Kondo lattice and heavy fermions in Heusler phases: CeInAg2−xCux

Magnetic properties, electrical resistivity, specific heat and magnetic excitations have been investigated in Heusler phases CeInAg_2–xCu_x. The hybridization continuously increases from CeInAg₂ (antiferromagnetic Kondo lattice) to CeInCu₂ (heavy fermion compound). The specific heat coefficient for this last compound is found to reach 1.2 J/mole. K² at 1.4 K, the Kondo temperature is 6 K and the Wilson ratio is close to 2.     

Dilute solution properties of poly(N-vinyl-3,6-dibromo carbazole)—III. Phase equilibrium studies

The phase relationships of poly(N-vinyl-3,6-dibromo carbazole) (PVK-3, 6-Br₂) were examined for four solvents, viz, o-chlorophenol, p-chloro-m-cresol, o-dichlorobenzene and bromobenzene. Upper critical solution temperatures (UCST) have been determined for solutions of PVK-3,6-Br, fractions in o-chlorophenol and p-chloro-m-cresol over the molecular weight range $\text{M}{}_{\mathrm{<mtext>w</mtext>}}\text{× 10}{}^{\mathrm{?4}}\text{= 125.0}\text{to}\text{4.8}$. The Flory temperature, θ, obtained from UCST for the PVK-3,6-Br₂/o-chlorophenol and PVK-3,6-Br₂/p-chloro-m-cresol systems are 66.0 and 112.9°C, respectively. The θ-temperatures were checked against molecular weight and viscosity data to determine the Mark-Houwink equations for these two theta solvents, with satisfactory agreement. The relations are

$\text{[ν] = 27.5}{}_4\text{× 10}{}^{\mathrm{?10}}\text{×}\text{M}{}^{0.50}{}_{\mathrm{<mtext>w</mtext>}}\text{(o-}\text{chlorophenol}\text{, 60.0°}\text{C}$

$\text{[ν] = 30.2}{}_4\text{× 10}{}^{\mathrm{?10}}\text{×}\text{M}{}^{0.50}{}_{\mathrm{<mtext>w</mtext>}}\text{(p-}\text{chloro}\text{-m}\text{cresol}\text{, 112.9°}\text{C}$

The characteristic ratio C_∞ = 〈R²〉₀/nl² was found to be 16.6 in o-chlorophenol at 60.0°C and 17.6 in p-chloro-m-cresol at 112.9°C. The value of the characteristic ratio C_∞ of PVK-3,6-Br₂ is of the same order of that for poly(N-vinyl carbazole). This indicates that the bromine atoms at the 3 and 6 (meta) positions have only an inappreciable effect on the hindering potential for rotation about the CC bond. This agreement of C_∞ for both polymers may also be taken as indicating that the effect of interaction between polar groups at the m-position on the hindering potential for rotation is small. The phase diagrams of PVK-3,6-Br₂ obtained in o-dichlorobenzene and bromobenzene seem to be characteristic of organized phase structures such as those found in systems exhibiting thermoreversible gelation. Light scattering measurement on PVK-3,6-Br₂ dissolved in o-dichlorobenzene, a gelation promoting solvent, and tetrahydrofuran, a very good solvent, strongly indicate that the macromolecular species in o-dichlorobenzene contain some extent supermolecular structures (aggregates, association of chain segments, etc.). These characteristic structures of PVK-3,6-Br₂ in o-dichlorobenzene and bromobenzene at 25°C are also characterized by high values of the Huggins' constant k′; for tetrahydrofuran solutions, the k′ values were in the range normally found for many good solvent-polymer systems.     

An ultrasensitive method for the determination of thiouracil and phenylthiouracil using capillary zone electrophoresis and laser-induced fluorescence detection

This paper reports the development of a method based on capillary electrophoresis with laser-induced fluorescence detection for the simultaneous determination of thiouracil (TU) and phenylthiouracil (PhTU) with high sensitivity (nanomolar range, i.e., attomoles detected). After derivatization with 5-iodoacetamidofluorescein, the analytes were separated by capillary zone electrophoresis using 20 mM phosphate buffer (pH 10.0) and quantified by fluorescence detection. The linearity range, precision, recovery, and detection limits were determined, and the method was shown to be applicable for the determination of TU and PhTU in spiked feed samples and urine.     

