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Sacred lotus (Nelumbo nucifera) belongs to Nelumbonaceae family. Its seeds are widely consumed in Asia countries as snacks or even medicine. Besides the market values, lotus seed also plays crucial roles in lotus life cycle. Consequently, it is essential to gain a comprehensive understanding of the development of lotus seed. During its development, lotus seed undergoes cell division, expansion, reserve accumulation, desiccation and maturation phases. We observed morphological and biochemical changes from 10 to 25 days after pollination (DAP) which was corresponding to the reserve synthesis and accumulation phase. The volume of the seed expanded until 20 DAP with the color of the seed coat changing from yellow-green to dark green and gradually fading again. Starch and protein rapidly accumulated from 15 to 20 DAP. To further reveal the metabolism adaptation, primary metabolites and proteins profiles were obtained using mass spectrometry based platforms. Metabolites and enzymes involved in sugar metabolism, glycolysis, TCA cycle and amino acids metabolism showed sequential dynamics enabling the clear separation of the different metabolic states during lotus seed development. The integration of the data revealed a highly significant metabolic switch at 15 DAP going through a transition of metabolically highly active tissue to the preparation of storage tissue. The results provide reference data set for the evaluation of primary metabolism during lotus seed development.

To identify the major factors contributing to the quality of commercial gochujang (fermented red pepper paste), metabolites were profiled by mass spectrometry. In principal component analysis, cereal type (wheat, brown rice, and white rice) and species of hot pepper (Capsicum annuum, C. annuum cv. Chung-yang, and C. frutescens) affected clustering patterns. Relative amino acid and citric acid levels were significantly higher in wheat gochujang than in rice gochujang. Sucrose, linoleic acid, oleic acid, and lysophospholipid levels were high in brown-rice gochujang, whereas glucose, maltose, and -aminobutyric acid levels were high in white-rice gochujang. The relative capsaicinoid and luteolin derivative contents in gochujang were affected by the hot pepper species used. Gochujang containing C. annuum cv. Chung-yang and C. frutescens showed high capsaicinoid levels. The luteolin derivative level was high in gochujang containing C. frutescens. These metabolite variations in commercial gochujang may be related to different physicochemical phenotypes and antioxidant activity. [ABSTRACT FROM AUTHOR]

Sacred lotus (Nelumbo nucifera) belongs to the Nelumbonaceae family. Its seeds are widely consumed in Asian countries as snacks or even medicine. Besides the market value, lotus seed also plays a crucial role in the lotus life cycle. Consequently, it is essential to gain a comprehensive understanding of the development of lotus seed. During its development, lotus seed undergoes cell division, expansion, reserve accumulation, desiccation, and maturation phases. We observed morphological and biochemical changes from 10 to 25 days after pollination (DAP) which corresponded to the reserve synthesis and accumulation phase. The volume of the seed expanded until 20 DAP with the color of the seed coat changing from yellow-green to dark green and gradually fading again. Starch and protein rapidly accumulated from 15 to 20 DAP. To further reveal metabolic adaptation, primary metabolites and proteins profiles were obtained using mass spectrometry based platforms. Metabolites and enzymes involved in sugar metabolism, glycolysis, TCA cycle and amino acid metabolism showed sequential dynamics enabling the clear separation of the different metabolic states during lotus seed development. The integration of the data revealed a highly significant metabolic switch at 15 DAP going through a transition of metabolically highly active tissue to the preparation of storage tissue. The results provide a reference data set for the evaluation of primary metabolism during lotus seed development. [ABSTRACT FROM AUTHOR]

The consumption of rice, especially brown rice, is known to promote cellular growth but the underlying mechanisms and key metabolites of this process are unclear. This study investigated the effects of brown rice on cellular growth and the underlying mechanisms using a metabolomics approach in vivo . C57BL/6J male mice were fed an isocaloric diet composed of control chow, Ilpum rice (IP; Oryza sativa L. cv. Ilpum), or Ilpum brown rice (IB) for 4 weeks, and then the metabolites of the liver were analyzed. The rice consumption reduced the liver enzyme levels in plasma and did not result in obesity. The plasma total-cholesterol levels were significantly reduced in the IB group compared with the IP group. The plasma concentrations of growth hormone and insulin growth factor-1 were significantly increased, along with increased thigh bone width in the IB group compared with the IP group, suggesting that the intake of brown rice promoted animal growth. Gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF-MS) was used for the metabolic profiling of liver samples obtained from IP- and IB-fed mice. The obtained data sets were subjected to multivariate statistical analysis to investigate which metabolites contributed to the differences between the IP and IB groups. GC-TOF-MS analysis revealed the presence of 31 metabolites consisting of 8 lipids, 4 sugars and sugar alcohols, 15 amino acids, and 4 organic acids. Partial least-squares regression analysis demonstrated significant correlations between the data collected from GC-TOF-MS and the levels of growth hormone. The levels of l -valine, l -glutamine, and d -mannose were significantly higher in the IB group than the control and IP groups. [ABSTRACT FROM AUTHOR]

Current occurrence data for polybrominated diphenyl ethers (PBDE) and hexa-bromocyclododecane (HBCD) measured in most commonly consumed foods (n = 156) and animal feeds (n = 51) sampled in the UK, demonstrates an ongoing ubiquity of these contaminants in human and animal diets. PBDE concentrations for the sum of 17 measured congeners ranged from 0.02 ng/g to 8.91 ng/g whole weight for food, and 0.11 ng/g to 9.63 ng/g whole weight for animal feeds. The highest concentration ranges, and mean values were detected in fish, processed foods and fish feeds. HBCD diastereomers (alpha-HBCD was the most commonly detected) generally occurred at lower concentrations (from <0.01 ng/g to 10.1 ng/g for food and <0.01 ng/g to 0.66 ng/g for animal feed) and less frequently than PBDEs, but tetrabromobisphenol A which was also measured, was rarely detected. The total bromine content of the samples was also determined in an attempt to use a mass balance approach to investigate some of these samples for the occurrence of novel and emerging BFRs. Although the approach was further refined by measuring organic bromine content, the concentrations of bromine were too high (in most cases by orders of magnitude) to allow use of the approach. A selected sub-set of samples was screened by GC–MS, for the presence of novel/emerging brominated flame retardants (PBT, TBX, PBEB, DBHCTD, HCTBPH and OBTMPI) but these were not detected at the higher limits of detection that result from full scan (GC–MS) screening. This data will contribute to the EU wide risk assessment on these contaminants. [ABSTRACT FROM AUTHOR]

