Volatile Nitriles Research Articles

Biosynthesis, herbivore induction, and defensive role of phenylacetaldoxime glucoside.

Aldoximes are well-known metabolic precursors for plant defense compounds such as cyanogenic glycosides, glucosinolates, and volatile nitriles. They are also defenses themselves produced in response to herbivory; however, it is unclear whether aldoximes can be stored over a longer term as defense compounds and how plants protect themselves against the potential autotoxic effects of aldoximes. Here, we show that the Neotropical myrmecophyte tococa (Tococa quadrialata, recently renamed Miconia microphysca) accumulates phenylacetaldoxime glucoside (PAOx-Glc) in response to leaf herbivory. Sequence comparison, transcriptomic analysis, and heterologous expression revealed that 2 cytochrome P450 enzymes, CYP79A206 and CYP79A207, and the UDP-glucosyltransferase UGT85A123 are involved in the formation of PAOx-Glc in tococa. Another P450, CYP71E76, was shown to convert PAOx to the volatile defense compound benzyl cyanide. The formation of PAOx-Glc and PAOx in leaves is a very local response to herbivory but does not appear to be regulated by jasmonic acid signaling. In contrast to PAOx, which was only detectable during herbivory, PAOx-Glc levels remained high for at least 3 d after insect feeding. This, together with the fact that gut protein extracts of 3 insect herbivore species exhibited hydrolytic activity toward PAOx-Glc, suggests that the glucoside is a stable storage form of a defense compound that may provide rapid protection against future herbivory. Moreover, the finding that herbivory or pathogen elicitor treatment also led to the accumulation of PAOx-Glc in 3 other phylogenetically distant plant species suggests that the formation and storage of aldoxime glucosides may represent a widespread plant defense response.

UV–Vis Light-induced Aging of Titan’s Haze and Ice

Abstract The study of the photochemical aging of aerosols is an important tool for understanding Titan’s stratosphere/troposphere composition and evolution, particularly the haze. Laboratory simulations of the photoreactivity of the haze aerosol analogs provide insight into the photochemical evolution of Titan’s atmosphere at and below the haze layers. Here we use experimental simulations to investigate the evolution of the laboratory analogs of these organic aerosols under ultraviolet (UV)–visible (Vis) photons, which make it through the haze layers during their sedimentation process. We present experimental results for the aging of Titan’s aerosol analogs obtained from two dominant nitrogen-containing organics, HC3N and HCN, under simulated Titan atmospheric conditions (photons and temperature). We report that volatile nitriles condensed on haze particles could be incorporated through photochemistry and provide one such sink mechanism for nitrile compounds. We provide laboratory evidence that the organic aerosols could photochemically evolve during their sedimentation through Titan’s atmosphere.

Herbivore‐induced poplar cytochrome P450 enzymes of the CYP71 family convert aldoximes to nitriles which repel a generalist caterpillar

Numerous plant species emit volatile nitriles upon herbivory, but the biosynthesis as well as the relevance of these nitrogenous compounds in plant-insect interactions remains unknown. Populus trichocarpa has been shown to produce a complex blend of nitrogenous volatiles, including aldoximes and nitriles, after herbivore attack. The aldoximes were previously reported to be derived from amino acids by the action of cytochrome P450 enzymes of the CYP79 family. Here we show that nitriles are derived from aldoximes by another type of P450 enzyme in P.trichocarpa. First, feeding of deuterium-labeled phenylacetaldoxime to poplar leaves resulted in incorporation of the label into benzyl cyanide, demonstrating that poplar volatile nitriles are derived from aldoximes. Then two P450 enzymes, CYP71B40v3 and CYP71B41v2, were characterized that produce aliphatic and aromatic nitriles from their respective aldoxime precursors. Both possess typical P450 sequence motifs but do not require added NADPH or cytochrome P450 reductase for catalysis. Since both enzymes are expressed after feeding by gypsy moth caterpillars, they are likely to be involved in herbivore-induced volatile nitrile emission in P.trichocarpa. Olfactometer experiments showed that these volatile nitriles have a strong repellent activity against gypsy moth caterpillars, suggesting they play a role in induced direct defense against poplar herbivores.

