Vivienne A. Tabner’s research while affiliated with Lancaster University and other places

The EPR spectrum of the 1,4-dinitrodurene radical anion, prepared by electrochemical reduction in dimethylformamide, has been studied between 223 and 343 K. The EPR spectrum presents a classic example of linewidth alternation (first observed in 1962) and can be computer-simulated on the basis of a two- or a four-jump model. The two-jump model, in which the nitrogen atoms interchange their environment, tends to give poor reproductions of the experimental spectra. However, the four-jump model, based on the change of environment of only one nitro group during a particular jump, gives a much better fit to the experimental spectra over the complete temperature range.

The ESR spectra of the stalks and skins of a number of non-irradiated and γ-irradiated citrus fruits suggest that ESR spectroscopy could be used to establish the irradiation history. Two major spectral changes occur up on irradiation. Two additional features appear and are only observed in irradiated specimens (Features B and D, the latter separated by c. 5.9mT) and these are accompanied by an increase in the intensity of the main central signal (Feature A). Observations on the stability of Features A and D indicate that they arise from different radicals. Experiments on the meso- and exo-carps indicate that Features B and D are located mainly in the former and Feature A mainly in the latter.

Infrared, Raman and solid state13C NMR spectra have been recorded for arange of inclusion compounds of urea containingstraight chain aliphatic carboxylic acids(butyric – decanoic) as guests. Inclusioncompounds are not formed with formic, acetic andpropionic acids. Thiourea does not forminclusion compounds with any of the C1 to C10acids. The vibrational and NMR data support theconclusion that the acids are present ashydrogen bonded dimers in the channels of thehost. The alkyl chain 13C chemical shiftvalues are very different from those of acidguests in the cavities formed in Dianin'scompound. These suggest that the alkyl chainsare present in the all-trans conformation,although weak bands observed in the spectrum ofthe decanoic acid inclusion compound lend somesupport to suggestions based on MM calculationsthat other conformations might be present.

Infrared, Raman and solid state 13C-NMR spectra have been recorded for a range of clathrates of Dianin''s compound containing straight chain aliphatic carboxylic acids (formic - octanoic) as guests. The IR, Raman and NMR spectra can be satisfactorily interpreted in terms of dimer (formic and acetic) and monomer (propionic - octanoic) occupation of the cavities. The clathrates containing straight chain alcohol guests (methanol - octanol) have also been prepared to aid in the interpretation of the NMR data.

The ESR spectra of the flesh of a selection of unirradiated and γ-irradiated citrus fruits have been obtained. When dried, the flesh from unirradiated fruits gives rise to virtually no ESR spectrum. However, the flesh of irradiated fruits exhibit a strong spectrum with radiation induced features which show a high degree of reproducibility within the fruits examined. These features have been previously observed in spectra from the intact skin and skin components of irradiated citrus fruits. It is believed that this is the first time that radicals have been observed by ESR in the flesh of irradiated fruits.

The ESR spectra of the stalks and skins of a selection of unirradiated and γ-irradiated citrus fruits have been obtained. The spectra from the stalks and skins of unirradiated fruits exhibit only a single line, the intensity of which varies markedly from fruit to fruit. The spectra from irradiated stalks exhibit extra features which can be used to detect irradiation, particularly at higher doses. The spectra obtained from the skins of the irradiated fruits also exhibit radiation-induced features which can easily be used to detect irradiation even at the lowest dose examined (2 kGy). The spectra from the irradiated skins show a high degree of reproducibility from fruit to fruit. These observations suggest that ESR spectroscopy could form the basis of a viable test to determine the radiation history of these fruits.

The ESR spectra of the seeds, skins and stalks of unirradiated and γ-irradiated Chilean white grapes have been obtained and the results compared to those previously reported for Cape black grapes. The high degree of reproducibility of the spectra obtained from the stalks of different varieties of grapes suggest that ESR spectroscopy could form the basis of a viable test to determine their irradiation history. The condition of the stalk prior to irradiation has been found to have little effect on the resulting spectra. The spectra from the stalks, skins and seeds of unirradiated and γ-irradiated apples, peers and cherries have also been examined. Although most of the spectra from irradiated components exhibit extra features, they are sometimes short-lived and restrict the development of ESR as a viable test.

The ESR spectra of the seeds, skins and stalks of unirradiated and γ-irradiated Chilean white grapes have been obtained and the results compared to those previously reported for Cape black grapes. The high degree of reproducibility of the spectra obtained from the stalks of different varieties of grapes suggest that ESR spectroscopy could form the basis of a viable test to determine their irradiation history. The condition of the stalk prior to irradiation has been found to have little effect on the resulting spectra. The spectra from the stalks, skins and seeds of unirradiated and γ-irradiated apples, pears and cherries have also been examined. Although most of the spectra from irradiated components exhibit extra features, they are sometimes short-lived and restrict the development of ESR as a viable test.

The ESR spectra of the seeds, skins and stalks of unirradiated and γ-irradiated Cape black grapes have been obtained. In the spectra of all parts of the grape a single line (g ca. 2.004) is observed both before and after irradiation. New spectral features are observed after irradiation with doses of between 2 and 10 kGy. Some of these features decline in intensity over a period of several days. However, in the case of stalks, new spectral features are readily observed over the shelf-life of the fruit and in samples irradiated to a dose of only 2kGy.

A pre-resonance Raman study of the yellow ß-quinol/SO2 clathrate has been carried out using 609.8, 586.8, 514.5, 488.0 and 457.9 run excitation. Pre-resonance enhancement is observed for the guest vl (Al) band at 1147 cm-1 and the host band at 1257 cm-1. These observations are consistent with a charge transfer interaction arising from the LUMO of S02 (S 3pz) and the HOMO of quinol, which consists mainly of the ring p electrons.