We performed mass spectrometry (MS)-based metabolite profiling of Cheonggukjang (CGJ) and three types of garlic (normal, sprouted, and fermented) added CGJ (G-CGJ). Metabolite profiling suggested that the major distinguishing factor between the four types of CGJ lay in whether garlic was added, although different metabolic states were observed in G-CGJ. Among the discriminant metabolites between CGJ and G-CGJ, the levels of four amino acids such as l -valine, l -isoleucine, l -leucine, and glycine were decreased in G-CGJ compared to CGJ because garlic inhibited the protease activity of Bacillus subtilis during fermentation. In addition, the relative contents of l -cysteine, s -allyl-cysteine, s -allyl-cysteine sulfoxide, soyasaponin βg, and soyasaponin γg, which showed positive correlation with antioxidant activities, were high in G-CGJ. These results suggest that MS-based metabolite profiling could be a useful tool for understanding the metabolic differences of fermented foods according to the additives, and their relationship with antioxidant activity. [ABSTRACT FROM AUTHOR]

Background: Plants produce and emit important volatile organic compounds (VOCs), which have an essential role in biotic and abiotic stress responses and in plant-plant and plant-insect interactions. In order to study the bouquets from plants qualitatively and quantitatively, a comprehensive, analytical method yielding reproducible results is required. Results: We applied in-tube extraction (ITEX) and solid-phase microextraction (SPME) for studying the emissions of Allium plants. The collected HS samples were analyzed by gas chromatography-time-of-flight-mass spectrometry (GC-TOF-MS), and the results were subjected to multivariate analysis. In case of ITEX-method Allium cultivars released more than 300 VOCs, out of which we provisionally identified 50 volatiles. We also used the VOC profiles of Allium samples to discriminate among groups of A. fistulosum, A. chinense (rakkyo), and A. tuberosum (Oriental garlic). As we found 12 metabolite peaks including dipropyl disulphide with significant changes in A. chinense and A. tuberosum when compared to the control cultivar, these metabolite peaks can be used for chemotaxonomic classification of A. chinense, tuberosum, and A. fistulosum. Conclusions: Compared to SPME-method our ITEX-based VOC profiling technique contributes to automatic and reproducible analyses. Hence, it can be applied to high-throughput analyses such as metabolite profiling. [ABSTRACT FROM AUTHOR]

Cerebral ischemia, resulting from compromised blood flow, is one of the leading causes of death worldwide with limited therapeutic options. Potential deleterious injuries resulting from reperfusion therapies remain a clinical challenge for physicians. This study aimed to explore the metabolomic alterations during ischemia-reperfusion injury by employing metabolomic analysis coupled with gas chromatography time-of-flight mass spectrometry (GC-TOF-MS) and ultraperformance liquid chromatography quadrupole (UPLC/Q)-TOF-MS. Metabolomic data from mice subjected to middle cerebral artery occlusion (MCAO) followed by reperfusion (MCAO/R) were compared to those of the sham and MCAO groups. A total of 82 simultaneously differentially expressed metabolites were identified among each group. The top three major classifications of these differentially expressed metabolites were organic acids, lipids, and organooxygen compounds. Metabolomics pathway analysis was conducted to identify the underlying pathways implicated in MCAO/R. Based on impactor scores, the most significant pathways involved in the response to the reperfusion after cerebral ischemia were glycerophospholipid metabolism, linoleic acid metabolism, pyrimidine metabolism, and galactose metabolism. 17 of those 82 metabolites were greatly elevated in the MCAO/Reperfusion group, when compared to those in the sham and MCAO groups. Among those metabolites, glucose-6-phosphate 1, fructose-6-phosphate, cellobiose 2, o-phosphonothreonine 1, and salicin were the top five elevated metabolites in MCAO/R group, compared with the MCAO group. Glycolysis, the pentose phosphate pathway, starch and sucrose metabolism, and fructose and mannose degradation were the top four ranked pathways according to metabolite set enrichment analysis (MSEA). The present study not only advances our understanding of metabolomic changes among animals in the sham and cerebral ischemia groups with or without reperfusion via metabolomic profiling, but also paves the way to explore potential molecular mechanisms underlying metabolic alteration induced by cerebral ischemia-reperfusion., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Chen, Zhou, Yuan, Xiong, Liu, Qiu, Hu, Lu, He, Liu and Yang.)

We performed mass spectrometry-based metabolites profiling in Lonicera caerulea fruits according to seven ripening stages. During ripening, fruit color significantly changed from green to red, with sugars, organic acids, phenolic acids, anthocyanins, and flavonoids significantly altered. In particular, the contents of cyanidin-3-glucoside, peonidin-glucoside, peonidin-3-rutinoside and cyanidin-3-rutinoside, which are closely associated with color, were elevated from stages four to seven. The changes of antioxidant activity during ripening were similar to those of total phenolic and flavonoid contents. L. caerulea fruits at stage six (pale-purple) had higher antioxidant activity and total phenolic and flavonoid contents with higher cyanidin-3,5-diglucoside contents than those at stage seven (fully purple). From this study, we revealed the changes in the contents of primary and secondary metabolites with antioxidant properties during ripening, and these results could be helpful to determine the optimal harvest stage of L. caerulea fruit. [ABSTRACT FROM AUTHOR]

