Determination of nonylphenol ethoxylate metabolites in vegetables and crops by high performance liquid chromatography-tandem mass spectrometry

A method has been developed for the simultaneous determination of the concentration of nonylphenol (4-NP), nonylphenol monoethoxylates (NP₁EO) and nonylphenol diethoxylates (NP₂EO) in vegetables and crops by liquid chromatography-tandem quadrupole mass spectrometry (HPLC-MS/MS). These target compounds were extracted from vegetable and crop samples with acetonitrile, and then the extracts were cleaned using solid phase extraction with graphitised carbon black tandem primary secondary amine (PSA) cartridges. The MS method enabled highly reliable identification by monitoring the corresponding ammonium adduct [M+NH₄]⁺ in the positive mode for NP₁EO and NP₂EO, and the deprotonated molecule [M−H]⁻ in the negative mode for 4-NP. Recoveries for the spiked samples ranged from 65% to 118%. The limit of detection (LOD) of 4-NP, NP₁EO and NP₂EO was 3, 5 and 0.1 μg kg⁻¹, respectively. This method would be useful for the quick and routine detection of the residues of 4-NP, NP₁EO and NP₂EO in vegetables and crops.     

Isolation and structural characterisation of five new and 14 known metabolites from the commercial starfish Archaster typicus

From the commercially available starfish Archaster typicus, five new (1–5) and 14 known (6–19) metabolites were isolated and identified. Detailed 1D and 2D NMR spectroscopic data, including ¹H, ¹³C, DEPT, HSQC, HMBC, and NOESY, established the structures of the new metabolites as sodium 5α-cholesta-9(11),24-dien-3β,6α,20β-triol-23-one 3-sulphate (1), sodium 5α-cholesta-9(11)-en-3β,6α,20β-triol-23-one 3-sulphate (2), sodium (25R)-5α-cholestane-3β,4β,6α,8,14α,15β,26-heptaol-15-sulphate (3), sodium (25R)-5α-cholestane-3β,6α,8,14α,15β,26-hexaol 15-sulphate (4), and sodium cholest-25(27)-ene-3β,4β,5α,6α,7β,8β,14α,15α,24,26-decanol 6-sulphate (5). Other spectroscopic techniques, including IR, ESI–MS, and HR-ESI–MS, were also adopted to further confirm the structures of the metabolites. These five steroids (1–5) are reported in nature for the first time. All of the steroids found in A. typicus (1–12) were tested for anticancer activities against MDA-MB-435 and Colo205 tumour cells. However, only sodium 5α-cholesta-9(11)-en-3β,6α,20β-triol-23-one 3-sulphate (2) and 27-nor-5α-cholestane-3β,4β,5,6α,7β,8,14,15α,24α-nonaol (6) exhibited weak activities.     

Metabolite profiling,antioxidant activity,and glycosidase inhibition property of the mesocarp tissue extracts of sugar date palm [Phoenix sylvestris (L.) Roxb.] fruits

Phoenix sylvestris is an underutilized seasonal fruit in West Bengal, India. Methanol extract and extracts after alkaline hydrolysis of the mesocarp tissue of full-mature edible fruits of P. sylvestris were analyzed by GC-MS following a metabolomics approach. The fractions were tested for their antioxidant and inhibitory properties against the two key enzymes involved in diabetes, α-amylase, and α-glucosidase. Total 71 metabolites belonging to organic acids, amino acids, sugars, sugar alcohols, fatty acids, and phenols were identified in the methanol extract and in fractions after saponification. All the extracts and fractions showed high antioxidant, α-glucosidase, and α-amylase inhibitory activities. Sugars like raffinose (IC₅₀ = 0.36 μM), sucrose (IC₅₀ = 0.51 μM), trehalose (IC₅₀ = 0.85 μM), and phenols like taxifolin (IC₅₀ = 0.31 μM), benzoic acid (IC₅₀ = 2.74 μM) inhibited only the enzyme α-amylase. Phenolic components which inhibited both the enzymes were caffeic acid (IC₅₀ = 1.42 μM for α-amylase and IC₅₀ = 1.8 μM for α-glucosidase), 3, 4-dihydroxy benzoic acid (IC₅₀ = 0.23 μM for α-amylase and IC₅₀ = 2.58 μM for α-glucosidase), and quinic acid (IC₅₀ = 4.91 μM for α-amylase and IC₅₀ = 4.95 μM for α-glucosidase). Ferulic acid (IC₅₀ = 0.52 μM) and 4-hydroxycinnamic acid (IC₅₀ = 0.23 μM) inhibited only α-glucosidase. This study suggested that the metabolites present in the fruit mesocarp tissue showed the potential antioxidant activity and properties to inhibit the enzymes α-amylase and α-glucosidase. Further in vivo study is to be carried out to prove the efficacy of the fruits.

