Re‐evaluation of distillation and comparison with HNO3 leaching/solvent extraction for isolation of methylmercury compounds from sediment/soil samples

Distillation was re‐evaluated for the formation of artifacts arising from increasing naturally occurring mercury(II) concentrations, as opposed to previous identification of artifacts by spiking standard mercury(II) into samples. Naturally occurring mercury(II) concentrations lower than 2 µg g^?1 were found not to affect methylmercury (MeHg) results. However, when the natural concentrations of mercury(II) were greater than 2 µg g^?1, in contrast to standard mercury(II) spiked in samples, the MeHg concentrations measured were found to decrease (not increase) with increasing naturally occurring mercury(II) concentrations. This indicated that standard mercury(II) spiked in samples behaved differently from naturally occurring mercury(II) in the formation of MeHg artifacts during distillation. As a result, spiking standard mercury(II) into samples to identify the formation of MeHg artifacts is not adequate. It is difficult to explain why high naturally occurring mercury(II) suppresses MeHg measurements during distillation. In comparison with HNO₃ leaching/solvent extraction (and other existing techniques), distillation was found to generate results comparable for samples containing less than 2 µg g^?1 mercury(II). The HNO₃ leaching/solvent extraction showed significant advantages over other procedures, as this technique generated the highest recoveries with good precision for all samples analyzed, and the results were found to be independent of mercury(II) concentrations for both naturally occurring and spiked standard mercury(II). Thus, except for samples from high mercury‐contaminated fields, distillation is still a good choice. Both the positive bias (possibly caused by artifact formation of MeHg) and the negative bias (due to incomplete leaching, back‐adsorption, and/or decomposition of MeHg) were investigated. Geologically, physically, and chemically different samples were used for the investigation. Copyright © 2004 John Wiley & Sons, Ltd.     

The influence of β-FeOOH nanorods on the thermal stability of poly(methyl methacrylate)

Colloidal dispersions consisting of β-FeOOH nanorods with three different aspect ratios (4, 75 and 120) were synthesized using thermal hydrolysis of FeCl₃ solutions. After surface modification with oleic acid, the β-FeOOH nanorods were incorporated in poly(methyl methacrylate). Transmission electron microscopy and X-ray diffraction were applied for structural characterization of the β-FeOOH nanorods. The influence of inorganic phase on the thermal properties of PMMA matrix was studied using thermogravimetry and differential scanning calorimetry. Improvement of the thermal stability and increase of the glass transition temperature were found with the increase of content of inorganic phase and the increase of aspect ratio.     

Investigation of the molybdate(II)-3-hydroxyflavone complex

Summary Investigations on the composition of the molybdate(II)-3-hydroxyflavone complex and its stability constant have been carried out in 70% ethanolic solutions at room temperature (20°C), in the presence of a buffer atpH 6.30±0.05 and ionic strength 0.015. It has been found that a complex [MoO₃(C₁₅H₉O₃) ₂ ^2– ] whose stability constant ranges from 15.13 atpH 6.25 to 13.02 atpH 7.00 is formed. Conditions are given for the determination of 3-hydroxyflavone by means of the reaction of complex formation in 50% ethanol atpH 6.60±0.05 and an ionic strength of 0.0225.

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Untersuchung des Molybdat(II)-3-hydroxyflavon-Komplexes

Zusammenfassung Die Untersuchungen der Zusammensetzung des Komplexes und seiner Stabilitätskonstante wurden in 70% Ethanol, bei Raumtemperatur (20°C), in Anwesenheit von Puffer beipH=6.30±0.05 und der Ionenstärke 0.015 ausgeführt. Es wird der Komplex [MoO₃(C₁₅H₉O₃) ₂ ^2– ] gebildet, die Stabilitätskonstanten reichen von 15.13 beipH 6.25 bis zu 13.02 beipH 7.00. Es wurden die Bedingungen zur quantitativen Bestimmung von 3-Hydroxyflavon mittels des Molybdenkomplexes in 50% Ethanol, beipH=6.60±0.05 und der Ionenstärke 0.0225 ermittelt.

     

Synthesis of copolymer brushes endowed with adhesion to stainless steel surfaces and antibacterial properties by controlled nitroxide-mediated radical polymerization

Novel copolymer brushes have been synthesized by a two-step "grafting from" method that consists of the electrografting of poly(2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-ethylacrylate) onto stainless steel, followed by the nitroxide-mediated radical polymerization of 2-(dimethylamino ethyl)acrylate and styrene or n-butyl acrylate, initiated from the electrografted polyacrylate chains. The grafted copolymers were quaternized in order to endow them with antibacterial properties. Peeling tests have confirmed the strong adhesion of the grafted copolymer onto the stainless steel substrate. Quartz crystal microbalance experiments have proven that fibrinogen adhesion is lower on the hydrophilic quaternized films compared to the nonionic counterpart. Such quaternized copolymers exhibit significant antibacterial activity against the Gram-positive bacteria S. aureus and the Gram-negative bacteria E. coli.     