[Display omitted] • Chemical profiles and key metabolic pathways in the HS were revealed by metabolomics. • Differences in microbiota and metabolome depending on the workshop factors. • HS exhibited potent antibacterial and anti-biofilm activities. • The flavor profiles of HS contained numerous well-known Baijiu compounds. Huangshui (HS) is a byproduct of Chinese Baijiu production that has tremendous potential to become a high-value product in the food industry. This study comprehensively analyzed the commonalities and differences in physicochemical properties, microbial structures, metabolomes, flavor profiles, and antibacterial properties among sources of HS. The HS samples were extracted from three different pits in three different workshops within an industrial Baijiu distillery. Lactobacillus was the dominant genus of bacteria in all of them, while Kazachstania , Aspergillus , and Pichia were the dominant genera of fungi. A total of 45 volatile compounds, including ethyl hexanoate, hexanoic acid, and 1-butanol, were detected in the HS by headspace solid-phase microextraction coupled with gas chromatography mass spectrometry, suggesting HS could be used to flavor liquor. Untargeted metabolomic analysis yielded 224 nonvolatile metabolites that were common in all HS samples. These metabolites included organic acids, carbohydrates, benzenoids, nucleic acids, and fatty acids, which are mainly involved in amino acid and sugar metabolism. While the compositions of the microbiome and metabolome among HS samples were affected by workshop factors, there were essentially no differences in the bactericidal properties of the HS samples among workshops. HS exhibited potent antibacterial activities against Escherichia coli and Staphylococcus aureus , and HS was effective in inactivating mature biofilms formed on polystyrene microplates, as confirmed by scanning electron micrographs. Our results provided a theoretical basis to increase the economic value of HS for applications in the food industry. [ABSTRACT FROM AUTHOR]

In this study, a comprehensive metabolite profile analysis of doenjang, a fermented soybean paste, at various steps of its industrial 5-step production process was conducted, by combining gas and liquid chromatography-mass spectrometry techniques with multivariate analysis. From the partial least squares discriminant analysis of primary and secondary metabolites, the patterns were clearly distinguishable between the various processing steps (step 1: steaming, step 2: drying, step 3: meju fermentation, step 4: brining, step 5: doenjang aging). Of the primary metabolites, most of the monosaccharides, amino acids, and fatty acids increased in steps 3-5. Isoflavone and soyasaponin derivatives were major secondary metabolites identified during the processing of doenjang. Isoflavone glycosides gradually decreased after step 1, while isoflavone aglycones distinctly increased in steps 4-5. Soyasaponins generally decreased during processing after step 2. Increased isoflavone aglycones, such as daidzein, glycitein, and genistein, were observed in steps 4-5 showed the strongest positive correlation with doenjang's antioxidant potential and total phenolic content. [ABSTRACT FROM AUTHOR]

To collect a large data set regarding the occurrence of organic substances in sediment, this study presents the examination of 20 micropollutants, as a national survey. The list of target compounds contains two alkylphenols, three polycyclic aromatic hydrocarbons (PAHs) not commonly included in monitoring programmes, six pesticides or metabolites, five pharmaceutical compounds, two hormones, one UV filter and bisphenol A. The selective and sensitive analytical methods, based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) or gas chromatography-time-of-flight mass spectrometry (GC-ToF-MS), allow the quantification at limits comprised between 0.5 and 23 ng/g, depending on the compound. The paper summarizes the analytical results from 154 sampling points. Of the 20 target compounds, 9 were determined at least once, and the sediments contained a maximum of 7 substances. The most frequently detected were PAHs (frequency, 77 %; max., 1,400 ng/g). The pharmaceutical compounds, hormones and pesticides were rarely detected in the samples; the most frequently detected was carbamazepine (frequency, 6 %; max., 31 ng/g). In some cases, the levels of PAHs and bisphenol A exceed the predicted no-effect concentration (PNEC) values. [ABSTRACT FROM AUTHOR]

To collect a complete dataset regarding the occurrence of organic substances in groundwater, this study presents the examination of 66 organic contaminants in the groundwater of overseas departments, including pesticides, pharmaceutical compounds, hormones and some industrial substances. The selective and sensitive analytical methods are described. These techniques begin with solid-phase extraction (SPE) followed by analysis using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-ToF-MS). The paper summarises the analytical results from 40 sampling points collected during two campaigns in Guadeloupe, Martinique, Reunion, Mayotte and Guiana, representing 80 samples. Of the 66 target substances, 36 were determined at least once. Among the most frequently detected are bisphenol A (frequency, 96 %; max., 7,400 ng/L), caffeine (frequency, 91 %; max., 1,240 ng/L), pentachlorophenol (frequency, 55 %; max., 418 ng/L), and carbamazepine (frequency, 56 %; max., 22 ng/L). The results do not put in evidence that the origin of the sample or climatic characteristics of these regions influence the dilution and release of micropollutants. [ABSTRACT FROM AUTHOR]

Electroencephalogram (EEG) responses and serum metabolite levels were used to investigate the effects of horticultural activities (seed-sowing) on the psychophysiological aspects of adults based on the presence or absence of the soil microorganism Streptomyces rimosus. In this case, 31 adults were subjected to seed-sowing activities using S. rimosus inoculated (experimental group) and medium (control group) soils. EEG was measured to analyze the resulting psychophysiological response, and blood samples (5 mL) were collected. The relative gamma power (RG), relative high beta (RHB), and SEF 50 and SEF 90 were significantly higher in the right than in the left occipital lobe (p < 0.05). In both occipital lobes, ratios of SMR to theta (RST), mid beta to theta (RMT), and SMR-mid beta to theta (RSMT) were high (p < 0.05). GC-TOF-MS-based serum metabolite analysis detected 33 metabolites. Compared to the control group, the experimental group showed a lower content of amino acids (except aspartic acid), lipids, and C6 sugar monomers after the activity (p < 0.05). Aminomalonic acid was decreased, and aspartic acid was increased (p < 0.05). This study confirmed a positive effect on improving the concentration and attention of adults when seed-sowing activity was performed using S. rimosus-inoculated soil.

