Enhanced Compound Analysis Using Reactive Paper Spray Mass Spectrometry: Leveraging Schiff Base Reaction for Amino Acid Detection.

Paper spray mass spectrometry (PS-MS) has evolved into a promising tool for monitoring reactions in thin films and microdroplets, known as reactive PS, alongside its established role in ambient and direct ionization. This study addresses the need for rapid, cost-effective methods to improve analyte identification in biofluids by leveraging reactive PS-MS in clinical chemistry environments. The technique has proven effective in derivatizing target analytes, altering hydrophobicity to enhance elution and ionization efficiency, and refining detection through thin-film reactions on paper, significantly expediting reaction rates by using amino acids (AAs) as model analytes. These molecules are prone to interacting with substrates like paper, impeding elution and detection. Additionally, highly abundant species in biofluids, such as lipids, often suppress AA ionization. This study employs the Schiff base (SB) reaction utilizing aromatic aldehydes for AA derivatization to optimize reaction conditions time, temperature, and catalyst presence and dramatically increasing the conversion ratio (CR) of formed SB. For instance, using leucine as a model AA, the CR surged from 57% at room temperature to 89% at 70 °C, with added pyridine during and after 7.5 min, displaying a 43% CR compared to the bulk reaction. Evaluation of various aromatic aldehydes as derivatization agents highlighted the importance of specific oxygen substituents for achieving higher conversion rates. Furthermore, diverse derivatization agents unveiled unique fragmentation pathways, aiding in-depth annotation of the target analyte. Successfully applied to quantify AAs in human and rat plasma, this reactive PS-MS approach showcases promising potential in efficiently detecting conventionally challenging compounds in PS-MS analysis.

Widespread Production of Polyunsaturated Aldehydes by Benthic Diatoms of the North Pacific Ocean's Salish Sea.

Diatoms are key primary producers across marine, freshwater, and terrestrial ecosystems. They are responsible for photosynthesis and secondary production that, in part, support complex food webs. Diatoms can produce phytochemicals that have transtrophic ecological effects which increase their competitive fitness. Polyunsaturated aldehydes (PUAs) are one class of diatom-derived phytochemicals that are known to have allelopathic and anti-herbivory properties. The anti-herbivory capability of PUAs results from their negative effect on grazer fecundity. Since their discovery, research has focused on their production by pelagic marine diatoms, and their effects on copepod egg production, hatching success, and juvenile survival and development. Few investigations have explored PUA production by the prolific suite of benthic marine diatoms, despite their importance to coastal trophic systems. In this study, we tested eight species of benthic diatoms for the production of the bioactive PUAs 2,4-heptadienal, 2,4-octadienal, and 2,4-decadienal. Benthic diatom species were isolated from the Salish Sea, an inland sea within the North Pacific ecosystem. All species were found to be producers of at least two PUAs in detectable concentrations, with five species producing all three PUAs in quantifiable concentrations. Our results indicate that production of PUAs from Salish Sea benthic diatoms may be widespread, and thus these compounds may contribute to benthic coastal food web dynamics through heretofore unrecognized pathways. Future studies should expand the geographic scope of investigations into benthic diatom PUA production and explore the effects of benthic diatoms on benthic consumer fecundity.

Sex Pheromone of the Saturniid Moth Hemileuca nevadensis from Southern California.

The major and possibly only component of the sex attractant pheromone of the moth Hemileuca nevadensis (Lepidoptera: Saturniidae) from southern California was determined to be (E10,Z12)-hexadecadienal (E10,Z12-16:Ald). Detectable quantities of the analogs (E10,Z12)-hexadecadien-1-yl acetate (E10,Z12-16:Ac) and (E10,Z12)-hexadecadien-1-ol (E10,Z12-16:OH) were also present in solvent extracts of sex pheromone glands, and stimulated male antennae in coupled gas chromatography-electroantennogram detector (GC-EAD) assays. GC-EAD traces from solid phase microextraction (SPME) wipe samples of sex pheromone glands of calling females confirmed the presence of E10,Z12-16:Ald and traces of E10,Z12-16:OH on the gland surface, but E10,Z12-16:Ac was not detected. Despite evidence for the presence of all three compounds in extracts, behavioral responses to synthetic compounds in the field suggested that only E10,Z12-16:Ald is required for optimal attraction.

