Peter J. Holloway

Some variations in the composition of suberin from the cork layers of higher plants

Abstract The monomeric composition of the suberins from 16 species of higher plants was determined by chromatographic methods following depolymerization of the isolated extractive-free cork layers with sodium methoxide-methanol. 1-Alkanols (mainly C18C28), alkanoic (mainly C16C30), α,ω-alkanedioic (mainly C16C24), ω-hydroxyalkanoic (mainly C16C21), dihydroxyhexadecanoic (mainly 10,16-dihydroxy- and 16-dihydroxyhexadecanoic), monohydroxyepoxyalkanoic (9,10-epoxy-18-hydroxyoctadecanoic), trihydroxyalkanoic (9,10, 18-trihydroxyoctadecanoic), epoxyalkanedioic (9,10-epoxyoctadecane-1,18-dioic) and dihydroxyalkanedioic (9,10-dihydroxyoctadecane-1 18-dioic) acids were detected in all species. The suberins differed from one another mainly in the relative proportions of these monomer classes and in the homologue content of their 1-alkanol, alkanoic, α,ω-alkanedioic and ω-hydroxyalkanoic acid fractions. C18 epoxy and vic-diol monomers were major components (32–59%) of half of the suberins examined (Quercus robur, Q. ilex, Q. suber, Fagus sylvatica, Castanea sativa, Betula pendula, Acer griseum, Fraxinus excelsior) where as ω-hydroxyalkanoic and α,ω-alkanedioic acids predominated in those that contained smaller quantities of such polar C18 monomers (Acer pseudoplatanus, Ribes nigrum, Euonymus alatus, Populus tremula, Solanum tuberosum, Sambucus nigra, Laburnum anagyroides, Cupressus leylandii). All species, however, contained substantial amounts (14–55 %) of ω-hydroxyalkanoic acids, the most common homologues being 18:1 (9) and 22: 0. The dominant α,ω-alkanedioic acid homologues were 16: 0 and 18: 1 (9) whereas 22: 0, 24: 0 and 26: 0, and 20: 0, 22: 0 and 24: 0 were usually the principal homologues in the 1-alkanol and alkanoic acid fractions, respectively. The most diagnostic feature of the suberins examined was the presence of monomers greater than C18 in chain length; most of the C16 and C18 monomers identified in the suberins also occur in plant cutins emphasizing the close chemical similarity between the two anatomical groups of lipid biopolymer.

Epoxyoctadecanoic acids in plant cutins and suberins

Abstract Three C 18 epoxy acids occur in plant cutins and suberins. 9,10-Epoxy-18-hydroxyoctadecanoic acid is a common constituent of both cutins and suberins whilst 9,10-epoxy-18-hydroxyoctadec-12-enoic acid is also present in some cutins. 9,10-Epoxyoctadecane-1,18-dioic acid occurs more commonly in suberins. Epoxy acids may comprise up to 60% of the total monomers obtained from some polymers. The epoxy compounds are readily converted into their corresponding alkoxyhydrin alkyl esters on depolymerization of cutin or suberin by alcoholysis. The chromatographic and MS properties of the alkoxyhydrin derivatives enable them to be readily distinguished from other cutin and suberin hydroxyfatty acids and to be used for the qualitative and quantitative determination of epoxy acids in the polymers.

EFFECTS OF SOME AGRICULTURAL TANK-MIX ADJUVANTS ON THE DEPOSITION EFFICIENCY OF AQUEOUS SPRAYS ON FOLIAGE

Abstract The effects of 10 commercially available tank-mix adjuvants on the retention and coverage of aqueous sprays on foliage were examined quantitatively under track sprayer conditions, following application at their maximum recommended rates. Substantial enhancement of fluorescein retention was observed only on water-repellent barley and peas, but the differences in performance between the additives were considerable. Addition of the water-soluble tallow amine and nonylphenol surfactants gave the largest increases in retention, whereas there was little improvement in efficiency compared with water alone after inclusion of either the latex- or pinolene-based products or ammonium sulphate. Retention enhancement was also achieved using the mineral oil, vegetable oil, methylated vegetable oil and phospholipid ECs and the organosilicone surfactant, but this was often much less than that obtained for the water-soluble surfactants; the best EC was the methylated vegetable oil which also had the highest emulsifier content. Although spray quality was altered significantly in the presence of many of the adjuvants, modifications to this parameter alone could not account for changes observed in deposition efficiency, because retention enhancement was recorded in sprays with volume median diameters both smaller and larger than water. There was a better correlation between retention efficiency and the dynamic surface tension of the corresponding spray liquids, with the exception of the organosilicone, which, as expected from its high surface activity, gave essentially complete spray coverage on leaves. Nevertheless, good coverage could still be achieved by adding the two water-soluble surfactants, as well as the methylated vegetable oil and phospholipid ECs. Coverage performance of the other adjuvants tested was poor in comparison, reflecting, in part, their inferior retention enhancing properties.

Occurrence of positional isomers of dihydroxyhexadecanoic acid in plant cutins and suberins

Abstract Positional isomers of dihydroxyhexadecanoic acid have been found in cutin and suberin hydrolysates and identified using combined gas chromatography—mass spectrometry of their TMS derivatives. The acid is usually a mixture of the 10,16-, 9,16-, 8,16- and 7,16-isomers which are eluted as a single peak using packed GLC columns. The major isomers are commonly 10,16- and 9,16- with the other isomers occurring in smaller quantities. The implications of the results in the biosynthesis of cutin and suberin are discussed.