The photoperiod is an important environmental signal for plants, and influences a wide range of physiological processes. For woody species in northern latitudes, cessation of growth is induced by short photoperiods. In many plant species, short photoperiods stop elongational growth after a few weeks. It is known that plant daylength detection is mediated by Phytochrome A (PHYA) in the woody hybrid aspen species. However, the mechanism of dormancy involving primary metabolism remains unclear. We studied changes in metabolite profiles in hybrid aspen leaves (young, middle and mature leaves) during short-day induced growth cessation, using a combination of gas chromatography–time-of-flight mass spectrometry, and multivariate projection methods. Our results indicate that the metabolite profiles in mature source leaves rapidly change when the photoperiod changes. In contrast, the differences in young sink leaves grown under long and short day conditions are less distinct. We found short daylength induced growth cessation in aspen was associated with rapid changes in the distribution and levels of diverse primary metabolites. In addition, we conducted metabolite profiling of leaves of PHYA overexpressor (PHYAOX) and those of the control to find the discriminative metabolites between PHYAOX and the control under the short-day conditions. The metabolite changes observed in PHYAOX leaves, together with those in the source leaves, identified possible candidates for the metabolite signature (e.g., 2-oxo-glutarate, spermidine, putrescine, 4-amino-butyrate and tryptophan) during short-day induced growth cessation in aspen leaves.

Abstract: We investigated the hypolipidemic effects of Goami-3 rice (GR; Oryza sativa L. cv. Goami-3), a newly developed strain with high levels of amylose and fibers. Diet-induced obese mice were fed three types of isocaloric diets for 8weeks: a high-fat diet, a high-fat diet with GR or control rice (CR; O. sativa L. cv. Ilpumbyeo). Mice fed GR exhibited a significant reduction in body fat (–23%), total cholesterol (–20%) and triglyceride concentrations (–30%) compared to mice fed CR. The mice fed GR showed induction of peroxisome proliferator-activated receptor (PPAR)-α and inhibition of γ expressions in the liver and adipose tissue. The reduced adiposity of mice fed GC was supported by changes in the expression of genes related to lipid accumulation and hydrolysis in adipose tissues and the plasma concentrations of insulin, adiponectin and leptin. Principal components analysis with gas chromatography–time-of-flight mass spectrometry-based metabolomic data revealed that the average level of specific plasma metabolites in the GR group was statistically different from that in the other groups after 4weeks. These metabolites included propionic acid, valine, leucine and proline. Based on partial least-squares analysis, the plasma concentrations of valine were inversely correlated with the high-density lipoprotein (HDL) to non-HDL and HDL to total cholesterol ratios. In conclusion, GR feeding for 8weeks significantly improved dyslipidemia and adiposity in diet-induced obese mice by regulating gene expression of PPARs and its target genes. Key plasma metabolites (including valine) were significantly altered by the hypolipidemic effects of GR. [Copyright &y& Elsevier]

Abstract: We investigated the mechanisms underlying the antiobesogenic properties of black-colored rice (BCR; Oryza sativa L. cv. Heugkwangbyeo) with high levels of anthocyanins. Stimulation of cultured adipocytes with BCR extract caused a significant decrease in cellular lipid reduction, and C57BL/6J mice fed BCR extract for 8weeks exhibited significant reductions in body weight and body fat. Plasma concentrations of leptin and insulin decreased, while levels of adiponectin increased in BCR group. These metabolic alterations were mediated by the activation of peroxisome proliferator-activated receptors (PPARs), activating PPAR-α while inhibiting PPAR-γ. These changes were accompanied by down-regulation and up-regulation of the genes involved in hepatic fatty acid synthesis and fatty acid oxidation, respectively. Evaluation of gene expression in adipocytes also suggested that those involved in lipid accumulation were reduced, with a concomitant induction of the genes involved in lipid hydrolysis. The plasma metabolites in mice rendered obese by intake of a high-fat-diet were analyzed using GC-TOF-MS and multivariate analysis after being fed different diets for 8weeks: control, Garcinia cambogia, control rice (O. sativa L. cv. Ilpumbyeo), and BCR. The BCR group could be distinguished from the others after 4weeks of the intervention using multivariate analysis. The major components related to this distinction were mannose, isoleucine, threonine, and phenylalanine. Also, body weight, glucose, and total cholesterol were positively correlated with the levels of propionic acid, butyric acid, cholesterol, alanine, ribitol, glucose, and galactose, whereas the high-density lipoprotein (HDL)/non-HDL ratio was negatively correlated with those of stearic acid, cholesterol, valine, leucine, glucose, and galactose. [Copyright &y& Elsevier]

Until recently, studies reporting the concentrations of polybrominated diphenyl ethers (PBDEs) as well as polybrominated biphenyls (PBBs) are generally scarce in the literature. Consequently, this study was aimed to investigate the occurrence and concentrations of certain PBDE congeners (BDE 28, 47, 100, 99, 154, 153, 183 and 209) and BB 153 in river water samples collected bi-monthly from the Diep River. The routine analyses of the target compounds were performed using a high-capillary GC-microelectron capture detection, while their structural elucidation was assessed using GC-TOF-MS technique. The overall mean concentrations of the sum of the eight PBDE congeners were 2.60, 4.83 and 4.29 ng/L for the upstream, point of discharge and downstream sampling points, respectively. Similarly, the overall mean concentrations of BB 153 were 0.25, 4.85 and 1.56 ng/L for the upstream, point of discharge and downstream sampling points, respectively. BDE 47 was the dominant congener found in these samples contributing between 19 and 26 % to the total PBDEs across the sampling points. The statistical analyses performed on the results obtained showed that all the congeners, except BDE 209 in certain instances, had strong positive correlations with one another, thus suggesting that these contaminants could be emanating from the same source. In this study, potential sources of these pollutants other than WWTP discharges into the investigated river were also identified. However, the relatively high concentrations of the target compounds found at the point of discharge sampling point coupled with the large volume of treated effluent being discharged suggested that the contributions from this source could be very significant over time. [ABSTRACT FROM AUTHOR]

