On-line preconcentration method for the determination of trace metals in water samples using a fully automated pretreatment system coupled with ICP-AES.

An automated on-line sample-preparation method using a computer-controlled pretreatment system (Auto-Pret AES system) coupled with ICP-AES was developed. In this work, an iminodiacetate chelating resin, packed in a mini-column and installed in the system was employed for the collection/concentration of 13 trace metals, including such toxic metals as Be, Cd, Cr, Cu and Pb. The limits of detection of the proposed method for trace metals were in the range of 0.001 (Be) -0.18 (Pb) ng mL-1. The enrichment factors for metal ions were about 19 times, when 5 mL of samples were used. The sample throughput was 11 h-1. The accuracy and the precision of the method were evaluated using river-water reference materials, SLRS-4 from NRCC, JSAC 0301-1 and JSAC 0302 from the Japan Society for Analytical Chemistry. The proposed method can be favorably applied to the collection/concentration of trace metals in natural water samples.     

Selective enzyme amplification of NAD/NADH using coimmobilized glycerol dehydrogenase and diaphorase with amperometric detection

A flow system for substrate recycling of NAD⁺/NADH was set up with an enzyme reactor containing coimmobilized glycerol dehydrogenase (GDH) and diaphorase. The product from the diaphorase catalysis, hexacyanoferrate(II), aws detected amperometrically at a glassy carbon electrode. The amplification factor was 150 for a reactor volume of 100 μ l at a flow-rate of 0.5 ml/min. With a stopped flow of four minutes, the signal increased another 88 times, resulting in a signal amplification of 13 300 times. Equations are derived for the amplification factor and used for a discussion of the optimization of amplification systems. The K_m for GDH with glycerol as a substrate was found to be 5 × 10⁻³ M at pH 8.0. GDH from Cellulomonas sp. was purified on a gel filtration column and the purified enzyme showed a specificity toward NAD⁺, compared to NADP⁺, that was higher than 99.9%. Due to the NAD⁺ specificity of the purified GDH, the enzyme amplification system reported here could be used in detection systems for enzyme immunoassays when using alkaline phosphatase as a label and NADP⁺ as a substrate. The stability of immobilized GDH and diaphorase is several orders of magnitude better than that of alcohol dehydrogenase, which is the enzyme commonly used for NAD⁺-specific detection in these applications.     

Solvophobically Driven Complexation of Adamantyl Mannoside with β-Cyclodextrin in Water and Structured Organic Solvents

The effects of solvent and temperature on the complexation of adamantyl mannoside with β-cyclodextrin and 6-O-monotosyl-6-deoxy-β-cyclodextrin were explored experimentally and by means of molecular dynamics simulations. Efficient binding was observed only in hydrogen-bonded solvents, which indicated solvophobically driven complexation. The stability of the inclusion complex was considerably higher in aqueous media. A pronounced temperature dependence of Δ_rH^○ and Δ_rS^○, resulting in perfect enthalpy–entropy compensation, was observed in water. The complexation thermodynamics was in line with classical rationale for the hydrophobic effect at lower temperatures and the nonclassical explanation at higher temperatures. This finding linked cyclodextrin complexation thermodynamics with insights regarding the effect of temperature on the hydration water structure. The complexation enthalpies and entropies were weakly dependent on temperature in organic media. The signs of Δ_rH^○ and Δ_rS^○ were in accordance with the nonclassical hydrophobic (solvophobic) effect. The structures of the optimized product corresponded to those deduced spectroscopically, and the calculated and experimentally obtained values of Δ_rG^○ were in very good agreement. This investigation clearly demonstrated that solvophobically driven formation of cyclodextrin complexes could be anticipated in structured solvents in general. However, unlike in water, adamantane and the host cavity behaved solely as structure breakers in the organic media explored so far.     

Tailoring thermal development of gamma alumina sorbents material using combustion synthesis: the effect of amino acids (G,A, N) and equivalence ratio

Using a combustion synthesis, the range of achievable textures is broader than using conventional synthesis methods and can be controlled more successfully. As a tool allowing the achievement and control of desired textures, here we bring about wet chemistry synthesis using aluminium nitrate nonahydrate (ANN) precursor systematically combined with different fuels (amino acids). The amino acids; glycine (G), alanine (A) and asparagine (N) have been specifically selected in order to show the role of gradual increase in their: (1) molar mass, (2) enthalpy of combustion, (3) amine groups content and (4) ratio to ANN. Detailed (micro) structural and thermal characterisations confirm that the nanocrystalline character and thermomechanical stability were not diminished in the course of this synthesis. The conditions leading to development of different morphologies from gels to powders were found to be heavily under the influence of fuel/oxygen ratio, i.e. of the smouldering versus flaming mechanism of the combustion. Higher content of nitrates (predominately from amino-rich amino acids) strongly promoted auto-combustion behaviour. As-derived alumina precursors have been thermally treated at various temperatures (quenched and soaked), to monitor γ- and α-alumina crystallisation, with respect to the development of morphology. Different texture types have been observed, such as porous wormhole, porous and porous expanded flakes. Higher fuel levels promote specific surface increase. This combustion synthesis allows facile tailoring of nanocrystalline γ-alumina with different morphological features, whereas samples having optimal parameters were suitable for catalyst support application on behalf of rapid sorption performance.

     

Tetraaquabis(d‐camphor‐10‐sulfonato)calcium(II)

The structure of the title compound, [Ca(C₁₀H₁₅O₄S)₂(H₂O)₄], is the first example in which two d ‐camphor‐10‐sulfonate anions are coordinated to a metal ion, in this case with direct Ca—O bonding. The molecule has crystallographically imposed twofold symmetry with the Ca atom on the twofold axis. Hydrogen bonds are formed between the coordinated water molecules and the O atoms of the SO₃⁻ groups of adjacent molecules, leading to the formation of a two‐dimensional layered network. The compound displays sharp wavelength‐selective transparency in the UV–visible spectrum, offering the potential for application as an optical filter.     

X-ray structural analysis and antitumor activity of new salicylic acid derivatives

Tetrakis-, tris-, bis-, and mono salicylic acid derivatives 1–4 were synthesized by reaction of methyl 2-hydroxy benzoate (methyl salicylate) with 2,2-bis (hydroxymethyl) propane-1,3-diol (pentaerythritol) in the presence of sodium. Yields of different salicyloyloxy derivatives were changed by varying the molar ratios of reactants. For compounds 2 and 3, X-ray structure analysis was performed, as well as molecular energy minimization, to define their conformation in terms of their energy minima. Comparison of crystal and energy minimized structures for these two compounds (2 and 3) revealed that the intramolecular hydrogen bonds play an important role, stabilizing conformation of the most part of the molecule. The antioxidant activity and cytotoxicity of the synthesized derivatives were evaluated in a series of in vitro tests, as well as 17β-hydroxysteroid dehydrogenase type 2 inhibition potency. Tetrakis salicyloyloxy derivative 1 expressed the highest antioxidant potency, tris salicyloyloxy derivative 2 was the best inhibitor of 17βHSD2 enzyme, while bis salicyloyloxy derivative 3 showed strong cytotoxicity against prostate and breast cancer cells with no cytotoxicity against healthy cells.     

Determination of total chromium in fresh water by atomic absorption spectrometry following flotation preconcentration

A flotation method is proposed for the quantitative preconcentration and determination of total chromium by electrothermal atomic absorption spectrometry in fresh water samples, without previous reduction or oxidation of the chromium ion state. Hydrated iron(III) oxide and iron(III) tetramethylenedithiocarbamate were used as precipitating collectors. The detection limit of the method is 0.01 g/L.