Origin differentiation based on volatile constituents of genuine medicinal materials Quisqualis indica L. via HS-GC-MS, response surface methodology, and chemometrics.

INTRODUCTION: Quisqualis indica L. (QIL) has a long history as a traditional Chinese herb in China, but the study of volatile components in QIL from different geographical sources has been relatively rare. OBJECTIVES: To establish an optimal headspace gas chromatography-mass spectrometry (HS-GC-MS) method to comprehensively analyse the volatile component profile and screen quality markers of QIL from different origins. METHODS: Response surface methodology (RSM) was used to optimise the conditions for headspace analysis. The volatile components of QIL from four main origins of southwest China were analysed and identified by HS-GC-MS. The similarity of all samples of QIL was evaluated by fingerprint. The differences of the volatile components in QIL from different origins were distinguished by chemometrics. RESULTS: According to the optimal conditions of RSM, a total of 31 volatile components were identified, including fatty acids, aldehydes, alcohols, alkyl pyrazines, and other volatile components. Similarity evaluation presented that there were 26 common volatile components with different contents in all samples. Principal component analysis (PCA) showed that QIL from four different origins could be roughly divided into four categories. Hierarchical cluster analysis (HCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) indicated that QIL from different origins had obvious regional characteristics. CONCLUSION: The optimised HS-GC-MS method provided a strategy to rapidly, effectively, and accurately elucidate the volatile component profile of QIL from different origins, and seven important differential components were screened for quality evaluation and origin traceability.

Volatile Compound Markers in Beef Irradiated with Accelerated Electrons.

This study focuses on the behavior of volatile organic compounds in beef after irradiation with 1 MeV accelerated electrons with doses ranging from 0.25 kGy to 5 kGy to find reliable dose-dependent markers that could be used for establishing an effective dose range for beef irradiation. GC/MS analysis revealed that immediately after irradiation, the chemical yield and accumulation rate of lipid oxidation-derived aldehydes was higher than that of protein oxidation-derived aldehydes. The nonlinear dose-dependent relationship of the concentration of volatile organic compounds was explained using a mathematical model based on the simultaneous occurrence of two competing processes: decomposition of volatile compounds due to direct and indirect action of accelerated electrons, and accumulation of volatile compounds due to decomposition of other compounds and biomacromolecules. A four-day monitoring of the beef samples stored at 4 °C showed that lipid oxidation-derived aldehydes, protein oxidation-derived aldehydes and alkanes as well as alcohol ethanol as an indicator of bacterial activity were dose-dependent markers of biochemical processes occurring in the irradiated beef samples during storage: oxidative processes during direct and indirect action of irradiation, oxidation due to the action of reactive oxygen species, which are always present in the product during storage, and microbial-enzymatic processes. According to the mathematical model of the change in the concentrations of lipid oxidation-derived aldehydes over time in the beef samples irradiated with different doses, it was found that doses ranging from 0.25 kGy to 1 kGy proved to be most effective for beef irradiation with accelerated electrons, since this dose range decreases the bacterial content without considerable irreversible changes in chemical composition of chilled beef during storage.

Exploration of Raw Pigmented-Fleshed Sweet Potatoes Volatile Organic Compounds and the Precursors.