The designer drug 3,4-methylenedioxybenzylpiperazine (3,4-MDBP), its positional isomer 2,3-methylenedioxybenzylpiperazine (2,3-MDBP) and three regioisomeric ring-substituted methoxybenzoylpiperazines (OMeBzPs) have identical elemental composition and no marked differences in their mass spectra with only the three methoxybenzoylpiperazine regioisomers showing one unique major fragment ion at m/z 152. Perfluoroacylation of the secondary amine nitrogen of these isomeric piperazines gave mass spectra with differences in the relative abundance of some fragment ions but did not alter the fragmentation pathway to provide unique ions for discrimination among these isomers. Exact mass determination using gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF-MS) did not provide any discrimination among these compounds since the main fragment ions are of identical elemental composition. Gas chromatography coupled to infrared detection (GC-IRD) provides direct confirmatory data for the identification of the carbonyl containing compounds and the differentiation of the psychoactive designer drug 3,4-MDBP from its direct (2,3-MDBP) and indirect (OMeBzPs) regioisomers. The mass spectra in combination with the vapour phase infrared spectra provide for specific confirmation of each of the isomeric piperazines. The underivatized and perfluoroacyl derivative forms of the five piperazines involved in this study were resolved on a stationary phase of 100% trifluoropropyl methyl polysiloxane (Rtx-200). Copyright © 2011 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: In order to determine how plant uptake of a sulfur-rich secondary metabolite, sinalbin, affects the metabolic profile of sulfur-deficient plants, gas chromatography time-of-flight mass spectrometry (GC–TOF-MS), in combination with liquid chromatography–mass spectrometry (LC–MS), was used to survey the metabolome of Arabidopsis seedlings grown in nutrient media under different sulfur conditions. The growth media had either sufficient inorganic sulfur for normal plant growth or insufficient inorganic sulfur in the presence or absence of supplementation with organic sulfur in the form of sinalbin (p-hydroxybenzylglucosinolate). A total of 90 metabolites were identified by GC–TOF-MS and their levels were compared across the three treatments. Of the identified compounds, 21 showed similar responses in plants that were either sulfur deficient or sinalbin supplemented compared to sulfur-sufficient plants, while 12 metabolites differed in abundance only in sulfur-deficient plants. Twelve metabolites accumulated to higher levels in sinalbin-supplemented than in the sulfur-sufficient plants. Secondary metabolites such as flavonol conjugates, sinapinic acid esters and glucosinolates, were identified by LC–MS and their corresponding mass fragmentation patterns were determined. Under sinalbin-supplemented conditions, sinalbin was taken up by Arabidopsis and contributed to the endogenous formation of glucosinolates. Additionally, levels of flavonol glycosides and sinapinic acid esters increased while levels of flavonol diglycosides with glucose attached to the 3-position were reduced. The exogenously administered sinalbin resulted in inhibition of root and hypocotyl growth and markedly influenced metabolite profiles, compared to control and sulfur-deficient plants. These results indicate that, under sulfur deficient conditions, glucosinolates can be a sulfur source for plants. This investigation defines an opportunity to elucidate the mechanism of glucosinolate degradation in vivo. [Copyright &y& Elsevier]

Abstract: A headspace SPME GC–TOF-MS method was developed for the acquisition of metabolite profiles of apple volatiles. As a first step, an experimental design was applied to find out the most appropriate conditions for the extraction of apple volatile compounds by SPME. The selected SPME method was applied in profiling of four different apple varieties by GC–EI-TOF-MS. Full scan GC–MS data were processed by MarkerLynx software for peak picking, normalisation, alignment and feature extraction. Advanced chemometric/statistical techniques (PCA and PLS-DA) were used to explore data and extract useful information. Characteristic markers of each variety were successively identified using the NIST library thus providing useful information for variety classification. The developed HS-SPME sampling method is fully automated and proved useful in obtaining the fingerprint of the volatile content of the fruit. The described analytical protocol can aid in further studies of the apple metabolome. [Copyright &y& Elsevier]

Metabolic footprinting has been applied as a non-invasive approach to study the behaviour and responses of cultured cells to a range of genetic and environmental perturbations. Gas chromatography interfaced with time-of-flight mass spectrometry (GC-ToF-MS) has become a powerful tool for the analysis of metabolome-derived samples. Generally, two data analysis strategies are used to interrogate and understand the biological patterns within the multi-dimensional data. The first strategy, a commoner one, uses multivariate analysis after chromatographic and mass spectral deconvolution, and the second strategy directly employs multivariate analysis of non-deconvoluted data. Here, two strategies have been assessed for the separation and classification of metabolic footprints (exometabolomes) of two strains of Candida albicans grown on three different carbon sources (glycerol, glucose and galactose). We describe a semi-automated approach that simultaneously processes all samples using the chromatographic dimension data with principal components analysis (PCA), which can include data pre-processing before PCA analysis. The preprocessed and non-deconvoluted total ion chromatogram (TIC) data showed good separation of classes defined by growth on different carbon sources and when comparing the two strains grown on the same carbon source separation was achieved for strains grown on glucose and glycerol after preprocessing. The discrimination observed is greater for preprocessed and non-deconvoluted TIC data than for that of preprocessed and non-deconvoluted single ion chromatogram data. The results from the proposed approach with those produced by MZmine were compared. The results from MZmine data depicted separations in PCA space according to carbon source, but no separation was seen when studying strains grown on the same carbon source. Our research showed that the non-deconvoluted strategy is suitable for fast comparison of large sets of GC-MS data although it will not directly provide biological information. The non-deconvoluted strategy can avoid problems of analyzing complex samples using deconvolution software. [ABSTRACT FROM AUTHOR]

