Carbocations and the Complex Flavor and Bouquet of Wine: Mechanistic Aspects of Terpene Biosynthesis in Wine Grapes.

Computational chemistry approaches for studying the formation of terpenes/terpenoids in wines are presented, using five particular terpenes/terpenoids (1,8-cineole, α-ylangene, botrydial, rotundone, and the wine lactone), volatile compounds (or their precursors) found in wine and/or wine grapes, as representative examples. Through these examples, we show how modern computational quantum chemistry can be employed as an effective tool for assessing the validity of proposed mechanisms for terpene/terpenoid formation

Enantiomeric Ratio Changes of Terpenes in Essential Oils from Hybrid Eucalyptus grandis × E. tereticornis and its Pure Species

Some Eucalyptus species produce oils with biological activities and the effect of their interspecifc hybridization on the enantiomeric composition of terpenes has not been reported. The enantiomeric excesses of monoterpenes in the essential oil of Eucalyptus grandis × E. tereticornis and its parental taxa were determined by gas chromatography-mass spectrometry (GC-MS), and to resolve coelutions problems by preparative high performance liquid chromatography (HPLC)and GC-MS with two columns in series. The essential oil composition of the hybrid presented qualitative and quantitative differences with the composition of its parental taxa. Great differences were found for the enantiomeric ratio in monoterpene alcohols among the three essential oils. Our results suggest that the enantiomeric analysis can be a reliable method for the study of how theinterspecifc hybridization can module the enantiomeric chemical profle in Eucalyptus essential oils. These results suggest the use of interspecifc hybridization to improve or expand the source of bioactive compounds.Fil: Naspi, Cecilia Veronica. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Alvarez Costa, Agustin. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Lucia, Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Gonzalez Audino, Paola Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; ArgentinaFil: Masuh, Hector Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad de Investigación y Desarrollo Estratégico para la Defensa. Ministerio de Defensa. Unidad de Investigación y Desarrollo Estratégico para la Defensa; Argentin

Effects of Nitrogen Fertilization on Monoterpenes of Jack Pine Seedlings and Weight Gain of Jack Pine Budworm (Lepidoptera: Tortricidae)

Nine-month old jack pine (Pinus banksiana) seedlings were grown in a greenhouse under four nitrogen fertilization regimes. Levels of total nitrogen and five monoterpenes in new foliage were measured. Fertilization resulted in four significantly different levels of foliar nitrogen; means ranged from 1.8-4.5 percent dry weight. Contrary to predictions of resource availability theory, seedlings grown under the highest fertilization regime had higher foliar monoterpene levels than seedlings in the other treatments. Newly molted, sixth-instar female jack pine budworm (Choristoneura pinus pinus [Lepidoptera: Tortricidae]) larvae were allowed to feed for four days on new foliage of the seedlings. Larvae that fed on low-nitrogen seedling gained less weight and process more vegetation than did larvae on high- nitrogen seedlings. Larval weight gain was positively related to foliar nitrogen

A method to detect baseline emission and plant damage induced volatile emission in a greenhouse

The objective of this research was to ascertain if 1) baseline emission and 2) damage induced emission of volatile plant substances could be detected under greenhouse conditions. A laboratory method was validated for analysing the air in a semi-closed greenhouse with 44 m2 floor area. This greenhouse, with a volume of 270 m3, was climate controlled and light was supplied with assimilation lamps. Sixty tomato plants (Lycopersicon esculentum Mill cv. Moneymaker) were grown in this greenhouse. These plants were artificially damaged on a weekly interval by stroking the stems. Continuous flow pumps were used to purge the air surrounding the plants through tubes containing an adsorbent. This sampling step was performed before and directly after damage of the plants. After sampling, the tubes were transferred to the lab for analysis. The analysis of volatile compounds was performed using a high-throughput gas chromatography-mass spectrometry system. The method enabled the detection of baseline level emission and the emission of volatiles released after artificially damaging the tomato plants during a 6 weeks growing period. Most dominant compounds for baseline emission were the monoterpenes ß-phellandrene, 2-carene, limonene, ¿-phellandrene and ¿-pinene. Directly after damage, these compounds showed an increase of up to 100 times compared to baseline level emission. With these results, we prove that it is possible to detect baseline- and plant damage induced volatile emission in a greenhouse. This area of research is promising but more research needs to be done to determine whether it is possible to detect plant damage due to pests and pathogens using volatile sensing

Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air

Effects of various penetration enhancers on percutaneous absorption of piroxicam from emulgels

A suitable emulgel formulation of piroxicam was prepared and its percutaneous permeation was investigated using Wistar rat skin and diffusion cell technique. The concentrations of the drug in receptor phase of diffusion cells were measured using HPLC method. The effect of three types of penetration enhancers (Myrj 52, cineol and Transcutol P) with different concentrations on transdermal permeation of the drug was also evaluated. Flux, Kp and enhancement ratios (ERs) of piroxicam in the presence of enhancers was measured and compared with emulgel base alone and simple commercial gel. The results showed a significant enhancement in the flux from emulgel base compared to hydroalcoholic gel formulation (9.91 folds over simple gel). The highest enhancement ratio (ER=3.11) was observed for Myrj 52 at the concentration of 0.25%. Higher concentrations of Myrj 52did not show any enhancement in the drug flux due to micelle formation and solubilization of the drug by micelles. The increase in solubility, in turn, increases the saturated concentration and reduces the thermodynamic activity of the drug. Transcutol® P with concentrations higher than 0.25% w/w showed burst transportation of the drug through the skin. All concentrations of cineol and Transcutol did not show any enhancing effects over emulgel base alone (ER <1)

Tolerance of Plant Monoterpenes and Diterpene Acids by Four Species of Lymantriidae (Lepidoptera) Exhibiting a Range of Feeding Specificities

Lymantriidae (Lepidoptera) is a family of leaf-feeding insects that includes some of the most damaging forest pests worldwide. Species within this family vary widely in feeding specificity. We evaluated the ability of four species, Douglas fir tussock moth (Orgyia pseudotsugata McDunnough), nun moth (Lymantria monacha L. ), rusty tussock moth (Orgyia antiqua (L.)), and white- marked tussock moth (Orgyia leucostigma (J. E. Smith)), to contend with one of the most ubiquitous and effective groups of plant defense compounds, terpenoids. We selected these species to provide a range of feeding specificities on conifer hosts, from obligate to occasional. We evaluated the effects of three monoterpenes (bornyl acetate, limonene, and myrcene) and two diterpene acids (isopimaric acid and neoabietic acid) on larval performance. Although these four species differ in their feeding ranges, utilization of conifers as hosts, and other life history processes, each shows a relatively high tolerance for conifer terpenes. The mean relative growth rates, relative consumption rates, and development times were not affected by these monoterpenes and diterpene acids when administered at concentrations present in the foliage of conifers in which they are most abundant. The most likely explanation seems to be metabolism, as a) no limonene or myrcene were recovered from frass or larvae, and b) borneol, an apparent metabolite of bornyl acetate, was recovered from frass of Douglas fir tussock moth, rusty tussock moth, and white-marked tussock moth, and from tissues of Douglas fir tussock moth and white-marked tussock moth