Sweet potato provides rich nutrients and bioactive substances for the human diet. In this study, the volatile organic compounds of five pigmented-fleshed sweet potato cultivars were determined, the characteristic aroma compounds were screened, and a correlation analysis was carried out with the aroma precursors. In total, 66 volatile organic compounds were identified. Terpenoids and aldehydes were the main volatile compounds, accounting for 59% and 17%, respectively. Fifteen compounds, including seven aldehydes, six terpenes, one furan, and phenol, were identified as key aromatic compounds for sweet potato using relative odor activity values (ROAVs) and contributed to flower, sweet, and fat flavors. The OR sample exhibited a significant presence of trans-ß-Ionone, while the Y sample showed high levels of benzaldehyde. Starch, soluble sugars, 20 amino acids, and 25 fatty acids were detected as volatile compounds precursors. Among them, total starch (57.2%), phenylalanine (126.82 ± 0.02 g/g), and fatty acids (6.45 µg/mg) were all most abundant in Y, and LY contained the most soluble sugar (14.65%). The results of the correlation analysis revealed the significant correlations were identified between seven carotenoids and trans-ß-Ionone, soluble sugar and nerol, two fatty acids and hexanal, phenylalanine and 10 fatty acids with benzaldehyde, respectively. In general, terpenoids and aldehydes were identified as the main key aromatic compounds in sweet potatoes, and carotenoids had more influence on the aroma of OR than other cultivars. Soluble sugars, amino acids, and fatty acids probably serve as important precursors for some key aroma compounds in sweet potatoes. These findings provide valuable insights for the formation of sweet potato aroma.

Analysis of changes in volatile compounds and evolution in free fatty acids, free amino acids, nucleotides, and microbial diversity in tilapia (Oreochromis mossambicus) fillets during cold storage.

BACKGROUND: Aquatic products are rich in nutrients and unique in flavor, and are popular among the public. However, aquatic products are extremely susceptible to quality degradation during storage, of which odor deterioration is the most obvious and influential aspect. Odor deterioration in aquatic products is widespread and severely affects overall flavor and quality. In this study, odor deterioration and flavor-related quality degradation of tilapia during cold storage are discussed, focusing on the changes in volatile compounds and the evolution of free fatty acids (FFAs), free amino acids (FAAs), nucleotides, and microbial diversity. RESULTS: A total of 63 volatile compounds were detected by gas chromatography-mass spectrometry, including 11 hydrocarbons, 10 alcohols, 6 aldehydes, 8 ketones, 6 esters, 9 aromatics, 3 phenols, and 10 other compounds. Microbial diversity analysis revealed that Acinetobacter, Psychrobacter, Vagococcus, and Myroides were the main dominant species of tilapia at the end of cold storage and predicted that microorganisms could influence the flavor of tilapia by participating in important metabolic pathways. Meanwhile, the evolution of FFAs, FAAs, and nucleotides also had a significant impact on odor deterioration, as evidenced by the contribution of unsaturated fatty acids (such as oleic acid and linoleic acid), Lys, and off-flavor nucleotides (HxR and Hx) to the undesirable flavor. Oxidation of oleic acid and linoleic acid resulted in changes in aldehydes, with Lys, HxR, and Hx being key flavor precursors and off-flavor contributors. CONCLUSION: This study contributes to a comprehensive overview of odor deterioration and the evolution of flavor-related quality in tilapia during cold storage, providing new insights into the regulation of overall flavor and quality. © 2023 Society of Chemical Industry.

The role of ultraviolet radiation in the flavor formation during drying processing of Pacific saury (Cololabis saira).

BACKGROUND: Traditional sun-drying aquatic products are popular and recognized by customers, owing to their unique flavor and long-term preservation. However, the product quality and production efficiency cannot be guaranteed. Cololabis saira is rich in unsaturated fatty acids, which are susceptible to hyperoxidation during the drying process. This study aimed to make clear the role of ultraviolet (UV) radiation in flavor formation during drying processes of Cololabis saira to develop a modern drying technology. RESULTS: Lipid oxidation analysis revealed that moderate hydrolytic oxidation occurred in the UV-assisted cold-air drying group due to the combined influence of UV and cold-air circulation, resulting in the thiobarbituric acid reactive substances value being higher than that of cold-air drying group but lower than the natural drying group. Hexanal, heptanal, cis-4-heptenal, octanal, nonanal, (trans,trans)-2,4-heptadienal, (trans,trans)-2,6-nonanedial, 1-octen-3-ol, heptanol, 2,3-pentanedione, 3,5-octadien-2-one and trimethylamine were identified as the characteristic flavor odor-active compounds present in all Cololabis saira samples. Yet, during the natural drying process, sunlight promoted the lipid oxidation, resulting in the highest degree of lipid oxidation among three drying methods. Light and heat promoted lipid oxidation in Cololabis saira prepared through natural drying process, leading to a large accumulation of volatile compounds, such as 3-methylbutyraldehyde, 2,3-pentanedione, 1-propanol, and 3-pentanone. Cold air circulation inhibited lipid oxidation to some extent, resulting in a blander flavor profile. More cis-4-heptenal, cis-2-heptenal, octanal and 2-ethylfuran accumulated during the UV-assisted cold-air drying process, enriching its greasy flavor and burnt flavor. CONCLUSION: UV-assisted cold-air drying could promote moderate lipid oxidation, which is beneficial for improving product flavor. To sum up, UV radiation played a crucial role in the flavor formation during the drying process of Cololabis saira. © 2024 Society of Chemical Industry.