The sorption of anthracene onto goethite and kaolinite in the presence of some benzene carboxylic acids

The uptake of anthracene from dilute aqueous solutions onto goethite and kaolinite was investigated at 25 degrees C, first in the absence and then in the presence of three benzene carboxylic acids: phthalic acid (benzene-1,2-dicarboxylic acid), trimesic acid (-1,3,5-), and mellitic acid (-1,2,3,4,5,6-). Carboxylic acid concentrations were 0.20, 0.10, and 0.05 mM. Anthracene (0.20 microM) did not adsorb strongly onto the pure mineral surfaces, but in the presence of phthalic acid a substantial increase in anthracene uptake was observed, particularly for the goethite systems. Trimesic and mellitic acids did not enhance anthracene uptake. Phthalate and proton adsorption data have been used to model phthalate adsorption onto the mineral surfaces using an extended constant capacitance surface complexation model. This model was then successfully adapted to account for the observed increase in anthracene uptake, where anthracene molecules were assumed to interact with adsorbed phthalate. We propose that the enhancement of anthracene adsorption in the presence of phthalic acid is due to an increase in the hydrophobicity of the mineral surface once phthalic acid molecules adsorb. The same effect was not observed for the other benzene carboxylates because of their greater polarity.     

Inclusion Complexation of Carbaryl and β-Cyclodextrin in Solution and in the Solid State

This study was carried out with the aim ofinvestigating the interactions between-cyclodextrin and carbaryl, a carbamatepesticide, and their effect on some physico-chemicalproperties of carbaryl, such as aqueous solubility andlipophilicity. The interactions between carbaryl and-cyclodextrin were thoroughly investigated bothin solution and in the solid state. The effect of-cyclodextrin on the aqueous solubility ofcarbaryl was evaluated by the phase solubility method.The amount of carbaryl dissolved increased linearlywith the addition of -cyclodextrin according toan A_L type plot and without precipitation of thecomplex. The apparent stability constant of thecomplex was 289 ± 21 M^-1, assuming a 1 : 1stoichiometry; this value was confirmed by a methodbased on circular dichroism measurements.Equimolar carbaryl/-cyclodextrin solid systemswere prepared by physical-mixing and freeze-drying,and fully characterised by Differential ScanningCalorimetry, X-ray powder diffractometry and FourierTransform Infra-Red analysis. The results of the solidstate study demonstrated that the freeze-drying methodyields a system with a high degree of amorphisationand yields an inclusion complex.The dissolution profile of the pesticide was affectedby the physico-chemical properties of each solidsystem, the freeze-dried form dissolving more rapidly. However, the physical association of-cyclodextrin and carbaryl enhanced the aqueoussolubility of the insecticide as well.     

Room temperature single-photon sources based on single colloidal nanocrystals in microcavities

Direct lithography of resist blends, embedding semiconductor colloidal nanocrystals (NCs) is an innovative way to achieve nanopositioning of NCs in quantum-confined optical resonators. In this work, we show a new appealing approach for the fabrication of single-photon sources operating at room temperature by localizing semiconductor colloidal NCs into vertical planar microcavities with lithographic techniques.     

Bi-hybrid coatings: polyaniline-montmorillonite filler in organic-inorganic polymer matrix

A bi-hybrid composite is represented by an organic-inorganic (O-I) filler dispersed in an O-I matrix. Polyaniline-montmorillonite, as a nanocomposite filler, was synthesised by two independent processes: (1) montmorillonite was surface-modified with a conducting polymer, polyaniline, during the in-situ oxidation of aniline or (2) montmorillonite was pre-treated with aniline, then the aniline was polymerised and the polyaniline subsequently produced penetrated the montmorillonite structure. The organic-inorganic polymer matrix was formed in two independent steps: (1) inorganic building units were formed in situ by the sol-gel process, (2) followed by organic polymeric matrix formation by polyaddition reactions of epoxy groups with amines. Polyaniline-montmorillonite filler was added to the reaction system between these two steps, i.e. when the inorganic structures of the O-I matrix have already been formed but prior to formation of the organic polymeric matrix. Two different O-I matrices were prepared from functionalised organosilicon precursors and oligomeric amines. 3-[(Glycidyloxy)propyl]trimethoxysilane reacted with α,ω-oligo(propylene oxide) diamine and diethoxy[3-(glycidyloxy)propyl]-methylsilane reacted with α,ω-oligo(propylene oxide) triamine. The resulting bi-hybrid coatings, the O-I filler dispersed in the O-I matrix, were characterised by atomic-force and optical microscopies, and also by tensile tests. The filler composition affected both the mechanical and surface properties of the coatings.     

Benefits of mesopores in sulfated zirconia catalyst

Activities of two catalysts obtained from hydroxide and alkoxide precursors were correlated to their different structural and textural properties. Activity is mainly determined by the presence of active tetragonal phase, which is more stable at high temperatures in the catalyst of alkoxide origin than in one from hydroxide. An appropriate structure must be accompanied with beneficial pore structure, as is the case of mesopores of the catalyst from alkoxide. In the case of very small pores of the catalyst from hydroxide precursor, activity is negligible due to pores plugged by coke.