Abbreviations: FM: crude methanol extract; SI: ethyl acetate extract after alkaline hydrolysis step I; SII: ethyl acetate extract after alkaline hydrolysis step II     

Physiological and structural events post mortem of importance for drip loss in pork

Early post mortem metabolism and structural changes from 3 to 24 h, together with pH, temperature and impedance Py development were investigated in 37 Duroc×Landrace×Large White (DLY) pigs covering a range of drip loss from 2.2 to 12.6%. Multivariate statistical analysis was used to assess the impacts of different metabolites, pH and temperature, impedance, cytoskeletal protein degradation and extracellular cross-sectional area on drip loss. Taken as single factors, the concentration of lactate could explain 80% of the variation in drip, inosine monophosphate (IMP) and adenosine triphosphate (ATP) concentration explained 71 and 68%, respectively, whereas inosin and glycogen levels explained only 59 and 60%. The extracellular area was found to explain 39% of the variation in drip. The area between fibres provided more significant information than did the area between fibre bundles. The degradation of the cytoskeletal proteins was not related to drip loss. Impedance Py development over 24 h could explain 66% of the variation in drip, whereas pH and temperature explained 85 and 87%, respectively. A model including all measured variables could explain 83% of the variation in drip. However, only pH, temperature, impedance, [ATP]_{1 h} and [lactate]_{1 h and 2 h} were significant in relation to drip. By reducing the variables in the multivariate analysis, 89% of the variation in drip could be explained by a model containing only pH_{2 h} and temperature_{1 min}. To explain variation in drip loss, pH and temperature measurements at significant time points were sufficient. Variation in post-mortem metabolites did, however, explain why variation in pH and temperature occurred. Development of drip channels was ruled by pH and temperature while impedance development was highly correlated to pH. This multi-faceted study shows those parameters, which can best be used to indicate or predict WHC, as well as those indicating the basic mechanism underlying variations in drip.     

Microbial and "de novo" transformation of dicarboxylic acids by three airborne fungi

Micro-organisms and organic compounds of biogenic or anthropogenic origins are important constituents of atmospheric aerosols, which are involved in atmospheric processes and climate change. In order to investigate the role of fungi and their metabolisation activity, we collected airborne fungi using a biosampler in an urban location of Montreal, Quebec, Canada (45 degrees 28' N, 73 degrees 45' E). After isolation on Sabouraud dextrose agar, we exposed isolated colonies to dicarboxylic acids (C(2)-C(7)), a major group of organic aerosols and monitored their growth. Depending on the acid, total fungi numbers varied from 35 (oxalic acid) to 180 CFU/mL (glutaric acid). Transformation kinetics of malonic acid, presumably the most abundant dicarboxylic acid, at concentrations of 0.25 and 1.00 mM for isolated airborne fungi belonging to the genera Aspergillus, Penicillium, Eupenicillium, and Thysanophora with the fastest transformation rate are presented. The initial concentration was halved within 4.5 and 11.4 days. Other collected fungi did not show a significant degradation and the malonic acid concentration remained unchanged (0.25 and 1.00 mM) within 20 days. Degradation of acid with formation of metabolites was followed using high performance liquid chromatography-ultraviolet detection (HPLC/UV) and gas chromatography-mass spectrometry (GC/MS), as well as monitoring of (13)C labelled malonic acid degradation with solid-state nuclear magnetic resonance spectroscopy (NMR). Using GC/MS we identified two processes driving chemical modifications of organic aerosol solutions: (I) formation of metabolites within several days, and (II) rapid release (< or =2 min) of organic molecules from fungal species upon the insertion of taxa in organic aerosol solutions. Metabolites included aromatic compounds and alcohols (e.g. trimethylbenzene and butanol). Potential atmospheric implications of our results are discussed.     

Targeting the gut microbiota by dietary nutrients: A new avenue for human health

The gut microbiota is a complex ecosystem consisted of trillions of microbes that have co-evolved with their host for hundreds of millions of years. During the last decade, a growing body of knowledge has suggested that there is a compelling set of connections among diet, gut microbiota and human health. Various physiological functions of the host, ranging from metabolic and immune regulation to nerve and endocrine development, are possibly mediated by the structural components of microbial cell or the products of microbial metabolism, which are greatly influenced by dietary macronutrients and micronutrients. Thus, governing the production and activity of these microbial-associated small molecules and metabolites through dietary intervention may provide promising strategies for the improvement of human health and disease. In this review article, we first provide an overview of current findings about the intimate interrelationships between diet and gut microbiota. We also introduce the physiological effects of some microbial-associated small molecules and metabolites on the host as well as the detailed signaling mechanisms.