1-Hexanol

Supramolecular solvent (SUPRASs) extraction method for detecting benzodiazepines and zolpidem in human urine and blood using gas chromatography tandem mass spectrometry.[Pubmed:33285339]

Leg Med (Tokyo). 2020 Nov 28;48:101822.

OBJECTIVE: A high-throughput and sensitive method using supramolecular solvent (SUPRASs) for detecting 9 benzodiazepines and zolpidem in human urine and blood by gas chromatography-tandem mass spectrometry (GC-MS/MS) was newly established and applied to authentic human urine and blood samples in this study. METHODS: Urine and blood samples were subjected to liquid-liquid extractions with supramolecular solvent mixture which consists of tetrahydrofuran and 1-Hexanol. The solvent layer was evaporated to dryness by stream of nitrogen. The residue was reconstituted with methanol, and subjected to analysis by GC-MS/MS in multiple reaction monitoring (MRM) mode; internal standard method was employed for quantifying of each targeted compound. RESULTS: The regression equation has a good linear relationship with correlation coefficients for all tested compounds were not lower than 0.9991. The lower limits of the quantification ranged from 0.20 to 5 ng/mL for tested compounds in urine; Meanwhile, the lower limits of the quantification in this method ranged from 1 to 50 ng/mL for tested compounds in blood. These results showed that excellent reproducibility and satisfactory extraction recovery rates could be obtained for the established analytical method for 10 drugs in both blood and urine samples. CONCLUSION: The established method in this study was high-throughput, simple and sufficiently sensitive for determining of benzodiazepinesand zolpidem in human urine and blood. Therefore, this newly established method could be of use for qualitative and quantitative determination of such drugs in urine and blood samples either for clinical poisoning monitoring or for forensic identification.

Noncovalently Linked Metallacarboranes on Functionalized Magnetic Nanoparticles as Highly Efficient, Robust, and Reusable Photocatalysts in Aqueous Medium.[Pubmed:33284598]

ACS Appl Mater Interfaces. 2020 Dec 7.

A successful homogeneous photoredox catalyst has been fruitfully heterogenized on magnetic nanoparticles (MNPs) coated with a silica layer, keeping intact its homogeneous catalytic properties but gaining others due to the easy magnetic separation and recyclability. The amine-terminated magnetic silica nanoparticles linked noncovalently to H[3,3'-Co(1,2-C2B9H11)2](-) (H[1]), termed MSNPs-NH2@H[1], are highly stable and do not produce any leakage of the photoredox catalyst H[1] in water. The magnetite MNPs were coated with SiO2 to provide colloidal stability and silanol groups to be tethered to amine-containing units. These were the MSNPs-NH2 on which was anchored, in water, the cobaltabis(dicarbollide) complex H[1] to obtain MSNPs-NH2@H[1]. Both MSNPs-NH2 and MSNPs-NH2@H[1] were evaluated to study the morphology, characterization, and colloidal stability of the MNPs produced. The heterogeneous MSNP-NH2@H[1] system was studied for the photooxidation of alcohols, such as 1-phenylethanol, 1-Hexanol, 1,6-hexanediol, or cyclohexanol among others, using catalyst loads of 0.1 and 0.01 mol %. Surfactants were introduced to prevent the aggregation of MNPs, and cetyl trimethyl ammonium chloride was chosen as a surfactant. This provided adequate stability, without hampering quick magnetic separation. The results proved that the catalysis could be speeded up if aggregation was prevented. The recyclability of the catalytic system was demonstrated by performing 12 runs of the MSNPs-NH2@H[1] system, each one without loss of selectivity and yield. The cobaltabis(dicarbollide) catalyst supported on silica-coated magnetite nanoparticles has proven to be a robust, efficient, and easily reusable system for the photooxidation of alcohols in water, resulting in a green and sustainable heterogeneous catalytic system.

