Characterization of Volatile Organic Compounds in Kiwiberries (Actinidia arguta) Exposed to High Hydrostatic Pressure Processing by HS-SPME/GC-MS

HS-SPME/GC-MS analysis was carried out to characterize the profile of volatile organic compounds (VOCs) in kiwiberry cultivars (Geneva and Weiki) exposed to high hydrostatic pressure (HHP) (450–550–650/5 and 15 min). The sum of individual VOCs in Geneva (6.493 mg/kg) and Weiki (11.939 mg/kg) samples was found to be significantly reduced after processing, particularly for pressurization conditions of 650 MPa/15 min (decrease of 62%) and 550 MPa/15 min (decrease of 84%), respectively. On the other hand, Geneva and Weiki exposed to 450 MPa/5 min manifested the lowest loss in the sum of the VOCs. Geneva exposure to 450 MPa/5 min led to an increase in the hexanal (r = 0.782) and linalool (r = 0.806) content. Sample pressurization (450 MPa/15 min) promoted the formation of methyl butanoate, ethyl hexanoate, and cis-geraniol, simultaneously increasing the benzaldehyde (r = 0.886) concentration. However, the treatment of Weiki at 450 MPa/5 min favored trans-2-heptenal (r = 0.999) and linalool (r = 0.970) formation, as well as the (-)-terpinen-4-ol (r = 0.848) and geraniol (r = 0.694) content. Ethyl butanoate, hexanal, and 1-octen-3-ol were highly concentrated in the HHP-treated (450 MPa/5 or 15 min) Weiki. Pressurization decreased the terpenoid contribution, but also increased the contribution of alcohols and aldehydes to the overall VOC number in both tested cultivars.     

Simultaneous distillation-extraction of high-value volatile compounds from Cistus ladanifer L

The present paper describes a procedure to isolate volatiles from rock-rose (Cistus ladanifer L.) using simultaneous distillation-extraction (SDE). High-value volatile compounds (HVVC) were selected and the influence of the extraction conditions investigated. The effect of the solvent nature and extraction time on SDE efficiency was studied. The best performance was achieved with pentane in 1 h operation. The extraction efficiencies ranged from 65% to 85% and the repeatability varied between 4% and 6% (as a CV%).The C. ladanifer SDE extracts were analysed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The HS-SPME sampling conditions such as fiber coating, temperature, ionic strength and exposure time were optimized. The best results were achieved with an 85 μm polyacrylate fiber for a 60 min headspace extraction at 40 °C with 20% (w/v) of NaCl. For optimized conditions the recovery was in average higher than 90% for all compounds and the intermediate precision ranged from 4 to 9% (as CV %). The volatiles α-pinene (22.2 mg g⁻¹ of extract), 2,2,6-trimethylcyclohexanone (6.1 mg g⁻¹ of extract), borneol (3.0 mg g⁻¹ of extract) and bornyl acetate (3.9 mg g⁻¹ of extract) were identified in the SDE extracts obtained from the fresh plant material.     

Characterization of coal tars by HPLC group type separation and capillary GC of volatiles

Summary Group separation of malthene fractions of tar samples obtained from brown coals of different ranks at two different temperatures (500 and 800°C) was performed by HPLC using amino-cyano bonded phase packing with two eluent systems of different polarities and backflushing technique. Group composition of different tar samples was compared and evaluated. Amount and distribution of volatile compounds in the malthene fractions were determined by capillary gas chromatography on a CP-Sil 5 WCOT column. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Isolation of volatiles with insecticidal properties from the genusTagetes (Marigold)

Summary The results of optimizing Soxhlet and Simultaneous Distillation-Extraction (SSDE) procedures for the isolation of natural insecticides fromTagetes erecta, Tagetes patula, andTagetes minuta, members of theCompositae family, are presented. Extraction procedures were developed and validated that produced the extract with the highest degree of biocidal activity. The highest activity was obtained with extracts isolated by SSDE using methylene chloride. Initial work was carried out on a micro-SSDE. Preparative SSDE was used to provide large quantities of extracts for bioassays. Bioassays were used to govern optimization procedures usingAedes aegypti andAnopheles stephensi adults and larvae as target organisms.Tagetes minuta was determined to be the most active of the three species studied. Evaluation of activity and recovery versus extraction time was investigated. It was determined that an extraction time of ten hours resulted in the highest activity and over 90% recovery of the oils. Finally, supercritical fluid extraction of the flowers with CO₂ was compared to SSDE.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

Analysis of volatiles emitted by potato plants by means of a Colorado beetle electroantennographic detector

An electroantennographic detector based on the antenna of the Colorado potato beetle (Leptinotarsa decemlineata Say, 1824) was used to investigate volatile organic compounds emitted by injured potato plants (Solanum tuberosum L., 1753). Samples were collected on charcoal traps using the CLSA method. Analyses were performed with a GC-EAD-FID setup as well as a GC-MS system. The experiments revealed that several groups of compounds are perceptible to the Colorado potato beetle. The ability of the Colorado potato beetle to detect green leaf odours (e.g. (Z)-3-hexen-1-ol and (E)-2-hexenal), linalool and some terpenes has been noticed before [Visser et al., J. Chem. Ecol. 5 (1979) 13]. In this work the presence of (Z)-3-hexen-1-ol, (E)-2-hexenal and linalool in the potato odour could be confirmed. Moreover, β-myrcene, benzeneethanol, and several sesquiterpenes (e.g. caryophyllene and germacrene-D) were identified. The GC-EAD experiments reveal that apart from the green leaf odours and linalool prominent reactions of the Colorado bettle antenna are induced by benzeneethanol and the sesquiterpene fraction.     