Coupled-column liquid chromatography method with photochemically induced derivatization for the direct determination of benzoylureas in vegetables

The coupled-column (LC-LC) system, consisting of a first column packed with internal surface reversed phase (ISRP) (50 x 4.6mm ID) and a Chrompack C18 (100 x 4.6 mm ID) as second column, allowed the simultaneous determination of five benzoylurea insecticides in dichloromethane (CH2Cl2) extracts of vegetable samples without any clean-up step. This system was combined with a photochemically induced fluorescence (PIF) post-column derivatization in order to provide strongly fluorescent photoproducts from the non-fluorescent benzoylureas. Limits of detection ranged from 0.21 to 0.98 microg L(-1) of pesticide (equivalent to 0.14-0.65 microg kg(-1) in vegetable samples) and limits of determination ranged from 4.0 to 10.0 microg L(-1) (equivalent to 2.7-6.7 microg kg(-1)). Linearity of the method was established between 2 and 1800 microg L(-1), depending upon the compound. Validation of the total method was performed by randomly analyzing recoveries of four vegetable samples (aubergine, cucumber, green bean, and tomato) spiked at two levels of concentration (10.0 and 33.3 microg kg(-1)). The combination of the LC-LC system with PIF detection provides a sensitive, selective, and rapid method for the determination of pesticides in vegetable samples at levels lower than the maximum residue levels (MRLs) established for these compounds by Spanish legislation.     

Protein adsorption in fused-silica and polyacrylamide-coated capillaries

The model proteins cytochrome c, myoglobin, ovalbumin, and beta-lactoglobulin were investigated with regard to their adsorption properties on capillaries for electrophoresis. The model compounds were selected to cover a wide range of properties. Cytochrome c is a basic protein (isoelectric point (pI): 9.6; M(r): 11.7 kDa), beta-lactoglobulin is rather acidic (pI: 5.4, M(r): 18.4 kDa), myoglobin was chosen as a neutral reference protein (pI: 6.8-7.4, M(r): 17.8 kDa), and ovalbumin (pI: 5.1, M(r): 45.0 kDa) was selected as a relatively larger analyte. First, the pH dependence of adsorption was investigated for the bare fused silica. A clear correlation to the respective pIs was noted. For myoglobin and ovalbumin, none or negligible adsorption was found above the pI, whereas strong adsorption was noted just below this parameter. Cytochrome c and beta-lactoglobulin already showed distinct adsorption above their pIs. However, none of the proteins showed any significant adsorption more than one pH unit above the pIs. For linear polyacrylamide-coated capillaries, a decreased but not a complete lack of adsorption was observed. Here, pH-dependent adsorption was noted as well. Regeneration of the capillaries by rinsing with buffers containing 200 mM SDS was also investigated. This method was completely successful for myoglobin, but that too for only freshly-adsorbed protein. After a storage time of 24 h and due to the aging of the adsorbate, a sufficient regeneration was no longer possible.     

Determination of personal care products in water using UHPLC–MS after solid phase extraction with mesoporous silica‐based MCM‐41 functionalized with cyanopropyl groups

A silica‐based MCM‐41 mesoporous material functionalized with cyanopropyl groups has been synthesized by cocondensation, characterized and applied to preconcentrate six parabens and three UV filters in river and swimming‐pool waters. The analytes were quantified by ultra‐high performance liquid chromatography‐tandem mass spectrometry, according to the Directive 96/23/EC. Even though matrix effect was negligible, quantification in river water samples with the standard addition approach improved the recoveries obtained using solvent‐based and even with matrix‐matched calibration. The method quantification limits in river water samples were 0.05 ng/mL for 2,4‐dihydroxybenzophenone and 0.01 ng/mL for the rest. Recoveries, evaluated for a concentration level of 0.5 ng/L, were in the range 93.5‐107.6% for parabens and in the range 64.2‐85.8% for UV filters, with relative standard deviations intraday ≤10.2 and 10.8%, respectively. This parameter, evaluated for a concentration level of 0.1 ng/L, ranged between 98.3 and 110.4% for parabens and between 61.9 and 89.9% for UV filters, with relative standard deviation intraday ≤15.3 and 15.5%, respectively. The two UV filters with lower recoveries were the most affected by the addition of sodium chloride. River and swimming pool waters were analyzed and all the personal care products were found in the swimming pool water, whereas only methylparaben was detected in the river water.     