Combined application of hot water and hexanal-based formulations preserves the postharvest quality of mango fruits.

BACKGROUND: Mango fruits undergo numerous postharvest quality losses during storage. Hence, the present study aimed to increase the shelf life of mango fruits by applying hexanal-based enhanced freshness formulations (EFF) in combination with hot water treatment (HWT). RESULTS: The findings revealed that, among all the tested applications, the combination of EFF 1.0% + HWT reduced the weight loss, decay incidence, and activity of cell wall degrading enzymes of mango fruits. Also, the combined treatment was effective in maintaining the fruit quality parameters such as soluble solid contents, titratable acidity, ascorbic acid and activity of antioxidant compounds. CONCLUSION: The present study concludes that the postharvest application of EEF 1.0% in combination with HWT can be used in extending the shelf life of mango cv. 'Langra,' fruits stored at 12° C and 85-90% relative humidity for 35 days. © 2024 Society of Chemical Industry.

Improving blueberry cold storage quality: the effect of preharvest hexanal application on chilling injuries and antioxidant defense mechanisms.

Blueberries are vulnerable to chilling injury (CI). This can lead to limited longevity when they are subjected to cold storage conditions. This study investigated the effectiveness of a preharvest spray containing 0.02% hexanal in reducing CI and improving the postharvest storage quality of 'Star' and 'Biloxi' blueberries. The blueberries were stored for a period of 5 weeks at 2 °C and in 90% relative humidity (RH). The findings revealed that the preharvest hexanal spraying of both cultivars delayed senescence by mitigating CI, as evidenced by the bolstering of the antioxidant defense system through increased superoxide dismutase (SOD), ascorbate peroxidase (APX), peroxidase (POD), catalase (CAT), and phenylalanine ammonia lyase (PAL) enzyme activity. The treated fruit also maintained elevated levels of total phenol content (TPC), total flavonoids (TFC), and vitamin C, demonstrating enhanced free radical scavenging capacity (FRSC), while exhibiting reduced polyphenoloxidase (PPO) activity, and reduced malondialdehyde (MDA), and H2O2 content in comparison with the control group. The preharvest hexanal treatment also suppressed fruit softening by maintaining greater firmness and higher membrane stability index (MSI) scores, inhibiting the activity of polygalacturonase (PG), pectinmethylesterase (PME), xylanase, and α-amylase, and reducing microbial counts (MC) and incidence of decay (DI) in comparison with the control. Preharvest hexanal treatment also improved the overall storage quality by reducing weight loss, total soluble solids (TSS), pH, and the TSS/acid ratio, while increasing titratable acidity (TA) in comparison with the control during cold storage. The findings suggest that hexanal, as a preharvest application, delays senescence effectively and preserves overall quality by enhancing cold tolerance through antioxidant defense mechanisms in blueberry storage under cold conditions. © 2024 The Author(s). Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Salivary lipid changes in young adult tobacco smokers and e-cigarette users: a hidden risk to oral health?