The pharmacokinetics, tissue distribution, and excretion of buagafuran (BF, 4-butyl-α-agarofuran), a promising antianxiety drug isolated from Gharu-wood (Aquilaria agallocha Roxb), were investigated in rats. BF plasma concentration was determined in rats after oral and intravenous doses by GC-TOF-MS. BF showed nonlinear pharmacokinetics after oral and intravenous administration of 4, 16, and 64 mg/kg. The AUC0-∞ and Cmax did not increase proportionally with doses, indicating the saturation in absorption kinetics of BF in rats after oral dosage. BF absorption was extremely poor with an absolute bioavailability below 9.5%. After oral administration of 3H-BF (4 mg/kg) to rats, radioactivity was well distributed to the tissues examined. The highest radioactivity was found in gastrointestinal tract, followed by liver and kidney. Radioactivity in brain, as a target organ, was about 20-40% of that in plasma at all time points. Total mean percent recovery of radioactive dose was about 80% in rats (51.2% in urine; 28.7% in feces). Bile elimination was also the major excretion route of BF, and 45.4% of the radioactive dose was recovered in bile. [ABSTRACT FROM AUTHOR]

Abstract: An important feature relevant to potato (Solanum tuberosum) tuber quality management is the susceptibility to blackspot bruising caused by melanin production after exposure to severe mechanical stress. We analyzed the previously neglected nature and sequence of responses in primary metabolism and compared the cultivars ‘Afra’ and ‘Milva’ that differ in tissue elasticity and susceptibility to blackspot bruising. Mechanical stress application was highly standardized and differential formation of bruising damage and occurrence of small cracks in the outer tuber layers were demonstrated. Concomitant GC–TOF-MS based metabolite profiling revealed characteristic changes in central metabolism, namely in intermediates of the TCA cycle and linked parts of amino acid metabolism, with the clear exception of phenylalanine and tyrosine, the immediate precursor of melanin biosynthesis. We conclude that the initial metabolic responses and the initiation of blackspot formation are distinct, and that melanin biosynthesis is not driven by early precursor accumulation through activation of the aromatic amino acid biosynthesis pathway. [Copyright &y& Elsevier]

Metabolic phenotyping at cellular resolution may be considered one of the challenges in current plant physiology. A method is described which enables the cell type-specific metabolic analysis of epidermal cell types in Arabidopsis thaliana pavement, basal, and trichome cells. To achieve the required high spatial resolution, single cell sampling using microcapillaries was combined with routine gas chromatography-time of flight-mass spectrometry (GC-TOF-MS) based metabolite profiling. The identification and relative quantification of 117 mostly primary metabolites has been demonstrated. The majority, namely 90 compounds, were accessible without analytical background correction. Analyses were performed using cell type-specific pools of 200 microsampled individual cells. Moreover, among these identified metabolites, 38 exhibited differential pool sizes in trichomes, basal or pavement cells. The application of an independent component analysis confirmed the cell type-specific metabolic phenotypes. Significant pool size changes between individual cells were detectable within several classes of metabolites, namely amino acids, fatty acids and alcohols, alkanes, lipids, N-compounds, organic acids and polyhydroxy acids, polyols, sugars, sugar conjugates and phenylpropanoids. It is demonstrated here that the combination of microsampling and GC-MS based metabolite profiling provides a method to investigate the cellular metabolism of fully differentiated plant cell types in vivo. [ABSTRACT FROM PUBLISHER]

The adaptive evolution of Saccharomyces cerevisiae to repeated vacuum fermentations was investigated by metabolomic analysis using gas chromatography coupled to time-of-flight mass spectrometry. The first round (VFI, 30 cycles) and second round (VFII, 10 cycles) of repeated fermentations could be clearly distinguished by principal components analysis on intracellular metabolites, indicating that significant difference of metabolic states occurred between them. Further investigation revealed that higher levels of glycerol, trehalose, myo-inositol and glutamate might be involved in response to vacuum stress during initial cycles, while the decreases in their levels indicated that yeast cells adapted to vacuum condition as the fermentation progressed. Furthermore, lower levels of glycerol, myo-inositol, trehalose and glutamate during VFII indicated that the adapted yeast represented better vacuum tolerance. Additionally, glycolysis and TCA cycle intermediates were enhanced whereas glycerol biosynthesis was depressed by vacuum. The decreases of most amino acids might be related to increases in intermediates of glycolysis and TCA cycle as VFI progressed. These findings provided new insights into underlying mechanisms in adaptive evolution of yeast under vacuum condition. [ABSTRACT FROM AUTHOR]

Abstract: The second-sphere interactions between ferrocene (Fc, guest) analogs and cyclodextrins (CD, host) have attracted sufficient attention in the past decades. However, there are some unanswered questions related with the interactions. For example, how such interactions are reflected by the thermal decomposition process? The present report describes our efforts to elucidate the correlation between the destruction of a second-sphere complex through the release of its members and the separate destruction of its members by a direct sample introduction device with programmed temperature in a gas chromatography coupled to time-of-flight mass spectrometry. Different kinds of mass spectra are analyzed to elicit accurate details about sample decomposition processes. It is found that on the one hand, the presence of Fc effectively delays the decomposition temperature of the complexed β-CD though a great part of Fc has been released from the complex. On the other hand, the special molecular structure of β-CD has served to prevent the sublimation of Fc to a certain degree. Furthermore, the thermal decomposition mode of the β-CD molecules complexed by Fc is drastically changed compared with that of free β-CD. Also, this study provides a paradigm that ferrocene decomposes in the β-CD cavity through the release of a CpFe+ moiety, and the remaining Cp ring remains contained in the host. [Copyright &y& Elsevier]

Abstract: To investigate the metabolic regulation against inoculum density and stress response to high cell density, comparative metabolomic analysis was employed on Saccharomyces cerevisiae under fermentations with five different inoculum sizes by gas chromatography time-of-flight mass spectrometry. Samples from these fermentations were clearly distinguished by principal components analysis, indicating that inoculum size had a profound effect on the metabolism of S. cerevisiae. Potential biomarkers responsible for the discrimination were identified as glycerol, phosphoric acid, succinate, glycine, isoleucine, proline, palmitoleic acid, myo-inositol and ethanolamine. It indicated that enhanced stress protectants in glycerol biosynthesis and amino acid metabolism, depressed citric acid cycle intermediates, as well as decreased metabolites relating to membrane structure and function were involved as the inoculum size of yeast increased. Furthermore, significantly higher levels of glycerol and proline in yeast cells of higher inoculum size fermentation (40gl−1) revealed that they played important roles in protecting yeast from stresses in high cell density fermentation. These findings provided new insights into characterizing the metabolic regulation and stress response depending on inoculum density during ethanol fermentation. [Copyright &y& Elsevier]

