, and in H₂O-H₂SO₄ and H₂O-H₃PO₄ solutions have been studied. Individual molar extinction coefficients of cerium (III) and cerium (IV) at different wavelengths (350 to 200 nm) have been estimated. In all the glasses and solutions, cerium (IV) produces a very strong and broad charge transfer band around 250 nm; the intensity, half-width, and position of this band change appreciably with glass composition. Cerium (III) in glass and in aqueous solution produces a number of absorption bands in the ultraviolet region corresponding to the f → d transitions. The cerium (III) bands are sharp and well resolved in Na₂O-P₂O₅ and in low-alkali borate glasses; the sharpness of resolution deteriorates in Na₂O-SiO₂, and in high-alkali borate glasses. The intensity of cerium (III) absorption also changes with glass composition. In all the glasses the molar extinction coefficient of cerium (IV) is 5 to 10 times stronger than that of cerium (III).     

Separation of Am(III) and Pu(IV) at Their Joint Oxalate Precipitation

A procedure was developed for purification of plutonium to remove americium by oxalate precipitation using diethyl oxalate as a precipitant. The developed procedure was tested under laboratory conditions and on an enlarged installation. It was shown that the decontamination factor of plutonium from americium can exceed 2 ×10³. The plutonium oxalate precipitate can be dissolved by heating with HNO₃ in the presence of V(V) catalyst and also by electrochemical dissolution at alternating current.     

Extraction of Antimony(III) Ions from Solutions by Sorbents Based on Titanium(IV) Compounds

Inorganic Materials - Sorbents based on titanium(IV) compounds have been shown to be potentially attractive for quantitative removal of antimony(III) anions from liquid radioactive waste with...     

Mechanochemically assisted synthesis of pristine Ca(II)Sn(IV)-layered double hydroxides and their amino acid intercalated nanocomposites

Syntheses of Ca(II)Sn(IV)-layered double hydroxides (LDHs) are attempted by the traditional co-precipitation as well as mechanochemical methods. Both the co-precipitation method and the one-step milling operation proved to be unsuccessful; these methods only produced physical mixtures of hydroxides and carbonates of the two metal ions. However, a two-step milling operation (dry milling followed by milling in the presence of minute amount of water) led to successful synthesis, verified by a range of characterisation methods. Surprisingly, it was found that ball-milling was not even necessary; the reaction proceeded on manual grinding of the components in an agate mortar with a pestle. The preparation of nanocomposites through intercalation of the anions of cystine or valine into Ca(II)Sn(IV)-LDH could also be achieved by the two-step milling method verified again by a range of instrumental methods.