STUDY DESIGN: A cross-sectional, age- and gender-matched study was conducted to investigate the effects of different forms of nicotine delivery on salivary lipid profiles among young adult novice smokers compared to non-smokers. OBJECTIVE: To assess the effect of smoking traditional cigarettes, e-cigarettes, and heated tobacco products (HTPs) on the levels of specific sphingolipids (sphingosine, sphinganine, and sphingosine-1-phosphate), various ceramides, and lipid peroxidation products [malondialdehyde (MDA) and 4-hydroxynonenal (4-HNE)] in both unstimulated and stimulated saliva samples collected from healthy young adults who had been smoking for 1-3 years and used only 1 of the 3 nicotine delivering methods. METHODS: Selection criteria included healthy young adults under 30 years old, with normal BMI and typical diet composition, and with no oral inflammatory lesions, orthodontic/dental appliances, or recent intake of medications or supplements. A total of 75 smokers and 25 non-smokers were enrolled in the study. Smokers were categorized into three groups, each comprising 25 individuals: traditional cigarette smokers, e-cigarette users, and HTPs smokers. Saliva samples were collected and analyzed for sphingolipid concentrations using ultra-high-performance liquid chromatography-tandem mass spectrometry. The concentrations of MDA and 4-HNE were measured using colorimetric and ELISA assays, respectively. RESULTS: The average smoking intensity in the traditional cigarette group was 10 cigarettes per day. Salivary sphingolipid and ceramides concentrations were significantly lower in smokers compared to non-smokers across all nicotine delivery methods (p < 0.0001). Moreover, traditional cigarette smokers exhibited higher levels of 4-HNE and MDA in both stimulated and unstimulated saliva, compared to non-smokers (p < 0.01). In stimulated saliva, both MDA and 4-HNE in e-cigarette users, and MDA in HTPs users, showed significantly lower concentrations than their comparators in traditional cigarette smokers (p < 0.01). CONCLUSION: Different nicotine delivery methods impact salivary lipid profile during the initial period of smoking habit. Reduced sphingolipids and elevated lipid peroxidation products suggest a disturbed lipid balance in the oral cavity due to enhanced oxidative stress within the salivary glands of novice smokers.

Analysis of a Broad Range of Carbonyl Metabolites in Exhaled Breath by UHPLC-MS.

Analysis of volatile organic compounds (VOCs) in exhaled breath (EB) has shown great potential for disease detection including lung cancer, infectious respiratory diseases, and chronic obstructive pulmonary disease. Although many breath sample collection and analytical methods have been developed for breath analysis, analysis of metabolic VOCs in exhaled breath is still a challenge for clinical application. Many carbonyl compounds in exhaled breath are related to the metabolic processes of diseases. This work reports a method of ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC-MS) for the analysis of a broad range of carbonyl metabolites in exhaled breath. Carbonyl compounds in the exhaled breath were captured by a fabricated silicon microreactor with a micropillar array coated with 2-(aminooxy)ethyl-N,N,N-trimethylammonium (ATM) triflate. A total of six subgroups consisting of saturated aldehydes and ketones, hydroxy-aldehydes, and hydroxy-ketones, unsaturated 2-alkenals, and 4-hydroxy-2-alkenals were identified in the exhaled breath. The combination of a silicon microreactor for the selective capture of carbonyl compounds with UHPLC-MS analysis may provide a quantitative method for the analysis of carbonyls to identify disease markers in exhaled breath.

Bitumen fumes and PAHs in asphalt road paving: Emission characteristics, determinants of exposure and environmental impact.

