四种单萜类查尔酮的合成

以2, 4, 6-三羟基苯乙酮和柠檬醛为起始原料经过环化、羟醛缩合和催化加氢合成四种单萜类查尔酮;关键步骤2, 4, 6-三羟基苯乙酮和柠檬醛是在吡啶的催化下经过电子环化、质子迁移及Diels-Alder反应合成天然产物desbenzylidenerubramin (1),中间体1合成一种天然产物产物rubraine (2~5),其结构经~1H NMR和HREIMS表征。     

Biotransformation of hop derived compounds by Brettanomyces yeast strains

Several hop derived compounds in wort are known to be converted by yeast during fermentation, influencing the overall perception of the beer. A deeper understanding of such metabolic processes during fermentation is needed to achieve better control of the outcome. Here, the interaction between hop derived compounds and the yeast genera Brettanomyces was studied. Several Brettanomyces strains with different genomic backgrounds were selected, focusing on two traits: beta-glucosidase activity and nitrate assimilation. The role of three beta-glucosidases present in Brettanomyces bruxellensis and Brettanomyces anomalus and their impact on the final monoterpene alcohol profile was analysed. The beta-glucosidase activity was highly strain dependent, with B. anomalus CRL-49 exhibiting the highest conversion. Such activity could not be related to the release of aglycones from hops during fermentation, as a substantial part of such activity was intracellular. Nevertheless, the reduction of geraniol to β-citronellol was remarkably efficient for all Brettanomyces strains during fermentation, and it is suggested that two oxidoreductases BbHye2 and BbHye3 may have an influence. Moreover, the transfer of nitrate from hops to wort and its further assimilation by Brettanomyces species was analysed. The amount of nitrate in wort proved to be linearly proportional to the contact time of the hops with the wort. The level of nitrate assimilation by yeast was shown to be dependent on the nitrate assimilation cluster (YNR, YNI, YNT). Hence, the desired yeast strains may be selected according to the genetic make-up. © 2020 The Authors. Journal of the Institute of Brewing published by John Wiley & Sons Ltd on behalf of The Institute of Brewing & Distilling     

Gene Discovery in Gelsemium Highlights Conserved Gene Clusters in Monoterpene Indole Alkaloid Biosynthesis

Genome mining is a routine technique in microbes for discovering biosynthetic pathways. In plants, however, genomic information is not commonly used to identify novel biosynthesis genes. Here, we present the genome of the medicinal plant and oxindole monoterpene indole alkaloid (MIA) producer Gelsemium sempervirens (Gelsemiaceae). A gene cluster from Catharanthus roseus, which is utilized at least six enzymatic steps downstream from the last common intermediate shared between the two plant alkaloid types, is found in G. sempervirens, although the corresponding enzymes act on entirely different substrates. This study provides insights into the common genomic context of MIA pathways and is an important milestone in the further elucidation of the Gelsemium oxindole alkaloid pathway.     

Investigation of emissions from heated essential‐oil‐rich fuels at 200 °C

Essential oil of fuels is closely linked with the behavior of forest fires, especially high intensity fires and eruptive fires. It is assumed that the potential reason is the large quantities of flammable gases released from essential oil‐rich fuels before pyrolysis in fire environment. However, few studies have been carried out on the hypothesis. The purpose of the present study is to investigate the emissions from essential oil‐rich fuels. The fuels were collected from three coniferous species. In the experiment, needles and twigs were heated in a vacuum oven at 200 °C, and the emissions within 15 min had been sampled using Tenax tubes. Gas chromatography–mass spectrometry served as an analytical instrument. The results showed that the emissions contained high proportion of monoterpenes, such as α‐pinene, camphene, β‐pinene, 3‐carene, and d ‐limonene. The monoterpene emissions from heated needles and twigs of Pinus pumila, Larix gmelinii, and Pinus sylvestris were 61.221, 49.606, and 37.853 µg g^?1 dry weight (needles), and 211.727, 139.957, and 121.505 µg g^?1 dry weight (twigs), respectively. Statistical analyses showed the significant differences not only among species but also between needles and twigs. Copyright © 2012 John Wiley & Sons, Ltd.     