The intracellular metabolic profile characterization of Saccharomyces cerevisiae throughout industrial ethanol fermentation was investigated using gas chromatography coupled to time-of-flight mass spectrometry. A total of 143 and 128 intracellular metabolites in S. cerevisiae were detected and quantified in continuous and batch fermentations, respectively. The two fermentation processes were both clearly distinguished into three main phases by principal components analysis. Furthermore, the levels of some metabolites involved in central carbon metabolism varied significantly throughout both processes. Glycerol and phosphoric acid were principally responsible for discriminating seed, main and final phases of continuous fermentation, while lactic acid and glycerol contributed mostly to telling different phases of batch fermentation. In addition, the levels of some amino acids such as glycine varied significantly during both processes. These findings provide new insights into the metabolomic characteristics during industrial ethanol fermentation processes. [ABSTRACT FROM AUTHOR]

Abstract: A new, simple, gas chromatographic method was developed for the direct analysis of 5-hydroxymethylfurfural (5-HMF), 2-furfural (2-F) and 5-methylfurfural (5-MF) in liquid and water soluble foods, using direct immersion SPME coupled to GC-FID and/or GC–TOF-MS. The fiber (DVB/CAR/PDMS) conditions were optimized: pH effect, temperature, adsorption and desorption times. The method is simple and accurate (RSD<8%), showed good recoveries (77–107%) and good limits of detection (GC-FID: 1.37μgL−1 for 2-F, 8.96μgL−1 for 5-MF, 6.52μgL−1 for 5-HMF; GC–TOF-MS: 0.3, 1.2 and 0.9ngmL−1 for 2-F, 5-MF and 5-HMF, respectively). It was applied to different commercial food matrices: honey, white, demerara, brown and yellow table sugars, and white and red balsamic vinegars. This one-step, sensitive and direct method for the analysis of furfurals will contribute to characterise and quantify their presence in the human diet. [Copyright &y& Elsevier]

• Pharmacodynamic analysis reveal the therapeutic effect of PVO on IUA rats. • Metabolomics reflects the changes of small molecular metabolites in IUA rats. • Metabolomics reveals the changes of pathway analysis after PVO treatment. Metabolomics is applied to explore the curative effect of complex systems, such as Chinese medicine. Intrauterine adhesion (IUA) harms the reproductive system and affects fertility, and hence is a significant public health concern. Prunella vulgaris oil (PVO) protects the reproductive system and exerts anti-inflammatory effects, but its effect on IUA and the underlying mechanism is unclear. In this study, we established a serum metabolomics method based on GC-TOF-MS to evaluate the mechanism of PVO in the IUA rat model established by mechanical injury and infection. Animal experiments showed that PVO improves the inflammatory response in the uterus of IUA model rats and reduces the content of inflammatory factors to improve the microenvironment of the reproductive system. It also regulates the expression of TGF-β1 and Smad-related mRNA and protein to inhibit fibrosis. Metabolomics indicated a significant abnormality in serum metabolism in IUA rats, and a total of 51 differential markers were screened and identified. After PVO treatment, these metabolic abnormalities improved significantly. The metabolic pathway analysis revealed that PVO affects glyoxylate and dicarboxylate metabolism, and β-alanine metabolism pathways. This study showed that PVO significantly improves inflammation and fibrosis in IUA rats combined with the pharmacological results. The primary mechanism is related to regulating the metabolism of amino acids and their derivatives to balance the associated disorders and control energy metabolism. [ABSTRACT FROM AUTHOR]

Abstract: An on-line screening method to analyse volatile organic compounds (VOCs) in faecal samples was developed. VOCs were isolated from a standard solution or faecal samples using a purge-and-trap system and identified and quantified by GC–MS. The experimental conditions were optimised and the performance of the system was evaluated. Linear calibration curves were obtained with correlation coefficients of at least 0.992. RSDs within and between days were less than 10%. The method was successfully applied to the analysis of faecal samples, yielding 135 different volatile organic compounds identified in 11 faecal samples. Of those, 22 VOCs were found in all volunteers, whereas 34 VOCs were person-specific. [Copyright &y& Elsevier]

Abstract: The thermal decomposition behavior of survived β-cyclodextrin in its inclusion complex of clove oil is investigated by nonisothermal thermogravimetry (TG) analysis at the heating rates of 5.0, 10.0, 15.0, 20.0 and 25.0Kmin−1. The TG profiles based on mass loss as a function of temperature show a clear trend of increased thermal decomposition temperature with increased heating rate. Gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF-MS) with a programmed temperature heating treatment is performed to experimentally investigate the relationship between procedural decomposition temperature and fragment composition of the sample. The results on the basis of fragment analysis explain the different mass loss of the sample corresponding to different temperatures on the gradient hot stage. [Copyright &y& Elsevier]

Abstract: Pine forests constitute some of the most important renewable resources supplying timber, paper and chemical industries, among other functions. Characterization of the volatiles emitted by different Pinus species has proven to be an important tool to decode the process of host tree selection by herbivore insects, some of which cause serious economic damage to pines. Variations in the relative composition of the bouquet of semiochemicals are responsible for the outcome of different biological processes, such as mate finding, egg-laying site recognition and host selection. The volatiles present in phloem samples of four pine species, P. halepensis, P. sylvestris, P. pinaster and P. pinea, were identified and characterized with the aim of finding possible host-plant attractants for native pests, such as the bark beetle Tomicus piniperda. The volatile compounds emitted by phloem samples of pines were extracted by headspace solid-phase micro extraction, using a 2cm 50/30mm divinylbenzene/carboxen/polydimethylsiloxane table flex solid-phase microextraction fiber and its contents analyzed by high-resolution gas chromatography, using flame ionization and a non polar and chiral column phases. The components of the volatile fraction emitted by the phloem samples were identified by mass spectrometry using time-of-flight and quadrupole mass analyzers. The estimated relative composition was used to perform a discriminant analysis among pine species, by means of cluster and principal component analysis. It can be concluded that it is possible to discriminate pine species based on the monoterpenes emissions of phloem samples. [Copyright &y& Elsevier]