Characterization of free and glycosidically bound volatile compounds, fatty acids, and amino acids in Vitis davidii Foex grape species native to China.[Pubmed:33282431]

Food Sci Biotechnol. 2020 Oct 6;29(12):1641-1653.

Berries of six Vitis davidii Foex (spine grape) cultivars ('Baiputao', 'Gaoshan 1', 'Gaoshan 2', 'Seputao', 'Miputao', and 'Tianputao') were harvested from a commercial vineyard in Hunan Province in China. Free and bound volatile compounds and fatty acids were analyzed by GC-MS, and amino acids were analyzed by HPLC. 'Tianputao' and 'Miputao' were characterized by relatively higher concentrations of aromatic amino acids and lower concentrations of branched-chain amino acids. The major free volatile compounds of spine grapes were hexanal, (E)-2-hexenal, 1-Hexanol, (E)-2-hexenol, (E)-beta-damascenone, and benzeneacetaldehyde. The major glycosidically bound volatile compounds identified were 1-Hexanol, menthol, nerol, 1-butanol, 3-methyl-3-butenol, benzenemethanol, beta-phenylethanol, eugenol, and guaiacol. (E)-beta-damascenone, benzeneacetaldehyde, guaiacol, and eugenol had odor activity values (OAVs) > 1 in all cultivar grapes. Partial least squares discriminant analysis (PLS-DA) revealed 'Tianputao' to be distinct from the other cultivars due to its relatively higher concentrations of major terpenoids, norisoprenoids, higher alcohols, and aromatic amino acids.

Analysis of Hop-Derived Thiols in Beer Using On-Fiber Derivatization in Combination with HS-SPME and GC-MS/MS.[Pubmed:33274918]

J Agric Food Chem. 2020 Dec 4.

The quantitation of the hop varietal thiols 4-mercapto-4-methyl-2-pentanone (4MMP), 3-mercapto-1-Hexanol (3MH), and 3-mercaptohexylacetate (3MHA) from beer is challenging. This primarily relates to their low concentration (ng/L levels) and their reactivity. Published assays for thiol quantitation from beer include complex and/or time-consuming sample preparation procedures involving manual handling and use reagents that are harmful because they contain mercury. To facilitate thiol analysis from beer, the current article is concerned with the implementation of an automated headspace solid-phase microextraction (HS-SPME) on-fiber derivatization (OFD) approach using 2,3,4,5,6-pentafluorobenzyl bromide followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). Optimization of HS-SPME and MRM conditions was based on a central composite design approach. The final OFD-HS-SPME-GC-MS/MS method yielded limits of quantitation below the sensory thresholds of 4MMP, 3MH, and 3MHA. Method validation and application on beers brewed with German, Australian, and US hops, as well as with added fruits displayed excellent method performance.

Effect of CO2 Preservation Treatments on the Sensory Quality of Pomegranate Juice.[Pubmed:33260509]

Molecules. 2020 Nov 28;25(23). pii: molecules25235598.

Due to the interest in identifying cost-effective techniques that can guarantee the microbiological, nutritional, and sensorial aspects of food products, this study investigates the effect of CO2 preservation treatment on the sensory quality of pomegranate juice at t0 and after a conservation period of four weeks at 4 degrees C (t28). The same initial batch of freshly squeezed non-treated (NT) juice was subjected to non-thermal preservation treatments with supercritical carbon dioxide (CO2), and with a combination of supercritical carbon dioxide and ultrasound (CO2-US). As control samples, two other juices were produced from the same NT batch: A juice stabilized with high pressure treatment (HPP) and a juice pasteurized at high temperature (HT), which represent an already established non-thermal preservation technique and the conventional thermal treatment. Projective mapping and check-all-that-apply methodologies were performed to determine the sensory qualitative differences between the juices. The volatile profile of the juices was characterized by gas chromatography-mass spectrometry. The results showed that juices treated with supercritical CO2 could be differentiated from NT, mainly by the perceived odor and volatile compound concentration, with a depletion of alcohols, esters, ketones, and terpenes and an increase in aldehydes. For example, in relation to the NT juice, limonene decreased by 95% and 90%, 1-Hexanol decreased by 9% and 17%, and camphene decreased by 94% and 85% in the CO2 and CO2-US treated juices, respectively. Regarding perceived flavor, the CO2-treated juice was not clearly differentiated from NT. Changes in the volatile profile induced by storage at 4 degrees C led to perceivable differences in the odor quality of all juices, especially the juice treated with CO2-US, which underwent a significant depletion of all major volatile compounds during storage. The results suggest that the supercritical CO2 process conditions need to be optimized to minimize impacts on sensory quality and the volatile profile.

