Mechanistic aspects of the biogenesis of rose oxide in Pelargonium graveolens L'Héritier

Mechanistic aspects of the biogenesis of the chiral monoterpenoid rose oxide in Pelargonium graveolens L'Héritier are investigated using deuterium-labelled precursors. After administration of the precursors using the cut-stem method, the dynamic headspace extracts of the plants are analysed using multidimensional gas chromatography-mass spectrometry (enantio-MDGC-MS). It is unequivocally shown that this plant is able to convert citronellol and menthocitronellol into cis-/trans-rose oxide. Menthocitronellol is converted into rose oxide with a clearly detectable enantiodiscrimination. These facts may be explained with the presence of an oxidase, which is able to oxidize citronellol and menthocitronellol in allylic position. A photooxygenation mechanism including singlet oxygen as the oxidizing agent is rather unlikely. Chirality 10:229–237, 1998. © 1998 Wiley-Liss, Inc.     

Xylitol Production by a Corynebacterium Species

The washed cells of a gluconate-utilizing Corynebacterium strain grown in a gluconate- xylose medium produced xylitol from D-xylose in the presence of gluconate. The amount of xylitol was progressively increased with increasing gluconate concentration.

An extract of cells grown in the gluconate-xylose medium showed NADPH-dependent D-xylose reductase activity and NADP-dependent 6-phosphogluconate dehydrogenase activity.

These enzymes in the cell-free extract were purified by Sephadex G–100 gel filtration.

The reduction of D-xylose to xylitol was demonstrated by the coupling the D-xylose reductase activity to the 6-phosphogluconate dehydrogenase activity with NADP as a cofactor using the cell-free extract and the fractionated enzymes.     

Effect of oxygen dosing point and mixing on the microaerobic removal of hydrogen sulphide in sludge digesters

Limited oxygen supply to anaerobic sludge digesters to remove hydrogen sulphide from biogas was studied. Micro-oxygenation showed competitive performance to reduce considerably the additional equipment necessary to perform biogas desulphurization. Two pilot-plant digesters with an HRT of ∼20 d were micro-oxygenated at a rate of 0.25 NL per L of feed sludge with a removal efficiency higher than 98%. The way of mixing (sludge or biogas recirculation) and the point of oxygen supply (headspace or liquid phase) played an important role on hydrogen sulphide oxidation. While micro-oxygenation with sludge recirculation removed only hydrogen sulphide from the biogas, dissolved sulphide was removed if micro-oxygenation was performed with biogas recirculation. Dosage in the headspace resulted in a more stable operation. The result of the hydrogen sulphide oxidation was mostly elemental sulphur, partially accumulated in the headspace of the digester, where different sulphide-oxidising bacteria were found.     

Developments in multiple headspace extraction

This paper reviews new developments in multiple headspace extraction (MHE), especially its combination with two miniaturized extraction techniques, solid-phase microextraction (SPME) and single-drop microextraction (SDME). The combination of the techniques broadens the applicability of SPME and SDME to quantitative determination of analytes in complex liquid and solid matrixes. These new methods offer several advantages over traditional liquid-solid, liquid-liquid and headspace extraction techniques. The potential applications include extraction of volatiles and semivolatiles from environmental and physiological samples and from different polymer products such as medical and biomedical materials, food packaging and building materials. The theoretical principals of the techniques are also briefly reviewed.     

Floral and vegetative cues in oil-secreting and non-oil-secreting Lysimachia species

Background and Aims

Unrelated plants pollinated by the same group or guild of animals typically evolve similar floral cues due to pollinator-mediated selection. Related plant species, however, may possess similar cues either as a result of pollinator-mediated selection or as a result of sharing a common ancestor that possessed the same cues or traits. In this study, visual and olfactory floral cues in Lysimachia species exhibiting different pollination strategies were analysed and compared, and the importance of pollinators and phylogeny on the evolution of these floral cues was determined. For comparison, cues of vegetative material were examined where pollinator selection would not be expected.