Bladder cancer (BCa) and prostate cancer (PCa) are some of the most common cancers in the world. In both BCa and PCa, the diagnosis is often confirmed with an invasive technique that carries a risk to the patient. Consequently, a non-invasive diagnostic approach would be medically desirable and beneficial to the patient. The use of volatile organic compounds (VOCs) for disease diagnosis, including cancer, is a promising research area that could support the diagnosis process. In this study, we investigated the urinary VOC profiles in BCa, PCa patients and non-cancerous controls by using gas chromatography-ion mobility spectrometry (GC-IMS) and gas chromatography time-of-flight mass spectrometry (GC-TOF-MS) to analyse patient samples. GC-IMS separated BCa from PCa (area under the curve: AUC: 0.97 (0.93–1.00)), BCa vs. non-cancerous (AUC: 0.95 (0.90–0.99)) and PCa vs. non-cancerous (AUC: 0.89 (0.83–0.94)) whereas GC-TOF-MS differentiated BCa from PCa (AUC: 0.84 (0.73–0.93)), BCa vs. non-cancerous (AUC: 0.81 (0.70–0.90)) and PCa vs. non-cancerous (AUC: 0.94 (0.90–0.97)). According to our study, a total of 34 biomarkers were found using GC-TOF-MS data, of which 13 VOCs were associated with BCa, seven were associated with PCa, and 14 VOCs were found in the comparison of BCa and PCa. [ABSTRACT FROM AUTHOR]

The present study investigated the biodegradation of polystyrene (PS) plastic by mealworm (Tenebrio molitor) on different diets followed by untargeted screening of larvae gut intestine tissue and frass (manure and feed residuals) to investigate the existence of polymer-generated organic residues. Three different diets, consisting of PS, rolled barley and water were tested. PS degradation rates ranged from 16% to 23% within 15 days, with no statistical differences in survival rates. The larvae fed with ad libitum barley:PS (20:1 w/w) and water had the highest growth rate, while higher PS consumption was observed for barley:PS of 4:1 w/w. A GC-TOF-MS analysis revealed no contaminating substances in the gut intestine tissue, nor styrene or PS oligomers, whilst several bioactive compounds and traces of alkanes, mostly with small carbon chains, were present. Metabolomics analysis on the collected frass, either on the lipophilic (CHCl 3) or the polar fraction (MeOH–H 2 O) was performed. Styrene and PS oligomers (dimers, trimers) were identified, though in a relatively low total amount, up to a total of 346.0 ng/mg 2,4 di-tert butylphenol was identified in both frass and tissue, coming from the PS polymer (Non-intentionally added substances; NIAS). Finally, in the polar fraction of frass, bioactive molecules (fatty acids, amides) were identified, together with several hydrocarbons, mostly with longer carbon chains. The formation of these substances indicated enzymatic and biochemical activity in the larvae-gut intestine. It was shown that degrading and contaminating organic compounds occur at low levels, in both gut intestine and frass, during bio-degradation of PS. • PS consumption ranged from 16 to 23% during 15 days of feeding. • Frass contained low mass fractions of plastic polymer-generated compounds. • No polymer-related chemical compounds formed in insects' gut intestine tissue. • GC-TOF-MS metabolic profiling performed. [ABSTRACT FROM AUTHOR]

The long-term effect of botulinum neurotoxin A (BoNT-A) on children with cerebral palsy (CP) is unclear, and how the dynamic changes of metabolites impact the duration of effect remains unknown. To tackle this, we collected 120 plasma samples from 91 children with spastic CP for analysis, with 30 samples in each time point: prior to injection and 1, 3, and 6 months after injection. A total of 354 metabolites were identified across all the time points, 39 of which exhibited significant changes (with tentative IDs) ( p values <0.05, VIP > 1). Principal component analysis and partial least-squares discriminant analysis disclosed a clear separation between different groups ( p values <0.05). Network analysis revealed the coordinated changes of functional metabolites. Pathway analysis highlighted the metabolic pathways associated with energy consumption and glycine, serine, and threonine metabolism and cysteine and methionine metabolism. Collectively, our results identified the significant dynamic changes of plasma metabolite after BoNT-A injections on children with CP. Metabolic pathways associated with energy expenditure might provide a new perspective for the effect of BoNT-A in children with CP. Glycine, serine, and threonine metabolism and cysteine and methionine metabolism might be related to the duration of effect of BoNT-A.

As important flavor precursors, glucosinolates are ubiquitous in the plant family of Brassicaceae. Glucosinolate degradation products are the major volatile flavor compounds of rapeseed oil, accounting for up to 80% of the total volatiles. However, up to now, little attention has been paid to the volatile flavor products of the nonenzymatic thermal degradation of glucosinolates. One of the most important factors that determine the flavor of hot-pressed rapeseed oil is the roasting process, where the thermal degradation of glucosinolates mainly occurs. The thermal degradation behavior and volatile products of progoitrin (the main glucosinolate of rapeseed) in different matrices (phosphate buffer at a pH value of 5.0, 7.0, or 9.0, sea sand, and rapeseed powder) at different temperatures (150-200 °C) and times (0-60 min) were studied using HPLC and GC-TOF-MS. Thereby, the degradation rate of progoitrin decreased in the following order: pH 9.0 > sea sand > rapeseed powder > pH 7.0 > pH 5.0. Further, a higher degradation was observed with increasing temperature and time. Under the applied conditions in this study, 2,4-pentadienenitrile was the major nitrile and thiophenes were the major sulfur-containing volatile compounds formed. Possible formation pathways of main sulfur-containing and nitrogen-containing volatiles were proposed.