First deep eutectic solvent-based (DES) stationary phase for gas chromatography and future perspectives for DES application in separation techniques.[Pubmed:33254003]

J Chromatogr A. 2020 Nov 14;1635:461701.

The paper presents the first application of deep eutectic solvents (DES) as stationary phases for gas chromatography. DES obtained by mixing tetrabutylammonium chloride (TBAC) as a hydrogen bond acceptor (HBA) with heptadecanoic acid being a hydrogen bond donor (HBD) in a mole ratio of HBA:HBD equal to 1:2 was characterized by its ability to separate volatile organic compounds (VOCs). The Rohrschneider - McReynolds constants determined reveal that the synthesized DES is a stationary phase of medium polarity. A detailed retention characteristic was determined for a number of groups of chemical compounds, including aromatic hydrocarbons, alcohols, ketones, sulfides and thiophene derivatives. The synthesized DES was found to have a high selectivity towards alcohols. At the same time, the investigated stationary phase was found to have specific interactions with some analytes. For example, a stronger retention was observed for 1-Hexanol and 1-heptanol compared to other alcohols. Retention times of these two alcohols are longer by 191% and 300%, respectively, relative to the expected value based on their boiling point. Such an increased retention is caused by a synergistic effect of various kinds of interactions - the possibility of formation of hydrogen bonds between the DES and the hydroxyl group of alcohols and hydrophobic interactions of alkyl chains of the DES with the alkyl chain of alcohols. The ability to modify properties of DESs by replacement of HBA or HBD with a different chemical compound or by dissolving in DES macromolecular substances makes the proposed stationary phase highly flexible. In addition to using the developed DES in chromatographic techniques, the retention data collected indicate the possibility of its application to other separation techniques, i.e. extractive distillation.

Geographical differentiation of apple ciders based on volatile fingerprint.[Pubmed:33233173]

Food Res Int. 2020 Nov;137:109550.

With the globalization of food trade, it's traceability and genuineness becomes increasingly more difficult. Therefore, it is necessary to develop analytical tools to define the authenticity and genuineness of food-derived products. In the current work, headspace solid-phase microextraction followed by gas chromatography-mass spectrometry (HS-SPME/GC-MS) combined with chemometric tools was used to establish the volatile fingerprint of apple ciders produced in different geographical regions of Madeira Island, in order to define their typicity and to identify putative geographical markers. A total of 143 volatile organic compounds (VOCs) belonging to different chemical families have been identified, of which 28 were found in all apple ciders independently of geographical region. Esters, terpenic and furanic compounds presented on average a higher contribution for the total volatile fingerprint in cider produced in northern region of the Island, whereas alcohols, acids, volatile phenols, carbonyl compounds and lactones in cider from southern region. Considering the relative areas of the VOCs, 43 revealed statistically significant differences (p < 0.001) between geographical regions, and 11 between northern and southern regions. A clear differentiation among cider-producing regions was observed on the developed partial least squares-discriminant analysis (PLS-DA) model. Two alcohols (1-Hexanol, 1-octanol), 6 esters (methyl acetate, (Z)-3-hexen-1-ol acetate, ethyl hexanoate, ethyl nonanote, ethyl octanoate, isoamyl octanoate) and 1 terpenic compound (limonene), can be considered putative geographic markers due to their discriminatory ability. The results obtained recognize the specific and typical geographical characteristics of the cider, which will allow the forthcoming guarantee for the construction of a sustainable platform for the establishment of the authenticity and typicality of the regional cider.

