Supercritical Fluid Extraction (SFE) Optimization by Full-Factorial Design for the Determination of Irganox 1076, Irgafos 168, and Chimassorb 81 in Virgin and Recycled Polyolefins

The performance and feasibility of supercritical fluid extraction (SFE) applied to the extraction of some antioxidants (Irganox 1076, Irgafos 168) and one UV-stabilizer (Chimassorb 81) from both virgin and recycled low density polyethylene (LDPE), and virgin high density polyethylene (HDPE) are studied. Due to the high number of variables a full-factorial design has been applied to minimize the number of experiments required to reach the optimum extraction conditions. Further analysis has been carried out off-line by reversed-phase HPLC. Modification of the physical properties of the polymeric matrix and increased number of recycling cycles as well as the influence of physical properties on the efficiency of SFE are also discussed.     

Gas-phase deprotonation of arylalkylamines. A collision-induced dissociation study

The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd.     

Isolation of NO(3)(-)-N as 1-phenylazo-2-naphthol (Sudan-1) for measurement of delta(15)N

The conversion of nitrate (NO(3)(-)) to 1-phenylazo-2-naphthol (Sudan-1) has been examined as a method for natural abundance measurement of delta(15)N of NO(3)(-). The reaction results in dilution of NO(3)(-)-N with only one reagent-derived N and the product is readily concentrated from dilute samples by reverse phase chromatography. There is systematic isotopic fractionation during the reaction, but this can be allowed for by analysing known NO(3)(-) standards along with each sample set. Sudan-1 prepared from surface water samples containing approximately 50 &mgr;g NO(3)(-)-N can be analysed by automated continuous flow isotope ratio mass spectrometry with a precision of 0.2 per thousand (one standard deviation) and the accuracy is not affected by interference from other nitrogenous species in the sample or reagents. Copyright 1999 John Wiley & Sons, Ltd.     

Densification of sol–gel silica thin films induced by hard X‐rays generated by synchrotron radiation

In this article the effects induced by exposure of sol–gel thin films to hard X‐rays have been studied. Thin films of silica and hybrid organic–inorganic silica have been prepared via dip‐coating and the materials were exposed immediately after preparation to an intense source of light of several keV generated by a synchrotron source. The samples were exposed to increasing doses and the effects of the radiation have been evaluated by Fourier transform infrared spectroscopy, spectroscopic ellipsometry and atomic force microscopy. The X‐ray beam induces a significant densification on the silica films without producing any degradation such as cracks, flaws or delamination at the interface. The densification is accompanied by a decrease in thickness and an increase in refractive index both in the pure silica and in the hybrid films. The effect on the hybrid material is to induce densification through reaction of silanol groups but also removal of the organic groups, which are covalently bonded to silicon via Si—C bonds. At the highest exposure dose the removal of the organic groups is complete and the film becomes pure silica. Hard X‐rays can be used as an efficient and direct writing tool to pattern coating layers of different types of compositions.     

Amino Acid Determination in Grape Juices and Wines by HPLC Using a Modification of the 6-Aminoquinolyl-N-Hydroxysuccinimidyl Carbamate (AQC) Method

Summary A novel rigid spherical biporous poly(glycidyl methacrylate-triallyl isocyanurate-divinylbenzene) resin (denoted Resin B) has been fabricated by radical suspension copolymerization, with superfine granules of calcium carbonate, and toluene andn-heptane, as porogenic agents, as the basis of a novel porogenic mode, cooperation of solid granules and solvents. The pore structure, static adsorption behavior, and chromatographic properties of Resin B were characterized and compared with those of Resin A (with only solvents as porogens). The results indicated that the biporous resin is a promising chromatographic medium for highspeed protein separation with good mechanical performance and high dynamic adsorption capacity and column efficiency at high flow rates.     

Use of solid-liquid distribution coefficients to determine retention properties of Porapak-Q resins. Determination of optimal conditions to isolate alkyl-methoxypyrazines and beta-damascenone from wine.