BACKGROUND: Asphalt road paving and its subsequent complex airborne emissions have raised concerns about occupational exposures and environmental impacts. Although several studies described bitumen fumes or Polycyclic Aromatic Hydrocarbons (PAH) emissions at specific worksites, no comprehensive studies have characterised road paving emissions and identified the main determinants of exposure. METHODS: A 10-year study from 2012 to 2022 was performed to examine the pollutants resulting from bitumen fume emissions and covering the main processes used in road paving (asphalt production, mechanical rolled asphalt paving, manual paving, mastic asphalt paving, emulsion paving, and coal-tar asphalt milling). A total of 623 air samples were collected at 63 worksites (on 290 workers, in the environment and near emission sources), and bitumen fumes, PAHs, aldehydes and volatile organic compounds were analysed. Biomonitoring campaigns were performed on 130 workers to assess internal exposure to PAHs. RESULTS: Fume emissions revealed complex mixtures of C10-C30 compounds, including linear saturated hydrocarbons (C6-C12), alicyclic hydrocarbons and aliphatic ketones. PAHs were dominated by 2-3 aromatic ring compounds (naphthalene, fluorene, and phenanthrene), and C1-C13 aldehydes were identified. Binder proportion, paving temperature, outdoor temperature, workload and job category influenced airborne concentrations. A significant temporal trend was observed over the time period of the study, with decreasing BF and PAH exposures. PAH biomonitoring was consistent with air samples, and urinary metabolites of 2-3 ring PAHs dominated over 4-5 ring PAHs. Occupational exposures were generally far lower than exposure limits, except coal-tar asphalt milling activities. Very low environmental concentrations were measured, which highlights a negligible contribution of paving emissions to global environmental pollution. CONCLUSION: The present study confirmed the complex nature of bitumen fumes and characterised the main determinants of exposure. The results highlight the need to reduce the paving temperature and binder proportion. Recycled asphalt pavement use was not associated with higher emissions. The impact of paving activities on environmental airborne pollution was deemed negligible.

Comparative Study on the Volatile Organic Compounds and Characteristic Flavor Fingerprints of Five Varieties of Walnut Oil in Northwest China Using Using Headspace Gas Chromatography-Ion Mobility Spectrometry.

Odor is an important characteristic of walnut oil; walnut oil aromas from different varieties smell differently. In order to compare the differences of volatile flavor characteristics in different varieties of walnut oil, the volatile organic compounds (VOCs) of walnut oil from five different walnut varieties in Northwest China were detected and analyzed using headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS). The results showed that 41 VOCs in total were identified in walnut oil from five different varieties, including 14 aldehydes, 8 alcohols, 4 ketones, and 2 esters. Walnut oil (WO) extracted from the "Zha343" variety was most abundant in VOCs. The relative odor activity value (ROAV) analysis showed that aldehydes were the main aroma substances of walnut oil; specifically, hexanal, pentanal, and heptanal were the most abundant. Fingerprints and heat map analysis indicated that WO extracted from the "Xin2", "185", "Xin'guang", and "Zha343" varieties, but not from the "Xinfeng" variety, had characteristic markers. The relative content differences of eight key VOCs in WO from five varieties can be directly compared by Kruskal-Wallis tests, among which the distribution four substances, hexanal (M), hexanal (D), pentanal (M), (E)-2-hexanal (M), presented extremely significant differences (P<0.01). According to the results of the principal component analysis (PCA), WO extracted from the "Zha343" variety was distinct from the other four varieties; in addition, WO extracted from the "Xin2" variety exhibited similarity to WO extracted from the "185" variety, and WO extracted from the "Xinfeng" variety showed similarity to WO extracted from the "Xin'guang" variety. These results reveal that there are certain differences in the VOCs extracted from five different WO varieties, making it feasible to distinguish different varieties of walnut oil or to rapidly detect walnut oil quality based on its volatile substances profile.

Differentiation of Goat Meat Freshness Using Gas Chromatography with Ion Mobility Spectrometry.

To investigate the flavor changes in goat meat upon storage, the volatile components observed in goat meat after different storage periods were determined using gas chromatography-ion mobility spectrometry (GC-IMS). A total of 38 volatile organic compounds (VOCs) were determined from the goat meat samples, including alcohols, ketones, aldehydes, esters, hydrocarbons, ethers, and amine compounds. 1-Hexanol, 3-Hydroxy-2-butanone, and Ethyl Acetate were the main volatile substances in fresh goat meat, and they rapidly decreased with increasing storage time and can be used as biomarkers for identifying fresh meat. When combined with the contents of total volatile basic-nitrogen (TVB-N) and the total numbers of bacterial colonies observed in physical and chemical experiments, the characteristic volatile components of fresh, sub-fresh, and spoiled meat were determined by principal component analysis (PCA). This method will help with the detection of fraudulent production dates in goat meat sales.

Flavor Quality Analysis of Ten Actinidia arguta Fruits Based on High-Performance Liquid Chromatography and Headspace Gas Chromatography-Ion Mobility Spectrometry.