Methods

Floral and vegetative scents and colours in floral oil- and non-floral oil-secreting Lysimachia species were studied by chemical and spectrophotometric analyses, respectively, compared between oil- and non-oil-secreting species, and analysed by phylogenetically controlled methods.

Key Results

Vegetative and floral scent was species specific, and variability in floral but not vegetative scent was lower in oil compared with non-oil species. Overall, oil species did not differ in their floral or vegetative scent from non-oil species. However, a correlation was found between oil secretion and six floral scent constituents specific to oil species, whereas the presence of four other floral compounds can be explained by phylogeny. Four of the five analysed oil species had bee-green flowers and the pattern of occurrence of this colour correlated with oil secretion. Non-oil species had different floral colours. The colour of leaves was similar among all species studied.

Conclusions

Evidence was found for correlated evolution between secretion of floral oils and floral but not vegetative visual and olfactory cues. The cues correlating with oil secretion were probably selected by Macropis bees, the specialized pollinators of oil-secreting Lysimachia species, and may have evolved in order to attract these bees.     

The chemical nature of fetid floral odours in stapeliads (Apocynaceae-Asclepiadoideae-Ceropegieae)

By emitting strong fetid scents, sapromyiophilous flowers mimic brood and food sites of flies to attract them as pollinators. To date, intensive comparative scent analyses have been restricted to sapromyiophilous Araceae. Here, we analysed flower volatiles of fetid stapeliads to improve our understanding of the floral biology of fly pollinated species, and to learn whether mimicry types comparable to those found in Araceae exist. Floral volatiles of 15 species out of 11 genera within the Asclepiadoideae-Ceropegieae-Stapeliinae were collected via headspace adsorption and thermal desorption and analysed by gas chromatography-mass spectometry (GC-MS). Data were analysed using CNESS-NMDS statistics. Sapromyiophilous stapeliads are highly diverse in their scent composition, in which sulphur compounds, benzenoids, fatty acid derivatives or nitrogen-containing compounds dominate. Four groups are evident: species with high p-cresol content but low amounts of polysulphides (herbivore faeces mimicry); species with mainly polysulphides and low amounts of p-cresol (carnivore/omnivore faeces or carcass mimicry); species with high amounts of heptanal and octanal (carnivore/omnivore faeces or carcass mimicry); and species with hexanoic acid (urine mimicry). Considering the findings in the unrelated Araceae, our results support the universality of different mimicry types that are obviously subsumed under the sapromyiophilous syndrome.     

Characterisation of different types of hay by solid-phase micro-extraction-gas chromatography mass spectrometry and multivariate data analysis

The volatile organic compounds of different ground hay samples from Austria, Italy and Switzerland were collected at 50 degrees C on a Supelco Carbowax Divinylbenzene headspace solid-phase microextraction fibre, separated by capillary gas chromatography on an HP5-ms column running a temperature programme and using helium as carrier gas, detected with a mass sensitive detector and studied with principal component analyses after autoscaling selected variables. The analytes, mainly mono- and sesquiterpenes, were able to cluster differences resulting from the site of production. Coumarin can be used to differentiate hay grown north and south of the main chain of the Alps. Acetic acid is appropriate for distinguishing between hay from Kastelruth and Passeier Valley, two South Tyrolean regions. The average linalool content in aftermath is higher than in hay.     

The inhibitory effects of rose powdery mildew infection on the oviposition behaviour and performance of beet armyworms

