Metabolomics analysis of the soapberry (Sapindus mukorossi Gaertn.) pericarp during fruit development and ripening based on UHPLC-HRMS.

Soapberry (Sapindus mukorossi Gaertn.) is a multi-functional tree with widespread application in toiletries, biomedicine, biomass energy, and landscaping. The pericarp of soapberry can be used as a medicine or detergent. However, there is currently no systematic study on the chemical constituents of soapberry pericarp during fruit development and ripening, and the dynamic changes in these constituents still unclear. In this study, a non-targeted metabolomics approach using ultra-high performance liquid chromatography-high resolution mass spectrometry (UHPLC-HRMS) was used to comprehensively profile the variations in metabolites in the soapberry pericarp at eight fruit growth stages. The metabolome coverage of UHPLC-HRMS on a HILIC column was higher than that of a C18 column. A total of 111 metabolites were putatively annotated. Principal component analysis and hierarchical clustering analysis of pericarp metabolic composition revealed clear metabolic shifts from early (S1-S2) to late (S3-S5) development stages to fruit ripening stages (S6-S8). Furthermore, pairwise comparison identified 57 differential metabolites that were involved in 18 KEGG pathways. Early fruit development stages (S1-S2) were characterized by high levels of key fatty acids, nucleotides, organic acids, and phosphorylated intermediates, whereas fruit ripening stages (S6-S8) were characterized by high contents of bioactive and valuable metabolites, such as troxipide, vorinostat, furamizole, alpha-tocopherol quinone, luteolin, and sucrose. S8 (fully developed and mature stage) was the most suitable stage for fruit harvesting to utilize the pericarp. To the best of our knowledge, this was the first metabolomics study of the soapberry pericarp during whole fruit growth. The results could offer valuable information for harvesting, processing, and application of soapberry pericarp, as well as highlight the metabolites that could mediate the biological activity or properties of this medicinal plant.

Metabolic analysis of unripe papaya (Carica papaya L.) to promote its utilization as a functional food.

Papaya (Carica papaya L.) is widely cultivated in tropical and subtropical countries. While ripe fruit is a popular food item globally, the unripe fruit is only consumed in some Asian countries. To promote the utilization of unripe papaya based on the compositional changes of biological active metabolites, we performed liquid chromatography-Orbitrap-mass spectrometry-based analysis to reveal the comprehensive metabolite profile of the peel and pulp of unripe and ripe papaya fruits. The number of peaks annotated as phenolics and aminocarboxylic acids increased in the pulp and peel of ripe fruit, respectively. Putative carpaine derivatives, known alkaloids with cardiovascular effects, decreased, while carpamic acid derivatives increased in the peel of ripe fruit. Furthermore, the functionality of unripe fruit, the benzyl glucosinolate content, total polyphenol content, and proteolytic activity were detectable after heating and powder processing treatments, suggesting a potential utilization in powdered form as functional material.

1,5-Diphenylpent-3-en-1-ynes and methyl naphthalene carboxylates from Lawsonia inermis and their anti-inflammatory activity.

Lawsonia inermis (Lythraceae) known as henna is one of the most popular and ancient plants used in cosmetics and hair dying. It is cultivated for its leaves but other parts such as seeds, flowers, stem bark and roots are also used in traditional medicine for millennia. Henna tattoo paste also proved to be beneficial for wound healing and in several skin diseases suggesting potent anti-inflammatory activity. To evaluate henna anti-inflammatory activity, 31 compounds, including three 1,5-diphenylpent-3-en-1-yne derivatives, lawsochylin A-C and three methyl naphthalene carboxylates, lawsonaphthoate A-C, were isolated from the stems and leaves of henna utilizing a bioassay-guided fractionation. The structures of the compounds were elucidated by spectroscopic data. Two compounds, lawsochylin A and lawsonaphthoate A showed potent anti-inflammatory activity by inhibition of superoxide anion generation (IC(50)=1.80 and 1.90 µg/ml) and elastase release (IC(50)=1.58 and 3.17 µg/ml) of human neutrophils in response to fMLP or cytochalasin B. Moreover, the known compounds, luteolin, apigenin, 4S-4-hydroxy-α-tetralone, and 2-butoxysuccinic acid, also showed potent inhibition of superoxide anion generation (IC(50)=0.75-1.78 µg/ml) and elastase release (IC(50)=1.62-3.61 µg/ml).

Characterization of selected organic compound classes in secondary organic aerosol from biogenic VOCs by HPLC/MSn.

