Development of a solid phase microextraction method for detection of the use of banned azo dyes in coloured textiles and leather

A new method to detect the use of banned azo dyes in the manufacture and treatment of coloured textiles and leather is described. The determination of the azo dyes was made by quantification of aromatic amines generated by reductive cleavage in a citrate buffer medium. The aromatic amines were then extracted from 1 mL of the reaction solution by means of solid phase microextraction (SPME) and determined by gas chromatography/mass spectrometry (GC/MS). We also evaluate accuracy, precision, range of linearity and limit of detection for the eighteen aromatic amines investigated, and show that the method is comparable with current established methods. Copyright 1999 John Wiley & Sons, Ltd.     

Reactivity and biological properties of a series of cytotoxic PtI2(amine)2 complexes, either cis or trans configured

Six diiodido-diamine platinum(II) complexes, either cis or trans configured, were prepared, differing only in the nature of the amine ligand (isopropylamine, dimethylamine, or methylamine), and their antiproliferative properties were evaluated against a panel of human tumor cell lines. Both series of complexes manifested pronounced cytotoxic effects, with the trans isomers being, generally, more effective than their cis counterparts. Cell cycle analysis revealed different modes of action for these new Pt(II) complexes with respect to cisplatin. The reactivity of these platinum compounds with a number of biomolecules, including cytochrome c, two sulfur containing modified amino acids, 9-ethylguanine, and a single strand oligonucleotide, was analyzed in depth by mass spectrometry and NMR spectroscopy. Interestingly, significant differences in the reactivity of the investigated compounds toward the various model biomolecules were observed: in particular we observed that trans complexes preferentially release their iodide ligands upon biomolecule binding, while the cis isomers may release the amine ligands with retention of iodides. Such differences in reactivity may have important mechanistic implications and a relevant impact on the respective pharmacological profiles.     

The control of the cholesteric pitch by some azo photochemical chiral switches

A few chiral azo compounds, which undergo reversible photochemical switching, are presented. Of these, the most interesting contain the binaphthyl moiety and belong to the C2 (derivatives 1 and 2) or C1 symmetry group (derivatives 3 and 4). These binaphthyl compounds display intense CD and high beta values. Photochemical switching has profound effects on both the CD and beta values of these compounds; in the case of compound 3, the sign of beta changes upon isomerisation. Compound 2 has, to our knowledge, the highest beta of the switches reported in the literature and also seems the most interesting owing to its fast response to photochemical stimuli. Nematic phases can be transformed into cholesteric phases with reflection bands in the visible region by doping with reasonable amounts of 1 and 2. The reflection colours can be changed reversibly by photoisomerisation of the switches. Thermal reversion of the colourless UV photostationary state to the green isomeric EE state or to intermediate coloured states is temperature dependent. This can allow the thermal history of a sample to be traced.     

Reactions of ionic species from acetonitrile with long-chain saturated and unsaturated alcohols

Ten long-chain saturated and unsaturated alcohols were reacted with the ionic species [C(2) H(2) N](+) and [C(3) H(4) N](+) generated by ionization of acetonitrile into an ion trap. The mass spectra of the compounds under investigation show the formation of [M -H](+), [M + C(2) H(2) N](+) and [M + C(2) H(4) N](+) ions in the case of saturated alcohols, whereas for monounsaturated and polyunsaturated derivatives additional peaks corresponding to [M + H](+) and [M + H -H(2) O](+) are observed. The reaction mechanisms were investigated by means of D- and (13)C-labelled acetonitrile. Collisional experiments were performed on the [M + C(3) H(4) N](+) species from the polyunsaturated alcohols in order to identify any possibly diagnostic fragments for the identification of the double bond positions. Copyright 1999 John Wiley & Sons, Ltd.     

Nucleophilic substitution of chlorobis(4-methoxyphenyl)methane: reactivity of carbenium ions in ILs-trifluoroethanol mixtures

The ionization of chlorobis(4-methoxyphenyl)methane (1-Cl) was performed in 1:1 mixtures of TFE/ILs (ILs = [emim][Tf₂N], [bmim][Tf₂N], [bpy][Tf₂N]), and TFE/CH₃CN. The decay of the immediately formed carbenium ion 1⁺ was followed by stopped flow, showing that the lifetime of this intermediate significantly decreases on going from CH₃CN to [emim][Tf₂N]. Ab initio calculations suggest an increase in the electrophilicity of the carbenium ion in ILs.     

Gel-like lyomesophases formed in organic solvents by self-assembled guanine ribbons

Lipophilic guanosine derivatives are self-assembled into ribbonlike aggregates, both in the crystal state and in solution. The structure of the ribbons has been characterised by single-crystal X-ray diffraction and, in solution, by NMR spectroscopy and ESI-MS. Two different ribbons with different patterns of hydrogen bonds are present in the solid state and in chloroform solutions. The gel-like phases obtained in hexadecane, toluene and chloroform have been investigated by optical microscopy and small-angle X-ray diffraction: the type of phase observed is related to the molecular structure of the compounds and depends dramatically on the solvent. The structures of the phases are discussed, with the presence of the two different ribbons being taken into account.     

Photoacoustic Generation: Optical Fiber Ultrasonic Sources for Non-Destructive Evaluation and Clinical Diagnosis

An innovative photoacoustic source for ultrasonic non destructive evaluation (NDE) and clinical diagnosis is proposed. The working principle is based on thermal conversion of laser pulses into a metallic film evaporated directly onto the tip of an optical fiber. Attractive advantages of the proposed transducer are high frequency, large bandwidth and good efficiency.     

Liquid chromatography tandem mass spectrometric quantitation of sulfamethazine and its metabolites: direct analysis of swine urine by triple quadrupole and by ion trap mass spectrometry

This work describes a new method for the quantitation of trace amounts of sulfamethazine (SMZ) and its main metabolite, N4-acetylsulfamethazine (Ac-SMZ), in swine urine, using high-performance liquid chromatography (HPLC) tandem mass spectrometric analysis of crude urine after addition of internal standard and simple dilution with water. The aim was to determine whether residues of this sulfamidic drug, normally administered to swine in order to prevent infectious diseases, were present in urine at levels lower than those permitted by regulatory authorities before human consumption (EU Project SMT, contract number CT 96-2092). A 10 microL volume of diluted urine was injected into a very short, narrow-bore chromatographic column (Zorbax SB-C18 2.1 i. d. x30 mm length, 3.5 microm pore size). Elution of the analytes of interest was achieved in less than seven minutes using a rapid gradient (from 20 to 80% methanol in 3 minutes). Either a PE Sciex API 365 triple quadrupole (QqQ), operated in the selected reaction monitoring (SRM) mode, or a Finnigan LCQ ion trap (IT) mass spectrometer, operated in narrow-range product ion scan, was used as the final detector. Electrospray (ESI) was used as the ionization technique. A comparison of the two tandem mass spectrometers was performed by analyzing the same set of test samples, at three concentration levels, on three different days. Linearity of responses of the calibration standards, intra- and inter-assay precision of the samples, specificity and limits of detection were evaluated for both systems. Both the QqQ and the IT instrument was suitable for rapid, sensitive and specific determination of the analytes, although the overall performance of the QqQ was slightly superior in terms of linearity, precision and sensitivity.     

Determination of the polarities of some ionic liquids using 2-nitrocyclohexanone as the probe

Solute-solvent interactions on the keto-enol tautomerism of 2-nitrocyclohexanone in several organic solvents and room-temperature ionic liquids (RTILs) have been analyzed in terms of multiparameter equations. Permittivity and cohesive pressure values of the RTILs, unavailable by direct measurements, have been derived.