Comparison of two quantitative GC–MS methods for analysis of tomato aroma based on purge-and-trap and on solid-phase microextraction

Two analytical procedures, one based on purge-and-trap and the other on solid phase microextraction, both followed by GC–MS measurement using an ion-trap mass spectrometer in the electron impact mode, have been developed for determination and quantitation of up to 39 aroma compounds in fresh tomatoes. The method based on purge-and-trap for isolation of the volatile compounds uses Tenax as adsorbent and a hexane–diethyl ether mixture as solvent for elution. The method was validated for linearity, precision (better than 20% for most compounds), and limit of detection, which was approximately 1 ng g⁻¹. This method enabled identification of up to 30 compounds in real samples. Use of SPME was considered as an alternative, to simplify sample treatment while maintaining the information level for the samples (e.g. the number of compounds detected) and quality of quantitation. A procedure based on SPME using a Carboxen/polydimethylsiloxane fibre was developed and validated for determination of 29 aroma compounds; precision was better than 20% and limits of detection ranged from 4 to 30 ng g⁻¹.     

Rapid and sensitive determination of aminoglycoside antibiotics in water samples using a strong cation-exchange chromatography non-derivatisation method with chemiluminescence detection

A simple and sensitive chemiluminescence (CL) detection approach was developed for the direct analysis of aminoglycoside antibiotics in water samples following strong cation-exchange chromatographic (SCX-HPLC) separation. This detection system, which eliminates the need for sample derivatisation, is based on the inhibitory effect of aminoglycosides on the CL reaction between luminol and hydrogen peroxide catalysed by copper(II). As the operational and chemical variables that affect the CL signal were optimised, ionic strength and the Triton X-100 micelles turned out to be the keys to obtain maximum CL efficiency. Aminoglycosides were successfully separated in 10 min on a SCX column using a mobile phase consisting of an aqueous solution containing 5.0 x 10(-3)mol/l sodium acetate and 0.65 mol/l sodium chloride at pH 6.1. Sample volumes of 50 ml were preconcentrated by passage through a weakly acidic IRC-50 exchange column. Limits of detection from 0.7 to 10 microg/l and relative standard deviations from 2.7 to 5.4% were thus obtained. The proposed method surpasses other chromatographic alternatives in terms of the limit of detection, sample requirements for analysis and cost.     

Continuous microwave-assisted extraction coupled on-line with liquid-liquid extraction: determination of aliphatic hydrocarbons in soil and sediments

This paper describes a new extraction method for the determination of aliphatic hydrocarbons (AHs) in soil and sediment samples, using continuous microwave-assisted extraction (MAE) combined with liquid-liquid extraction, for clean-up purposes. Analytical determinations were carried out by gas chromatography coupled with impact ionization mass spectrometry. The influence of the experimental conditions was tested using an agricultural soil spiked with standards (stored at 4 degrees C for 1 month) as reference soil. Maximum extraction efficiencies (80-90%) were achieved using 0.1-1.0g of sample, 60microl of water and 3ml of n-hexane (extractant) and 5min of extraction time; less than 70% of the most volatile hydrocarbons (C(9)-C(12)) were recovered since many evaporated during the drying step of the sample. MAE was compared with a conventional extraction method such as Soxhlet and a good agreement in the results was obtained (average recovery percentage value of 105% by comparing MAE against Soxhlet). Quality parameters such as linear range (0.5-800microg/g), limits of detection (LODs) (0.1-0.2microg/g) and precision (RSD, 4-6%) were determined using spiked soil samples. This method was successfully applied to the analysis of aliphatic hydrocarbons (C(9)-C(27) including pristane and phytane) in contaminated real samples.     

Self‐Assembly in Helical Columnar Mesophases and Luminescence of Chiral 1H‐Pyrazoles

Chiral polycatenar 1H‐pyrazoles self‐assemble to form columnar mesophases that are stable at room temperature. X‐ray diffraction and CD studies in the mesophase indicate a supramolecular helical organization consisting of stacked H‐bonded dimers. The liquid‐crystalline compounds reported are 3,5‐bis(dialkoxyphenyl)‐1H‐pyrazoles that incorporate two or four dihydrocitronellyl chiral tails. It can be observed that the grafting of these branched chiral substituents onto the 3,5‐diphenyl‐1H‐pyrazole core has a beneficial role in inducing mesomorphism, because isomeric linear‐chain compounds are not liquid crystalline; this is not the usual scheme of behavior. Furthermore, the molecular chirality is transferred to the columnar mesophase, because preferential helical arrangements are observed. Films of the compounds are luminescent at room temperature and constitute an example of the self‐organization of nondiscoid units into columnar liquid‐crystalline assemblies in which the functional molecular unit transfers its properties to a hierarchically built superstructure.     