Application of several modified peak purity assays to real complex multicomponent mixtures by high-performance liquid chromatography with diode-array detection.

Simple to use interactive self-modelling mixture analysis (SIMPLISMA), orthogonal projection (OPA) and Needle Search (NS) approaches have been applied to the determination of a number of compounds present in a complex multicomponent system. None of these three approaches succeeded completely when they were tested using the whole data matrix. When OPA and NS were applied to three simpler submatrices, obtained by dividing the total data matrix, and where a smaller number of compounds were present, better performance was achieved.     

Metal-doped apatitic calcium phosphates: preparation,characterization, and reactivity in the removal of hydrogen sulfide from gas phase

With the expansion of human activities, there are more and more living areas adjacent to industrial and/or agricultural activities such as chemical processes, petroleum processes, paint finishing, food processing, livestock farming, composting plants etc. Bad odor is part of several nuisances caused by industrial and/or agricultural activities. Hydrogen sulfide (H₂S) is a typical odorous molecule which causes foul odor at very low concentration. This molecule is formed in different industrial installations, in particular in coal combustion, and petrochemical refinery. The separation and/or transformation of H₂S from gas phase to odorless products are important processes for sustainable development. In this paper, we communicate the preparation of new sorbents for the sorption of H₂S from a synthetic gas effluent. These sorbents consist in an inorganic phase (hydroxyapatite) as host particles, and well-dispersed particles of a metal oxide as guest particles which are the active phase for the removal of H₂S. At room conditions, iron, lead, and zinc doped calcium phosphates were found to be effective for the removal of H₂S. The performance of the sorbents depends on preparation method and the nature of active phases. This opens new prospects for the treatment of H₂S from gas phase.     

Elimination of spectral interferences in the reaction of 2-thiobarbituric acid with malonaldehyde, 2-furfuraldehyde and 5-hydroxymethyl-2-furfuraldehyde by partial least squares multivariate calibration (PLS)

Summary The spectral resolution of ternary mixtures of malonaldehyde (MLD), 2-furfuraldehyde (FUR) and 5-hydroxymethyl-2-furfuraldehyde (HMF) in the presence of glyoxal and biliverdine is achieved by partial least squares multivariate calibration (PLS). The spectrophotometric method is based on the reaction of these substances with 2-thiobarbituric acid (TBA). A calibration set of standard samples has been statistically designed in the presence of adequate amounts of both interferent compounds in several degrees of concentration. The possibility of a spectrophotometric determination of mixtures of MLD, FUR and HMF in the presence of glyoxal and biliverdine is demonstrated. A comparative study of the results found by application of PLS-1 and PLS-2 methods is presented.     

Solid-phase microextraction for the determination of benzoylureas in orange juice using liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection

A solid-phase microextraction (SPME) method has been developed for the determination of six benzoylureas (diflubenzuron, triflumuron, hexaflumuron, teflubenzuron, lufenuron, and flufenoxuron) in natural orange juice based on the direct immersion mode of a 60 microm polydimethylsiloxane/divinylbenzene fiber. An orange juice was obtained from blended, homogenized, and diluted ecological natural orange juice samples. An aliquot of 3 mL of a spiked sample was extracted under optimum SPME conditions. The determination of benzoylureas was carried out using HPLC combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection. The limits of quantification obtained in matrix were within the range of 0.02 to 0.04 mg/kg and these limits are lower than the maximum residue levels established in Spanish regulations for all pesticides in this study. Recoveries in juice samples ranged between 85 and 110% and relative standard deviations between 1.8 and 7.4%.