The solid-liquid distribution coefficients of different analytes--all of which are important aroma compounds--between hydroalcoholic solutions or wines and different sorbents have been determined by measuring the amount of analyte removed by a given mass of sorbent in equilibrium with a given volume of standard solution. These data have shown that the best extraction conditions for non-polar compounds from wine are the use of Porapak-Q resins and 6% (v/v) alcoholic solutions. Phase ratio, hold-up volumes and number of plates for Porapak-Q beds have been measured in different experiments. With all these data it has been possible to calculate breakthrough volumes in good agreement with experimental results. The L?vkvist-J?nsson model is more appropriate for estimating breakthrough volumes of a 2-cm Porapak-Q bed. The model estimates that a 5-cm bed is needed to achieve a quantitative recovery of 3-alkyl-2-methoxypyrazines and beta-damascenone from 500 ml of wine (diluted to 1000 ml with water). Experimental results confirm the predictions of the model and show that in a single isolation step detection limits below 10 ng/l can be reached for these compounds using GC-MS detection.     

Determination of HCHs in sediments of the River Gallego

Summary The capacity of adsortion of the River Gallego's sediments in relation to HCHs versus time was studied as well as the recoverys of extraction of sediments. Two series of dried and homogeneous sediments from the river were prepared as follows. A well-known amount of HCHs was added to two series of river's sediments containing 25% and 60% (w/w) of water each. After some controlled period of time the samples were centrifugated and the content of HCH was analyzed after the extraction and using gas chromatography and an electron capture detector for the final determination. The liquid phase was extracted with a mixture of hexane-diethylether (85:15) and the solid phase using acetone and a mixture of hexane-acetone (1:1). It has been found that between 18% and 36.9% of HCHs added were irreversibly adsorbed. Also, the elimination of sulfur compounds which act as interferences and led to incorrect quantification in the chromatogram was studied. It has been found that the main compounds present in these sediments are very soluble in water and they remain in the water after the extraction with hexane. This fact permits to avoid these interferences from the sediments only by rinsing them with distilled water.Projekt P IT 8/88 (Diputación General de Aragón)     

Structural studies and T c dependence in La2−x Dy x Ca y Ba2Cu4+y O z type mixed oxide superconductors

A new series of mixed oxide superconductors with the stoichiometric composition La_2−x Dy _x Ca _y Ba₂Cu_4+y O _z (x=0.0 − 0.5, y=2x) has been studied for structural and superconductiong properties. Our earlier studies on La_2−x (Y/Er) _x Ca _y Ba₂Cu_4+y O _z series, show a strong dependence of T _c on hole concentration (p _sh). In the present work, the results of the analysis of the neutron diffraction measurements at room temprerature on x=0.3 and 0.5 samples are reported. It is interesting to know that Ca substitutes for both La and Ba site with concomitant displacement of La onto Ba site. Superconductivity studies show that maximum T _c is obtained for x=0.5, y=1.0 sample (T _c ∼ 75 K), for La_1.5Dy_0.5Ca₁Ba₂Cu₅O _z (La-2125).     

Behaviour of several solid adsorbents for sampling tetraalkyllead compounds in air

The behaviour of various solid adsorbents for collecting tetraalkyllead compounds has been studied. A synthetic atmosphere containing a known concentration of tetraethyllead was produced and the tetraethyllead compound was trapped in a glass tube containing the solid adsorbent. The trapped compound was extracted with hexane in an ultrasonic bath, and the resulting solution was analysed by GC-MS. Porapak and Tenax, with retention efficiencies of 92 and 96%, respectively, were shown to be the more efficient at trapping this alkyllead compound than Chromosorb, active charcoal, Amberlites and polyurethane foam. The behaviour of both Porapak and Tenax for trapping other tetraalkyllead compounds in the presence of gasoline vapour was also studied.