Mass spectrometric methodology for the analysis of highly oxidized diterpenoid acids in Old Master paintings

Diterpenoid resins from larch and pine trees and the corresponding fractions in a >100-year-old wax-resin adhesive and varnish and a 200-year-old resin/oil paint sample were analysed with by gas chromatography/mass spectrometry (GC/MS) using several off-line and on-line derivatization methods. The main resin compounds were highly oxidized abietic acids. Important products found are hydroxydehydroabietic acids (OH-DHAs), 7-oxoDHA, di-OH-DHAs and 15-OH-7-oxoDHA. The last two compounds have not been reported to occur in artworks before. Larixyl acetate, an important marker from larch resins, was found to be still present in high amounts in the adhesive. A large number of mass spectra of the different oxidation products and larixol and larixyl acetate are presented and their fragmentation behaviour under electron impact conditions is discussed. An index for the degree of oxidation (IDOX) of the abietic acids is presented as an indicator of the degree of oxidation of the matrix in which the resin is present. The IDOX was 0.10, 0.67, 0.81 and 0.76 for the fresh resins, the dark-aged adhesive, the aged varnish and the resin/oil paint, respectively (measured with pyrolysis (Py)-tetramethylammonium hydroxide (TMAH)-GC/MS). Py-TMAH-GC/MS and direct temperature-resolved mass spectrometry are reliable, valuable and fast techniques for the assessment of the presence and degree of oxidation of diterpenoid resins. Copyright 2000 John Wiley & Sons, Ltd.     

Reversed phase liquid chromatographic separation of some mono-substituted phenols with calix[6]arene-ρ-sulfonate-modified eluents

Summary The utility of water-soluble calix[6]arene--sulfonate as a mobile phase additive has been investigated for the reversed phase liquid chromatographic separation of some monosubstituted phenol isomers. Retention factors and separation factors for regioisomers of methoxyphenol, aminophenol, and nitrophenol were measured using methanol — water and acetonitrile —water mobile phases of varying composition containing calix[6]arene--sulfonate, and the values were compared with those obtained using mobile phases containing no additive. It was observed that addition of calix[6]arene--sulfonate to both acetonitrile — water and methanol —water caused a reduction in the retention of the phenol isomers but generally increased the separation between them, thereby improving the overall separation efficiency.     

Determination of Stereoisomers of Heteronuclear Clusters by a Symmetry-Based Algorithm

A general methodology for the determination of all possible stereoisomers of heteronuclear clusters is reported. The paper is divided into three parts: (1) nomenclature—wherein a systematic numbering system for multi-component clusters under which each and every stereoisomer of a given cluster can be uniquely identified is presented; (2) methodology—wherein the general principles for the determination of symmetry analogs are discussed; and (3) computer algorithm—wherein the implementation of the symmetry principles is described. These principles and algorithms are applied to binary (two-component) systems using octahedral and icosahedral clusters as examples.     

Photochromism of novel molybdate/alkylamine composite thin films.

Novel inorganic/organic composite films of molybdates with photochromic properties have been prepared by self-assembly using alkylammonium ions as a supramolecular template. Both 1-hexadecylammonium/polyoxomolybdate (C16-Mo) and 1-octadecylammonium/polyoxomolybdate (C18-Mo) composite films have been successfully fabricated. The elemental analysis and thermal gravimetric analysis show that the main product in the C16-Mo film was (C16H33NH3)4Mo8O26. The X-ray diffraction (XRD) results indicate that the composite films were lamellar in nature. The IR, Raman and X-ray photoelectron spectroscopy (XPS) results show that the polyoxomolybdate anions present as MoO6 octahedra and that the Mo species exists as Mo6+ in the freshly prepared films. The alkyl chains in the 1-hexadecylammonium chains were linear and the alkyl groups are an all-trans configuration. Upon UV irradiation of the C16-Mo films, some Mo6+ was reduced to Mo5+, some -NH3+ became -NH2 with a concomitant increase in the concentration of -OH groups on the molybdate moieties, and the films were colored. Thus, the photochromism of the films involves the reduction of Mo6+ to Mo5+, coupled with a proton transfer from 1-hexadecylammonium ions to an oxygen atom at the Mo site. In contrast to thin films of transition-metal oxides, which all show photochromism in the blue region of the electromagnetic spectrum, these composite films show photochromism in the violet region with the greatest absorbance change at 472 nm.     

An investigation into the effect of electric field on the performance of Dielectric Barrier Discharge plasma actuators

The influence of the inter-electrode electric field of a single Dielectric Barrier Discharge (DBD) actuator on the performance of the device was investigated. The electric field of the actuator was manipulated through the variation of the angle between the electrodes of the actuators. Response forces generated by the plasma actuators were used as performance indicators for these devices. These forces were measured directly utilizing a highly sensitive balance scale. It was verified that depending on the orientation of the variation of the angle between the electrodes, the performance of the actuator may be decreased or increased when compared to a DBD on a flat dielectric plate more commonly investigated in literature. The manner in which the ionic wind flows over the actuators was also explored in the effort to elucidate the influence of the variation of the angle between the electrodes on the response force generated by the device. Results demonstrated that the response forces generated by the actuators may be improved by up to 50% compared to the actuator configuration on a flat dielectric plate commonly investigated. These results indicate the potential available to advance plasma technology by physically manipulating these devices to increase the performances of the actuators.