In this study, we investigated whether the oviposition behaviour and performance of the beet armyworm, Spodoptera exigua (Hübner) (Lepidoptera: Noctuidae), on the rose cultivar Rosa chinensis Jacq. (Rosaceae) were affected when the plants were infected by rose powdery mildew, Podosphaera pannosa (Wallr.: Fr.) de Bary (Erysiphales). The bioassays revealed that the moths significantly avoided ovipositing on mildew‐infected rose leaves when compared to healthy leaves. Pupal weights, emergence rates, and fecundity decreased when the caterpillars were fed mildewed rose leaves. Further laboratory bioassays aimed to elucidate the effects of two volatile headspace extracts (separately collected from healthy and mildewed rose plants) on the oviposition behaviour and performance of the moths. The moths clearly preferred to oviposit on healthy rose leaves that were not sprayed with additional volatiles rather than on healthy leaves sprayed with the volatile extracts from mildewed plants. The mean number of eggs laid on the former leaves was more than six times higher than that laid on the latter leaves. Olfactory bioassays demonstrated that ovipositing moths were significantly more attracted to volatiles emitted by healthy rose leaves than to those emitted by mildew‐infected leaves. Similar results were obtained when comparisons were made between the volatile extracts collected from healthy and mildewed rose plants. Thus, volatiles from mildew‐infected roses have a strong inhibitory effect against the moths. These results indicated that rose volatiles play a role in the oviposition behaviour of the moths, and that the volatiles induced by powdery mildew might be used for insect control.     

基于GC-IMS技术的不同红火蚁监测诱饵的风味成分分析

探讨不同红火蚁Solenopsis invicta Buren监测诱饵的风味成分,以期获得优化诱饵配方的科学依据。本文采用顶空气相色谱-离子迁移谱法分析不同红火蚁监测诱饵在60℃下的气味指纹图谱,并通过主成分分析法分析其风味物质的差异。结果共鉴定出93个信号峰和87种挥发性化合物,载体物质(CK)中具有较高强度峰的化合物包括3种苯、2种醇、3种酮、2种酯、4种醛、1种呋喃和1种烯;自主配制的诱饵(JR、ZR、JZ)的风味组成相似,较高强度峰的化合物包括2种醇、1种酸、12种醛和1-8桉叶素等;市售火腿肠(HT)中的3种烯、10种酮、1种苯、5种醛、1种呋喃、3种醚、7种醇和4种酯是具有较高强度峰的化合物。主成分分析表明,CK、HT与自主研发的诱饵聚集距离较远,三者均单独聚为一类,相互风味成分区别较大。综上所述,JR、ZR和JZ诱饵中醛类物质较多,而HT中酮类与醇类物质较为丰富。上述诱饵的风味成分分析结果能为研发精准高效的红火蚁监测专用诱饵提供重要信息。     

中高温大曲制作过程中火圈真菌菌群演替规律及其风味功能

[背景] 大曲真菌为白酒发酵过程提供发酵剂和糖化剂,火圈为白酒生产提供重要的风味物质,但针对火圈真菌的菌群演替规律及风味功能尚不清楚。[目的] 探索中高温大曲火圈真菌菌群演替规律及风味功能,为优化制曲工艺,提升白酒品质提供理论支撑。[方法] 使用顶空固相微萃取结合气相色谱质谱联用技术和内转录间隔区扩增子测序技术,结合中高温大曲制作过程火圈的理化参数,采用冗余分析的手段对大曲制作过程中火圈真菌演替规律及风味功能进行解析。[结果] 大曲火圈中的乙酸乙酯、丁酸乙酯、正己酸乙酯、乳酸吡喃糖苷甲酯和油酸乙酯等酯类化合物,苯乙酸乙酯、2,4-二甲基苯甲醛、苯甲醇和苯乙醇等芳香族化合物,酸类化合物乙酸,醇类化合物3-辛醇、糠醇等化合物的含量高于曲皮、曲心中的含量。大曲制作过程中从第4阶段开始,火圈位置温度>40℃,还原糖的含量>2%,产生美拉德反应,火圈逐渐形成。库德里阿兹威氏毕赤酵母（Pichia kudriavzevii）、扣囊复膜酵母（Saccharomycopsis fibuligera）是火圈中的优势真菌,在大曲制作的第2-3阶段占据了95%以上的丰度,此时火圈真菌的多样性最低。[结论] 中高温大曲火圈真菌群落演替主要受还原糖含量和温度的影响。大曲火圈为白酒生产提供了重要的酯类、芳香族、酸类、醇类化合物等风味物质,以及P.kudriavzevii、S.fibuligera等白酒发酵的核心酵母菌群,对白酒的生产起着重要的作用。研究结果进一步加深了对火圈的认识,为制曲工艺的调整、白酒品质的提升提供理论依据。