The constituent acids of angiosperm cutins

Abstract The composition of the cutin from the cuticles of twenty-four angiosperm leaves and fruits has been compared by GLC. The most abundant acid found in angiosperm cutin is confirmed as 10,16-dihydroxyhexadecanoic with 9,10,18-trihydroxyoctadecanoic occurring frequently and 16-hydroxyhexadecanoic less frequently. Other hydroxy acids, as yet unidentified, have also been found. Monobasic acids, especially hexadecanoic, are important constituents of cutin. Wide variations of cutin composition occur between species, within species and between leaves and fruits of the same species.

Cutins of Malus pumila fruits and leaves

Abstract The cutins of fruits and leaves of four apple cultivars have been analysed using TLC, GLC and GC-MS. They are similarly composed of saturated, monounsaturated and diunsaturated fatty, hydroxy-fatty and epoxyhydroxy-fatty acids. The most abundant monomers are 18-hydroxyoctadeca-9,12-dienoic, 10,16-dihydroxyhexadecanoic, 9,10-epoxy-18-hydroxyoctadec-12-enoic, 9,10-epoxy-18-hydroxyoctadecanoic and 9,10,18-trihydroxyoctadecanoic acids. The fruit cutins have high contents of epoxides (35–40%) and unsaturated components ( > 40%) and C 18 compounds predominate over C 16 . The leaf cutins contain smaller amounts of unsaturated components than the fruits and higher proportions of C 16 compounds. The adaxial leaf cutin differs in composition from the abaxial. 10,16-Dihydroxyhexadecanoic and 9,10-epoxy-18-hydroxoctadecanoic acids are the major constituents (each ca . 30%) of the adaxial leaf cutin and 10,16-dihydroxyhexadecanoic acid (55–65%) predominates in the abaxial.

Effects of sterol biosynthesis-inhibiting fungicides and plant growth regulators on the sterol composition of Barley plants

Abstract A number of sterol biosynthesis-inhibiting (SBI) fungicides and plant growth regulator analogs were applied as root drenches to barley seedlings and their effect on the total sterol composition of the roots and shoots was measured by gas-liquid chromatography. Prochloraz was found to be inactive in this system, probably because of poor uptake, while the other compounds could be divided into two groups according to their mode of action as assessed by sterol profiling. The morpholines tridemorph and fenpropimorph inhibited the enzyme cycloeucalenol—obtusifoliol isomerase whereas triadimenol, nuarimol, paclobutrazol, and triapenthenol (RSW 0411) inhibited the enzyme responsible for the removal of the C-14 methyl group. Effects of individual diastereo-isomers and enantiomers of some compounds on sterol profiles were compared with their known fungicidal and anti-gibberellin properties. Shoot growth was reduced by all the compounds tested, paclobutrazol, nuarimol, and triapenthenol being the most effective. As well as inducing accumulation of abnormal sterols, SBI fungicide treatment changed the ratio of campesterol to stigmasterol and sitosterol. It is hypothesized that this may reflect changes in membrane architecture and may offer an explanation for the increased frost hardiness sometimes observed with SBI fungicide-treated plants.

Chemical composition and ultrastructure of the epicuticular wax in three lines of Brassica napus (L)

Abstract The epicuticular wax in three lines of Brassica napus (rape) has been investigated and the detailed chemistry and ultrastructure of the waxes examined. A distinct chemical make-up has been found for all three waxes which is correlated with three distinct crystallite structures. A tentative scheme for classification of Brassica wax mutants is described in which the two newly analysed rape mutants can be placed. Mass spectral analysis of all wax components confirms and extends previous ideas about the chemistry of Brassica waxes.

Plant Cuticles: Physicochemical Characteristics and Biosynthesis

Cuticles are the thin continuous layers of predominantly lipid material deposited on the outer walls of epidermal cells and, thus, the interface between higher plants and their aerial environment. The main function of this extracellular, non-living layer, commonly referred to as a membrane, is to protect and waterproof the plant surface. Although not structurally or chemically homogeneous, cuticles are usually characterised by two specific classes of lipid substances. The insoluble high molecular weight polyester cutins constitute the framework of the membrane, the monomeric units of which are biosynthesised in the epidermal cells from CIO and Cis fatty acid precursors. The soluble long-chain wax constituents are also synthesised by these cells and are eventually deposited not only on the cuticular surface but also within the cutin matrix. Epicuticular waxes have a considerable influence on the wettability of a plant surface whereas the presence of intracuticular waxes governs cuticular permeability. The cuticles of some species also contain variable amounts of another aliphatic biopolymer, cutin, which is non-saponifiable and, consequently, extremely resistant to biodegradation. Because the cuticle is an integral part of the epidermal cell wall, polysaccharides and probably, phenolic compounds are also involved in its construction.

Adjuvants and glyphosate activity

Additives can be used to enhance the biological performance of glyphosate, as well to improve the physical characteristics of its prediluted formulations. Their effects on efficacy can be mapped through a series of consecutive processes that the herbicide has to follow from spray tank to ultimate biological site of action. Key factors affecting dose transfer are discussed, including retention on foliage in the glasshouse and field, the effects of adjuvants on foliar uptake and the relationship between potential adjuvant effects and glyphosate concentration. A better understanding of the relative importance of the main barriers to glyphosate activity and the ability of adjuvants to overcome them should enable a more rational approach to the design of glyphosate formulations in the future.