Laboratory-scale biofiltration of acrylonitrile by Rhodococcus rhodochrous DAP 96622 in a trickling bed bioreactor

Acrylonitrile (ACN), a volatile component of the waste generated during the production of acrylamide, also is often associated with aromatic contaminants such as toluene and styrene. Biofiltration, considered an effective technique for the treatment of volatile hydrocarbons, has not been used to treat volatile nitriles. An experimental laboratory-scale trickling bed bioreactor using cells of Rhodococcus rhodochrous DAP 96622 supported on granular activated carbon (GAC) was developed and evaluated to assess the ability of biofiltration to treat ACN. In addition to following the course of treatability of ACN, kinetics of ACN biodegradation during both recycle batch and open modes of operation by immobilized and free cells were evaluated. For fed-batch mode bioreactor with immobilized cells, almost complete ACN removal (>95%) was achieved at a flow rate of 0.1 microl/min ACN and 0.8 microl/min toluene (TOL) (for comparative purposes this is equivalent to 6.9 mg l(-1) h(-1) ACN and 83.52 mg l(-1) h(-1) TOL). In a single-pass mode bioreactor with immobilized cells, at ACN inlet loads of 100-200 mg l(-1) h(-1) and TOL inlet load of approximately 400 mg l(-1) h(-1), with empty bed retention time (EBRT) of 8 min, ACN removal efficiency was approximately 90%. The three-dimensional structure and characteristics of the biofilm were investigated using confocal scanning laser microscopy (CSLM). CLSM images revealed a robust and heterogeneous biofilm, with microcolonies interspersed with voids and channels. Analysis of the precise measurement of biofilm characteristics using COMSTAT agreed with the assumption that both biomass and biofilm thickness increased along the carbon column depth.

Identification and variation of volatile compounds in sternal gland secretions of male koalas (phascolarctos cinereus)

The content of the sternal gland secretion from four male koalas (Phascolarctos cinereus) was analyzed using gas chromatography–mass spectrometry. Volatile fatty acids, aldehydes, ketones, mono- and sesquiterpenes were identified, together with various volatile nitriles and oximes, some of which had not previously been described from any mammalian skin gland. Benzyl cyanide and phenylacetaldehyde oxime were identified as major components of the secretions, together with smaller amounts of the novel 3-methylthiopropanal oxime. The relative abundance of the identified compounds was highly variable between individuals and the scent composition was found to be partly determined by the scent of surrounding conspecifics. Principal component analysis revealed a high similarity between related individuals.

Detoxification of Rapeseed Meal by Extrusion with an Added Basic Salt

ABSTRACTA commercial, high‐glucosinolate, rapeseed meal with no added salt or mixed with 2, 5, or 10% NH4HCO3 was extruded under different processing conditions using the Wenger TX‐52 twin‐screw extruder. Male Wistar rats were fed 13 diets containing 15% rapeseed meals (including nonextruded) or a casein‐based control diet. After six weeks, blood samples were taken, and serum was analyzed for thyroid hormones. Extrusion processing under all salt and steam conditions tested reduced glucosinolate levels in the meal, but no significant correlation was found between intensity of the treatment conditions and glucosinolate reduction. Higher weight gains, feed efficiencies, and thyroid hormone profiles were observed with use of the extruded meals; but no treatment completely detoxified the meal. Histopathological evaluation showed that thyroid and other tissue abnormalities occurred in all animals except those fed the casein diet. Antinutrients, including glucosinolates and probably volatile nitriles, in the meal were reduced by extrusion processing under the basic conditions of this experiment.