The formation of secondary organic aerosols (SOA) has been investigated intensively during the last two decades in numerous field and laboratory studies and a general understanding exists about the major particle-phase products. However, recent studies show that several new product classes, such as esters, peroxides or organosulfates, also have to be considered in order to understand the detailed chemical mechanisms leading to SOA as well as to predict the aerosol mass loadings. For the identification and quantification of these three compound classes as well as for carboxylic SOA compounds, liquid chromatography (LC)/mass spectrometry (MS) is the most appropriate analytical method. In this article we try to summarize briefly the work that has been done for the determination of SOA-related carboxylic acids and we present new LC/tandem MS results on the characterization of esters, peroxides and organosulfates. In contrast to earlier work, the mass-spectrometric characterization of the individual compounds is always based on the comparison with authentic reference compounds.

Synthesis of 3,8,9-trisubstituted-1,7,9-triaza-fluorene-6-carboxylic acid derivatives as a new class of insulin secretagogues.

beta-Carbolines stimulate insulin secretion in a glucose-dependent manner, probably by acting on I(3)-binding site. Knowing the in vitro glucose-dependent insulinotropic potential of beta-carbolines, in this project, three series of substituted-triaza-fluorene-6-carboxylic acids (5a-v, 6a-t, and 7a-t) were designed (analogs of beta-carboline) as a new class of insulinotropic agents. The in vitro glucose-dependent insulinotropic activities of test compounds were evaluated using RIN5F assay. Interestingly, with respect to the control, test compounds showed concentration-dependent insulin release, only in presence of glucose load (16.7 mmol). Some of the test compounds from each series were found to be equipotent to standard compound (Harmane), indicating that the pyridine ring systems of substituted-triaza-fluorenes act as bioisosteres of benzene ring in beta-carbolines.

Lipase-catalyzed condensation of p-methoxyphenethyl alcohol and carboxylic acids with different steric and electrical properties in acetonitrile.

The substrate selectivity of Candida antarctica lipase for various carboxylic acids was systematically investigated for their condensation with p-methoxyphenethyl alcohol in acetonitrile. The electron density of a carboxylic carbon and the projection area of an acid molecule were numerical indicators for evaluating the substrate selectivity. Both the electron density and projection area had an influence on the V/Km value, while only the projection area affected the Km value. The presence of conjugation with a carboxyl group in an acid and a branched structure in the non-carboxylic region independently lowered the V/Km value by an order of 1.

Enhanced sensitivity to and classification of volatile carboxylic acids using arrays of linear poly(ethylenimine)-carbon black composite vapor detectors.

Vapor detectors formed from composites of conductors and insulating organic polymers have been tailored to produce increased sensitivity toward specific classes of analyte vapors. Upon exposure to acetic acid at 1% of its vapor pressure, detectors consisting of linear poly(ethylenimine) (1-PEI)-carbon black composites showed an approximately 10(3) increase in signal/noise relative to the performance of typical insulating organic polymer-carbon black composite vapor detectors. Compositional diversity in an array of such vapor detectors was obtained by varying the degree of plasticization of the 1-PEI films. The resulting vapor detector array produced sensitive detection of, and robust discrimination between, various volatile organic acids and relatively little response from nonacidic organic vapors or from water vapor. Measurements of the mass uptake, thickness change, and electrical conductivity of such composites indicate that swelling of the polymer film, and thus its normalized resistance response, is beyond that expected by mass uptake alone upon exposure to acetic acid vapor. This additional thickness increase is attributed to charge-induced polymer swelling occurring from polymer-analyte interactions. Electrical percolation also plays a significant role in producing the large increase in normalized resistance response of these composites upon exposure to acetic acid vapor.

On robust partial discriminant analysis as a decision-making tool with clinical and analytical chemical data.

Classification is one of the fundamental goals of science and is basic to the diagnosis of disease. Unfortunately, classifying objects (e.g., patients) on the basis of clinical and/or laboratory experimental observations into various groups can be difficult when the groups overlap or contain outlying points. Recently, Broffitt, Randles, and co-workers proposed a procedure, robust partial discriminant analysis (RPDA) for dealing with such problems, but testing of the procedure was limited to Monte Carlo simulation. In this study, RPDA was applied to real data, in order to compare its effectiveness with ordinary discriminant analysis, as well as to determine if RPDA was a suitable procedure to use to classify chemical compounds on the basis of experimental observations and as a tool in the diagnosis of disease (in particular, multiple sclerosis and thyrotoxicosis), with data based on experimental and clinical observations. The resulting RPDA classifications were an improvement over those obtained from ordinary discriminant analysis.