Larval osmeterial secretions of the swallowtails (Papilio)

The larval osmeterial secretions of sixPapilio species examined displayed a remarkable qualitative change at the fourth larval ecdysis. The secretions of 4th (penultimate) instar larvae ofP. machaon, P. memnon, P. helenus, P. bianor, andP. maackii principally comprised mono- and/or sesquiterpenoids. The compounds identified from these species included -pinene, sabinene, -myrcene, limonene, -phellandrene, (Z)--ocimene, (E)--ocimene, -elemene, -caryophyllene, (E)--farnesene, -selinene, (E,E)--farnesene, germacrene-A, germacrene-B, caryophyllene oxide, methyl 3-hydroxy-n-butyrate, and acetic acid. In contrast, the secretion of 4th larval instar ofP. xuthus, although containing similar terpenic compounds, was accompanied by large amounts of aliphatic acids and their esters: isobutyric acid, 2-methylbutyric acid, methyl isobutyrate and methyl 2-methylbutyrate. On the other hand, the osmeterial secretions of 5th (last) instar larvae varied little in quality among the six species, and the identified compounds consisted of isobutyric acid, 2-methylbutyric acid, methyl isobutyrate, ethyl isobutyrate, methyl 2-methylbutyrate, ethyl 2-methylbutyrate, and isovaleric acid, the last of which was specific toP. bianor andP. maackii. The chemical alteration of osmeterial exudate synchronized at the final larval ecdysis with the larval morphological change (particularly in body coloration) that appears to be of defensive significance against predators.     

Enantiomeric Composition of Monoterpene Hydrocarbons in Some Conifers and Receptor Neuron Discrimination of α-Pinene and Limonene Enantiomers in the Pine Weevil, Hylobius abietis

The enantiomeric composition of seven monoterpene hydrocarbons in headspace volatiles of spruce sawdust and seedlings (Picea abies), pine seedlings (Pinus sylvestris), and branches of juniper (Juniperus communis) was determined by gas chromatographic separation on a -Cyclodextrin column. For the six monoterpenes, -pinene, camphene, -pinene, sabinene, limonene, and -phellandrene, both enantiomers were present, whereas for 3-carene only the (+)-configuration was found. The amount of each enantiomer varied considerably both in relation to total amount of all of them, and for the six pairs also in relation to the opposite enantiomer. One olfactory receptor neuron in the pine weevil (Hylobius abietis) showed a strong response to -pinene when stimulated with all four headspace materials via a GC equipped with a DB-WAX column. The same neuron was subsequently tested with repeated stimulations via the GC effluent containing the (+)- or (–)-enantiomer. A marked better response to (+)- than to (–)--pinene was elicited. Another olfactory receptor neuron that responded strongly to limonene when stimulated with the spruce volatiles was tested for enantiomers of limonene. This neuron responded more strongly to (–)- than to (+)-limonene, when stimulated alternately with each of the limonene enantiomers. Discrimination between enantiomers by plant olfactory receptor neurons suggests that the enantiomeric ratios of volatile compounds may be important in host location by the pine weevil.     

Quantification of aroma vapours sorbed in polyethene films using supercritical carbon dioxide

Extraction with supercritical carbon dioxide was used to quantity the amounts of seven different aroma vapours sorbed in polyethene films. The method was found to completely extract all aroma compounds from the films. The solution of aroma compounds in the polymer films decreased with increasing polymer density. Monoterpenes were always completely sorbed in the films, whereas aldehydes and ketones had a much lower affinity for the films. The sulphur-containing compound, thiophene, was difficult to analyse due to its adsorption on metal surfaces.