Actinidia arguta is a fruit crop with high nutritional and economic value. However, its flavor quality depends on various factors, such as variety, environment, and post-harvest handling. We analyzed the composition of total soluble sugars, titratable acids, organic acids, and flavor substances in the fruits of ten A. arguta varieties. The total soluble sugar content ranged from 4.22 g/L to 12.99 g/L, the titratable acid content ranged from 52.55 g/L to 89.9 g/L, and the sugar-acid ratio ranged from 5.39 to 14.17 at the soft ripe stage. High-performance liquid chromatography (HPLC) showed that citric, quinic, and malic acids were the main organic acids in the A. arguta fruits. Headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) detected 81 volatile compounds in 10 A. arguta varieties, including 24 esters, 17 alcohols, 23 aldehydes, 7 ketones, 5 terpenes, 2 acids, 1 Pyrazine, 1 furan, and 1 benzene. Esters and aldehydes had the highest relative content of total volatile compounds. An orthogonal partial least squares discriminant analysis (OPLS-DA) based on the odor activity value (OAV) revealed that myrcene, benzaldehyde, methyl isobutyrate, α-phellandrene, 3-methyl butanal, valeraldehyde, ethyl butyrate, acetoin, (E)-2-octenal, hexyl propanoate, terpinolene, 1-penten-3-one, and methyl butyrate were the main contributors to the differences in the aroma profiles of the fruits of different A. arguta varieties. Ten A. arguta varieties have different flavors. This study can clarify the differences between varieties and provide a reference for the evaluation of A. arguta fruit flavor, variety improvement and new variety selection.

Investigation of Fenebrutinib Metabolism and Bioactivation Using MS3 Methodology in Ion Trap LC/MS.

Fenebrutinib is an orally available Bruton tyrosine kinase inhibitor. It is currently in multiple phase III clinical trials for the management of B-cell tumors and autoimmune disorders. Elementary in-silico studies were first performed to predict susceptible sites of metabolism and structural alerts for toxicities by StarDrop WhichP450™ module and DEREK software; respectively. Fenebrutinib metabolites and adducts were characterized in-vitro in rat liver microsomes (RLM) using MS3 method in Ion Trap LC-MS/MS. Formation of reactive and unstable intermediates was explored using potassium cyanide (KCN), glutathione (GSH) and methoxylamine as trapping nucleophiles to capture the transient and unstable iminium, 6-iminopyridin-3(6H)-one and aldehyde intermediates, respectively, to generate a stable adducts that can be investigated and analyzed using mass spectrometry. Ten phase I metabolites, four cyanide adducts, five GSH adducts and six methoxylamine adducts of fenebrutinib were identified. The proposed metabolic reactions involved in formation of these metabolites are hydroxylation, oxidation of primary alcohol to aldehyde, n-oxidation, and n-dealkylation. The mechanism of reactive intermediate formation of fenebrutinib can provide a justification of the cause of its adverse effects. Formation of iminium, iminoquinone and aldehyde intermediates of fenebrutinib was characterized. N-dealkylation followed by hydroxylation of the piperazine ring is proposed to cause the bioactivation to iminium intermediates captured by cyanide. Oxidation of the hydroxymethyl group on the pyridine moiety is proposed to cause the generation of reactive aldehyde intermediates captures by methoxylamine. N-dealkylation and hydroxylation of the pyridine ring is proposed to cause formation of iminoquinone reactive intermediates captured by glutathione. FBB and several phase I metabolites are bioactivated to fifteen reactive intermediates which might be the cause of adverse effects. In the future, drug discovery experiments utilizing this information could be performed, permitting the synthesis of new drugs with better safety profile. Overall, in silico software and in vitro metabolic incubation experiments were able to characterize the FBB metabolites and reactive intermediates using the multistep fragmentation capability of ion trap mass spectrometry.

Electronic Nose and Head Space GC-IMS Provide Insights into the Dynamic Changes and Regularity of Volatile Compounds in Zangju (Citrus reticulata cv. Manau Gan) Peel at Different Maturation Stages.