Volatile compounds reveal age: a study of volatile organic compounds released by Chrysomya rufifacies immatures.[Pubmed:33230566]

Int J Legal Med. 2020 Nov 23. pii: 10.1007/s00414-020-02471-1.

Age determination of insects collected from vertebrate remains is an essential step in estimating time since colonization as related to the post-mortem interval. Long-established methods for making such estimates rely on determining age related to stage of development at the time of collection in relation to conditions experienced. However, such estimates are based on the completion of a stage of development. Methods allowing for more precise estimates of age (i.e., within a stage of development) are sorely needed. This study examined the potential of volatile organic compounds emitted by blow fly, Ch. rufifacies (Macquart), immatures to determine stage of development, which could potentially be used to estimate the age. Volatile organic compounds (VOCs) from the larval and pupal stages of Ch. rufifacies were collected by headspace solid-phase micro-extraction followed by gas chromatography-mass spectrometry (GC-MS). Analyses indicated 37 compounds shift quantitatively, as well as qualitatively, as the larvae and pupae age. Furthermore, compounds, such as 2-ethyl-1-Hexanol, phenol, butanoic acid, hexadecanoic acid, octadecanoic acid, 2-methyl propanamide, and 2-methyl butanoic acid, serve as indicator compounds of specific stages within Ch. rufifacies development. This information could be important to determine if these compounds can be used in the field to predict the presence of certain developmental stages, in order to determine the potential of using volatile markers to estimate time of colonization.

Quantification of seven microbial volatile organic compounds in human serum by solid-phase microextraction gas chromatography-tandem mass spectrometry.[Pubmed:33228985]

Chemosphere. 2020 Nov 13:128970.

Microbial volatile organic compounds (MVOCs) are primary and secondary metabolites of fungal and bacterial growth. Changes in environmental conditions (e.g., humidity, light, oxygen, and carbon dioxide) influence microbial growth in indoor environments. Prolonged human exposure to MVOCs has been directly associated with sick building syndrome (SBS), respiratory irritation, and asthma-like symptoms. However, no method exists for assessing MVOC exposure by quantifying them in human serum. We developed a novel, high-throughput automated method for quantifying seven MVOCs (3-methylfuran, 2-hexanone, 2-heptanone, 3-octanone, 1-octen-3-ol, 2-ethyl-1-Hexanol, and geosmin) in human serum. The method quantifies the target analytes using solid-phase microextraction gas chromatography-tandem mass spectrometry at low parts-per-billion levels. Limits of detection ranged from 0.076 to 2.77 mug/L. This method provides excellent linearity over the concentration range for the analytes, with coefficients of determination >0.992. Recovery in human serum was between 84.5% and 113%, and analyte precision ranged from 0.38% to 8.78%. The intra-day and inter-day reproducibility showed coefficients of variation

Coupling Transcriptomics and Behaviour to Unveil the Olfactory System of Spodoptera exigua Larvae.[Pubmed:33150456]

J Chem Ecol. 2020 Dec;46(11-12):1017-1031.