Infrared spectra of gaseous mononitriles: Application to the atmosphere of Titan

A list of volatile nitriles, not yet detected in the atmosphere of Titan, but likely to be present in this environment, has been selected: acetonitrile, propionitrile, acrylonitrile, crotononitrile, allyl cyanide, methacrylonitrile, and cyanopropyne. The spectra of these compounds in the gas phase have been systematically studied, in the mid- and far-infrared ranges. For each selected nitrile, the most intense vibration bands have been determined. Their strengths have been characterized by estimating the monochromatic absorption coefficient at the maximum(s) of the bands, and the integrated absorbance over the entire band. Then, in order to estimate the detectability of the selected compounds by infrared spectroscopy in the atmosphere of Titan, the data obtained have been extrapolated to the case of Titan.

Organic syntheses from CH4-N2 atmospheres: implications for Titan.

Numerous experiments have already been performed, simulating the evolution of gaseous mixtures containing CH4 when submitted to energy flux. From their results, it appears that a variety of organic compounds, including unsaturated hydrocarbons and nitriles such as HCN, can be synthesized into noticeable amounts from CH4-N2 mixtures. In particular, systematic studies of the influence of the composition of the mixture on the nature and amount of synthesized compounds show that organic volatile nitriles, and particularly cyanoacetylene and cyanogen, are formed only in media rich in nitrogen. Those nitriles have been identified very recently in the atmosphere of Titan, and thus, data from such laboratory experiments may provide important indirect information on the organic chemistry occurring at the periphery of this satellite of Saturn. However, during these experiments, there is a continuous formation and accumulation of molecular hydrogen, which does not occur in the atmosphere of Titan, because of H2 escape. In order to reassess the data already available from this type of laboratory studies, experiments on CH4-N2 atmospheres, with and without H2 escape, have been recently performed. The influence of this parameter on the chemical evolution of the atmosphere and on the nature and relative quantities of organic compounds has been studied. After reviewing these experiments, implications of the obtained results on the organic chemistry at the periphery of Titan are discussed.

Cuprous hydrometallurgy: Part VIII. Solvent extraction and recovery of copper(I) chloride with organic nitriles from an iron(III), copper(II) chloride, two-step oxidative leach of chalcopyrite concentrate

Water-immiscible organic nitriles selectively extract copper(I) chloride as CuCl from aqueous chloride solutions. The distribution coefficients for the extraction of metal chlorides are in the order Ni 2+ ⪡ Fe 2+ < Na + < Cu 2+ ≈ Co 2+ < Cu + ⩽ Fe 3+. The equilibrium Cu 2+ + Fe 2+ ⇌ Cu + + Fe 3+ lies strongly to the right in nitrile solutions containing a small amount of water. When volatile nitriles containing some water are used as extractants, CuCl may be recovered from the organic phase by stripping the solvent with steam. Pure CuCl, suitable for reduction to electrolytic-grade copper, is precipitated from the residual aqueous phase. A process is demonstrated for the recovery of pure CuCl from chalcopyrite concentrate, in which a two-stage, iron(III), copper(II) chloride leach is used to maximize the amount of CuCl relative to CuCl 2 formed in solution.

Application de la chromatographie en phase gazeuse à l'étude des nitrilases et amidases

Use of gas—liquid chromatography for the study of nitrilases and amidases A gas—liqued chromatographic procedure is described for the determination of nitrilasic and amidasic activities. This method allows to monitor the kinetics of the hydrolysis of volatile nitriles and amides and because of its sensitivity, to determine the Michaelis constants K m of the acetonitrilase and the acetamidase of Brevibacterium R 312. For these enzymes, a correlation is shown between the kinetics monitored by proton nuclear magnetic resonance spectroscopy and gas—liquid chromatography.

A Phosphoric Acid Treated Reactive GLC Column for the Analysis of Long Chain Amides

Abstract The conversion of nonvolatile amides to more volatile nitriles on a reactive column was studied. It was found that pyrophosphoric acid was necessary for the conversion, that the amide reacts 100% on the first 6 inches of the column to produce one nitrile and 3 carboxylic acid groups for every 4 amide groups injected and that a quantitative analytical procedure is possible.

Value and Use of Volatile Nitriles for Household Fumigation1

Value and Use of Volatile Nitriles for Household Fumigation1