Identification of Free and Glycosidically Bound Volatiles and Glycosides by Capillary GC and Capillary GC‐MS in “Lulo del Chocó” (Solanum topiro)

The volatile constituents of lulo del Chocó (Solanum topiro) fruit pulp obtained by liquid‐liquid extraction were analyzed by capillary GC and capillary GC‐MS. In total, 30 components were identified with methyl salicylate, hexadecanoic acid, hexanal, guaiacol, ethyl butanoate, and ethyl acetate being the major components. Chirospecific MDGC analysis revealed the predominance of (R)‐ethyl‐3‐hydroxybutanoate (ee 40%) and the presence of racemic mixtures both of δ‐octalactone and of δ‐decalactone. For γ‐hexalactone, γ‐octalactone, and γ‐decalactone enantiomeric distributions of 22.4 : 77.6, 22.9 : 77.1, and 20.0 : 80.0, (R) : (S), respectively, were determined. Glycosidically bound aroma compounds were identified by capillary GC and capillary GC‐MS after isolation of the glycosidic fraction obtained by Amberlite XAD‐2 adsorption and methanol elution followed by hydrolysis with a commercial pectinase enzyme. In total 13 bound aroma compounds (aglycones) were identified. These aglycones mainly consisted of compounds exhibiting aromatic structures. Additionally, with the aid of capillary GC and capillary GC‐MS (EI and NCI) of trifluoroacetylated derivatives we identified eight glucosides: the novel 3,6‐epoxy‐7‐megastigmen‐5,9‐diol β‐D‐glucopyranoside and the hexyl, benzyl, linalyl oxide (furanic), 2‐phenylethyl, vomifolyl (isomer 1), (6S,9R)‐vomifolyl, and scopoletin β‐D‐glucopyranosides.     

Multicolour Fluorescent Memory Based on the Interaction of Hydroxy Terphenyls with Fluoride Anions

Memory operations based on variation of a molecule’s properties are important because they may lead to device miniaturization to the molecular scale or increasingly complex information processing protocols beyond the binary level. Molecular memory also introduces possibilities related to information‐storage security where chemical information (or reagents) might be used as an encryption key, in this case, acidic/basic reagents. Chemical memory that possesses both volatile and non‐volatile functionality requires reversible conversion between at least two chemically different stable or quasi‐stable states. Here we have developed the phenol–phenoxide equilibrium of phenol fluorophores as a data storage element, which can be used to write or modulate data using chemical reagents. The properties of this system allow data to be stored and erased either in non‐volatile or volatile modes. We also demonstrate non‐binary switching of states made possible by preparation of  a composite containing the molecular memory elements.     

Detailed Chemical Prospecting of Volatile Organic Compounds Variations from Adriatic Macroalga Halopteris scoparia

The present study aimed to isolate volatile organic compounds (VOCs) from fresh (FrHSc) and air-dried (DrHSc) Halopteris scoparia (from the Adriatic Sea) by headspace solid-phase microextraction (HS-SPME) and hydrodistillation (HD) and to analyse them by gas chromatography and mass spectrometry (GC–MS). The impact of the season of growth (May–September) and air-drying on VOC composition was studied for the first time, and the obtained data were elaborated by principal component analysis (PCA). The most abundant headspace compounds were benzaldehyde, pentadecane (a chemical marker of brown macroalgae), and pentadec-1-ene. Benzaldehyde abundance decreased after air-drying while an increment of benzyl alcohol after drying was noticed. The percentage of pentadecane and heptadecane increased after drying, while pentadec-1-ene abundance decreased. Octan-1-ol decreased from May to September. In HD-FrHSc, terpenes were the most abundant in June, July, and August, while, in May and September, unsaturated aliphatic compounds were dominant. In HD-DrHSc terpenes, unsaturated and saturated aliphatic compounds dominated. (E)-Phytol was the most abundant compound in HD-FrHSc through all months except September. Its abundance increased from May to August. Two more diterpene alcohols (isopachydictyol A and cembra-4,7,11,15-tetraen-3-ol) and sesquiterpene alcohol gleenol were also detected in high abundance. Among aliphatic compounds, the dominant was pentadec-1-ene with its peak in September, while pentadecane was present with lower abundance. PCA (based on the dominant compound analyses) showed distinct separation of the fresh and dried samples. No correlation was found between compound abundance and temperature change. The results indicate great seasonal variability of isolated VOCs, as well among fresh and dried samples, which is important for further chemical biodiversity studies.     

Group-type quantitative analysis of flavor compounds in ripening avocados

Avocados are a superfood gaining popularity in people's diet. Profiling and quantifying the volatiles associated with flavor can further help in understanding the fruit. However, this is challenging due to relatively low abundance of volatile compounds. The complex mixtures inherent to avocado flavor can result in coelutions using classical chromatographic techniques. To overcome these challenges, solid-phase microextraction was used to extract and preconcentrate volatiles, then separated and quantified using two-dimensional gas chromatography with a flame ionization detector. This technique enhances separation power and produces well-ordered chromatograms, allowing for templated groupings of compounds of similar chemical composition into regions. Using the flame ionization detector, an average response factor was determined and used for quantification of these templated group-type regions, as well as individual compounds. This group-type quantification improved the overall precision of compound classes in 50 avocados by at least a factor of 2, when compared to that of the individual components. Overall, the abundance of associated flavor groups, such as terpenes and alcohols decreased, whereas aldehyde groups remained constant throughout ripening. The combination of solid-phase microextraction with two-dimensional gas chromatography and group-type quantification allows for an overall better understanding of the volatiles associated with flavor of avocados.