Insect chemosensation is crucial for many aspects related to food seeking, enemy avoidance, and reproduction. Different families of receptors and binding proteins interact with chemical stimuli, including odorant receptors (ORs), ionotropic receptors (IRs), gustatory receptors (GRs), odorant binding proteins (OBPs) and chemosensory proteins (CSPs). In this work, we describe the chemosensory-related gene repertoire of the worldwide pest Spodoptera exigua (Lepidoptera: Noctuidae), focusing on the transcripts expressed in larvae, which feed on many horticultural crops producing yield losses. A comprehensive de novo assembly that includes reads from chemosensory organs of larvae and adults, and other larval tissues, enabled us to annotate 200 candidate chemosensory-related genes encoding 63 ORs, 28 IRs, 38 GRs, 48 OBPs and 23 CSPs. Of them, 51 transcripts are new annotations. Fifty ORs are expressed in larval heads based on RNA-seq and reverse transcription PCR analyses. Fourteen OBPs are expressed in larval, but not in adult heads. We also observe that expression profiles of ORs are strongly and non-specifically up-regulated upon pre-exposure of larvae to single volatile organic compounds (VOCs). Finally, we develop a behavioural assay to study the attraction/repellence to VOCs in S. exigua larvae and thus identify candidate ecologically relevant odours. A single-dose assay demonstrated that 1-Hexanol triggers attraction and indole repels larvae at any timepoint. This work establishes the foundation for the study of chemosensation in S. exigua larvae, allowing further studies aimed to characterize chemosensory-related genes that underlie the ecologically relevant behaviours of larvae.

Duck breast muscle proteins, free fatty acids and volatile compounds as affected by curing methods.[Pubmed:33091978]

Food Chem. 2021 Feb 15;338:128138.

The aim of this study was to investigate the effects of different curing methods on protein structure, protein and lipid oxidation, lypolysis and volatile compounds in duck breast meat. The results showed that compared to static brining and pulsed pressure salting, the vacuum tumbling curing significantly decreased the oxidation of proteins and lipids, and the surface hydrophobicity of proteins, increased alpha-helix structure but decreased the proportion of beta-sheet, and increased actomyosin dissociation, liplysis and the free fatty acid content in meat. Meanwhile, vacuum tumbling curing decreased the amount of volatile flavor compounds, hexanal, 2,3-octanone, and off-flavor compounds 1-octen-3-ol and 1-Hexanol. This study suggests that concerns on healthiness and the sensory quality of processed meat products should be paid in the selection of curing methods and vacuum tumbling curing is superior in terms of both aspects.

Screening of volatile decay markers of minced pork by headspace-solid phase microextraction-gas chromatography-mass spectrometry and chemometrics.[Pubmed:33077278]

Food Chem. 2020 Oct 10:128341.

Headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) was used to analyze the volatile compounds of minced pork meat during storage. The origin of aromatic hydrocarbons in pork was verified by migration test. Principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) were applied to characterize the profile of volatile compounds in pork meat and identify the potential volatile markers associated with the spoilage of pork. A total of 41 compounds were identified. Migration test showed that the aromatic hydrocarbons in raw pork are from packaging. Three compounds: ethanol, 2,3-butanediol and 2-ethyl-1-Hexanol were selected based on the loading plot and their variables importance in the projection (VIP) values, since they contribute mainly to the discrimination of pork with different storage times. These compounds can be used as additional indicators for quality control of pork.

Unusual Debye relaxation in 4-methyl-2-pentanol evidenced by high-pressure dielectric studies.[Pubmed:33052889]

J Phys Condens Matter. 2021 Jan 13;33(2):025401.

The Debye relaxation is the main signal in the dielectric measurements of monoalcohols arising from the hydrogen-bonded superstructures, but its physics remains to be cleared. In this work, a monoalcohol of 4-methyl-2-pentanol is studied using dielectric spectroscopies recorded at high pressures. The dynamic parameters of the Debye and structural relaxations are extracted. The calculation of the Kirkwood factor of the Debye relaxation indicates chain-like H-bond molecular configurations. Remarkably, we found that both ratios of the relaxation strength and relaxation time between the Debye and structural dynamics, Deltaepsilon D/Deltaepsilon alpha and tau D/tau alpha , decreases upon compression, indicating a positive correlation. This is different from the results reported in primary 2-ethyl-1-Hexanol and secondary 4-methyl-3-heptanol, where the two ratios are inversely correlated. The discussion and interpretation of these different results are provided.