Alternative synthetic strategies for Schiff base derived liquid crystal polymers: A comparative study

Semiflexible liquid crystalline polymers based on Schiff bases as mesogenic cores have been synthesized through different synthetic strategies. The mesogenic cores are derived from 1,5-naphthalenediamine linked to a polymethylenic spacer by means of ether or ester groups. The synthetic strategies differ in the disconnection of the molecules to design the synthesis of the repeating units. Polymers were synthesized either as polyazomethines, where imine bonds are formed in the polymer synthesis, or as polyethers or polyesters, where the ether or ester groups are formed at the polymer-forming stage. The influence of the synthetic method and the linking groups between mesogenic core and flexible spacer on the thermal and mesogenic properties has been analyzed by DSC, thermogravimetry, and optical microscopy. The possibility of obtaining hydroxy-functionalized polymers by different synthetic strategies has been studied as well as the influence of these groups on the thermal and mesogenic properties. © 1996 John Wiley & Sons, Inc.     

Columnar Phases from Covalent and Hydrogen-Bonded Liquid-Crystalline Ferrocene Derivatives

The synthesis and liquid-crystalline properties of tetracatenar covalent and H-bonded bis-ferrocene derivatives 1 and 2 , respectively, are reported. Both compounds gave rise to enantiotropic columnar liquid-crystalline behavior with a hexagonal molecular organization. To explore the possibility to obtain also calamitic liquid-crystalline phases from H-bonded ferrocene-containing liquid crystals, a rod-shaped ferrocene mesogen 3 was synthesized, which gave rise to enantiotropic smectic C and smectic A phases. For the first time, a rational synthetic design at the ferrocene level led to ferrocene-based liquid-crystals with columnar behavior and to H-bonded metallomesogens.     

Kinetic investigations on the photopolymerization of di- and tetrafunctional methacrylic monomers in polymeric matrices. ESR and calorimetric studies. II. Postpolymerization reactions

The reaction kinetics in the dark of photopolymerized mono- and dimethacrylates in a polymeric binder has been studied. Electron spin resonance spectroscopy (ESR) provided useful information regarding the nature of the radicals involved in postpolymerization reactions. Computer simulations were performed to study the decay of the propagating radicals by considering normal bimolecular termination and transfer reactions of the radicals to the binder. Differences were found in the termination reactions for mono- and difunctional monomers when they were photopolymerized in a solid medium. Absolute kinetic constants for H-transfer reaction with the binder, relative kinetic rate constants for radical–radical coupling, and average lifetimes for the radicals have been calculated. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2785–2791, 1998     

Kinetic investigations on the photopolymerization of di- and tetrafunctional (meth)acrylic monomers in polymeric matrices. ESR and calorimetric studies. I. Reactions under irradiation

The photopolymerization of several di- and tetrafunctional (meth)acrylic monomers in the presence of a styrene–butadiene–styrene polymeric matrix (SBS) has been studied. Electron spin resonance spectroscopy (ESR) and differential scanning photocalorimetry (photo-DSC) were used as monitoring techniques to identify the photogenerated radicals and analyze photopolymerization profiles, radical environments, and radical secondary reactions. The study of the photopolymerization and/or photocrosslinking reactions of these monomers in the solid media was carried out by taking into consideration different factors, such as the influence of both monomer and photoinitiator structures on the hydrogen abstraction in the binder with formation of benzylic and allylic radicals, the polymerization of the monomers itself and the hydrogen abstraction reaction in the polymerized acrylic chains. Finally, irradiation of the system SBS/photoinitiator in the absence of monomer was also accomplished. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2775–2783, 1998     

Gelation of an epoxy resin and percolation theory

The percolation theory has been applied to the isothermal hardening of the TGDDM-DDS system (tetraglycidyldiaminodiphenyl-methane-diaminodiphenylsulfone). At each temperature, the variations of viscosity as a function of the extent of reaction are well described by a percolation law. The variations of the critical threshold and of the percolation parameter with temperature may be explained by a modification of the reaction mechanism. The percolation threshold is in agreement with the gel point defined on the experimental curves of the logarithm of loss modulus as a function of time log G″ = f(t).     

XRD Line Broadening Studies on Mullite

An X-ray diffraction microstructural study on 110, 220, 001 and 111 peaks has been performed on mullite in the temperature range of primary mullite formation in order to monitor nucleation and growth process. Considering the crystallinity of the starting kaolinites, a greater disorder of the kaolinite has been found to enhance the mullite formation. Isothermal growth is related to a decrease in the Al₂O₃ content of mullite.