Zangju (Citrus reticulata cv. Manau Gan) is the main citrus cultivar in Derong County, China, with unique aroma and flavour characteristics, but the use of Zangju peel (CRZP) is limited due to a lack of research on its peel. In this study, electronic nose, headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS), and partial least squares-discriminant analysis (PLS-DA) methods were used to rapidly and comprehensively evaluate the volatile compounds of dried CRZP and to analyse the role of dynamic changes at different maturation stages. The results showed that seventy-eight volatile compounds, mainly aldehydes (25.27%) and monoterpenes (55.88%), were found in the samples at four maturity stages. The contents of alcohols and aldehydes that produce unripe fruit aromas are relatively high in the immature stage (October to November), while the contents of monoterpenoids, ketones and esters in ripe fruit aromas are relatively high in the full ripening stage (January to February). The PLS-DA model results showed that the samples collected at different maturity stages could be effectively discriminated. The VIP method identified 12 key volatile compounds that could be used as flavour markers for CRZP samples collected at different maturity stages. Specifically, the relative volatile organic compounds (VOCs) content of CRZP harvested in October is the highest. This study provides a basis for a comprehensive understanding of the flavour characteristics of CRZP in the ripening process, the application of CRZP as a byproduct in industrial production (food, cosmetics, flavour and fragrance), and a reference for similar research on other C. reticulata varieties.

Cold pressed pumpkin seed oil fatty acids, carotenoids, volatile compounds profiles and infrared fingerprints as affected by storage time and wax-based oleogelation.

BACKGROUND: Pumpkin seed and sunflower oil are rich in bioactive compounds, but are prone to oxidation during storage. Their fatty acids, carotenoid and volatile compounds and their Fourier-transform infrared (FTIR) profiles were studied during 8 months storage in order to assess the overall quality, but also to assess the impact of the oleogelation as conditioning process. RESULTS: The fatty acids methyl esters were analyzed by gas chromatography-mass spectrometry (GC-MS). The linoleic acid was the most abundant in the oils (604.6 g kg-1 in pumpkin and 690 g kg-1 in sunflower), but also in oleogels. Through high-performance liquid chromatography (HPLC), lutein and ß-carotene were determined as specific carotenoid compounds of the pumpkin seed oil and oleogel, in a total amount of 0.0072 g kg-1 . The volatile compounds profile revealed the presence of alpha-pinene for the pumpkin seed oil and oleogels and a tentative identification of limonene for the sunflower oil. Hexanal was also detected in the oleogels, indicating a thermal oxidation, which was further analyzed through infrared spectroscopy. CONCLUSIONS: During 8 months storage, the decrease of polyunsaturated fatty acid total amount was 5.72% for the pumpkin seed oil and 3.55% for the oleogel, while in the sunflower oil samples of 2.93% and 3.28% for the oleogel. It was concluded that oleogelation might protect specific carotenoid compounds, since the oleogels displayed higher content of ß-carotene at each storage time. Hexanal and heptanal were detected during storage, regardless of the oil or oleogel type. FTIR analysis depicts the differences in the constituent fatty acids resulting due to thermal oxidation or due to storage. © 2022 Society of Chemical Industry.

Alcohol-free and low-alcohol beers: Aroma chemistry and sensory characteristics.

Alcohol-free beers have gained popularity in the last few decades because they provide a healthier alternative to alcoholic beers and can be more widely consumed. Consumers are becoming more aware of the benefits of reducing their alcohol consumption, and this has increased the sales of nonalcoholic alternatives. However, there are still many challenges for the brewing industry to produce an alcohol-free beer that resembles the pleasant fruity flavor and overall sensory experience of regular beers. The aim of this review is to give a comprehensive overview of alcohol-free beer focusing on aroma chemistry. The formation of the most important aroma compounds, such as Strecker aldehydes, higher alcohols, and esters, is reviewed, aiming to outline the gaps in current knowledge. The role of ethanol as a direct and indirect flavor-active compound is examined separately. In parallel, the influence of the most common methods to reduce alcohol content, such as physical (dealcoholization) or biological, on the organoleptic characteristics and consumer perception of the final product, is discussed.