Linseed, Baru, and Coconut Oils: NMR-Based Metabolomics, Leukocyte Infiltration Potential In Vivo, and Their Oil Characterization. Are There Still Controversies?

Different fatty acid proportions produce potential inflammatory and metabolic changes in organisms. However, the evidence for how each fatty acid mediates the metabolic pathway, and its lipid stability remains controversial. To resolve this controversy, the present study investigated the metabolic effects of cold-pressed linseed (LG), coconut (CG), and baru (BG) oils in comparison to those of soybean oil (SG) in mice, in terms of their oil characterization and stability. The quality analysis showed less oxidative behavior among PUFA-rich oils (SO, BO, and LO, with induction periods lower than 2 h compared to 39.8 h for CG), besides the high contents of tocopherols and carotenoids in SG and LG. In the experimental study, CG presented higher triglyceride (257.93 ± 72.30) and VLDL-cholesterol levels (51.59 ± 14.46, p < 0.05), while LG reduced LDL levels (59.29 ± 7.56, p < 0.05) when compared to SG (183.14 ± 22.06, 36.63 ± 4.41 and 131.63 ± 29.0, respectively). For visceral fats, the adiposity index was lower for BG (7.32 ± 3.13) and CG (9.58 ± 1.02, p < 0.05) in relation to SG (12.53 ± 2.80), and for leukocyte recruitment, CG presented lower polymorphonuclear (PMN) (p < 0.0001) and mononuclear (MN) (p < 0.05) cell infiltration, demonstrating anti-inflammatory potential. In NMR-based metabolomics, although CG presented higher values for the glucose, lactate, and LDL/VLDL ratio, this group also evidenced high levels of choline, a lipotropic metabolite. Our study emphasized the controversies of saturated fatty acids, which impair serum lipids, while alfa-linolenic acid presented cardioprotective effects. However, coconut oil also has a positive immunomodulatory pathway and was found to reduce visceral bodyfat in mice. Therefore, for future applications, we suggest a combination of lauric and al-fa-linolenic acid sources, which are present in coconut and linseed oil, respectively. This combination could be less obesogenic and inflammatory and exert cardioprotective action.

NMR-based metabolomics of dried berries in comparison with dietary supplements.

Consumption of dried berries is increasing worldwide due to their health benefits. This popularity has introduced berry-based supplements as an easier way to take in berry nutrients. The chemical composition of six dried berries (blueberry, cranberry, goji berry, golden berry, maqui berry, and raspberry) were compared to their berry-based supplements by metabolomics using nuclear magnetic resonance spectroscopy (NMR). Thirty-three metabolites were identified and 23 were quantified. Chemometric analysis of berries revealed that goji berry showed the highest content of amino and organic acids, while cranberry and golden berry showed a high carbohydrate content. Fatty acids were predominant in blueberry, golden berry, maqui berry, and raspberry. Additionally, an exploratory analysis of phenolic compounds in berry extracts were conducted. phenolic compounds in berry extracts could be correlated with their antioxidant activity. Additionally, derived supplements did not show similarities with their respective berry, suggesting the minimal addition of dried berry in their formulation. Thus, non-declared additives have highlighted the importance of food safety investigation.

Vegetable oils: Are they true? A point of view from ATR-FTIR, 1H NMR, and regiospecific analysis by 13C NMR.

Problems related to oil authenticity make it difficult to obtain the benefits associated with each type of vegetable oil. Fraudulent practices have been revealed by several targeted and nontargeted methods. In this paper, spectroscopic techniques (FT-IR, 1H NMR, and 13C NMR) were applied to determine the chemical profiles of 23 Brazilian commercial vegetable oils obtained from five different high-value aggregated matrices (andiroba, babassu, baru, castor, and sweet almond oils) and investigate their adulteration, by comparison with the corresponding reference samples. Each technique is useful for the particular information it provides: differences in free fatty acids by FT-IR; adulteration with omega-3-enriched oils by 1H NMR, and adulteration of unsaturated-enriched oil with another unsaturated oil without linoleic acid by regiospecific analysis. Our findings highlight the importance of fusion-based methods in providing precise information for use in oil quality authentication.

Sodium quantitation in soft drinks: A rapid methodology by qNMR.

High sodium dietary intake has a positive association with an increase in blood pressure and can be correlated with risk factors of disease. Considering that the World Health Organization recommends a sodium intake lower than 2 g day-1 for adults, the hidden sodium content in processed foods is an important factor that compromises the assessment of a healthy diet. Accordingly, the present paper aimed to quantitate the sodium content of conventional soft drinks and their diet versions using nuclear magnetic resonance spectroscopy as a quantitative analytical technique (23 Na qNMR). The results show one free sodium signal (Na+ ) displayed as a singlet at 0 ppm in the 23 Na NMR spectrum, making its quantitation highly specific. This signal alone was used to directly determine the concentration of sodium in soft drinks. Flame photometry analysis was used to validate the method, and an excellent linearity was found in qNMR analysis (r = 0.9994) in comparison with flame photometry (r = 0.9958). In addition, a good correlation was found between sodium concentrations obtained by 23 Na NMR and flame photometry in the evaluated commercial soft drinks. Since the intensity of the resonance line is directly proportional to the number of nuclei (spins), the concentration of sodium in soft drinks can be determined via this straightforward method without the need for external calibration. The experimental acquisitions are fast (approximately 15 min), allowing the analysis of several samples in a short period of time. This is a novel alternative for sodium quantitation using an efficient NMR methodology.

Metabolic response of soybean plants to Sclerotinia sclerotiorum infection.

White mold is a disease caused by the fungus Sclerotinia sclerotiorum, a highly destructive necrotrophic pathogen that infects soybean crops, among others. Usually, the infection triggers the plant defense system to minimize the damages. However, the effects of the infection on soybean plant metabolism are still unclear. In this work, the metabolic profiles of soybean stems and leaves were accessed using 1H HR-MAS NMR spectroscopy to identify metabolic changes as a response to S. sclerotiorum infection. This fungus widely affects the central metabolism of soybean plants, and most of the altered metabolites are involved in carbon metabolism, as suggested by the results. Furthermore, the metabolites of central metabolism can be associated with the production of several polyphenolic metabolites. Changes in metabolic profile of leaves indicate systemic effects.

NMR-based and chemometric approaches applicable to adulteration studies for assessment of the botanical origin of edible oils.

The health benefits of edible oils, especially promoted by ω3 and ω9 fatty acids, have been associated with their botanical origin. In order to investigate fatty acid profiles, we assessed Brazil nut, chia, linseed, sesame (toasted and raw), and soybean oils by 1H nuclear magnetic resonance (1H NMR) and chemometrics. PCA plots revealed important relationships between chemical composition and botanical origin for reference and commercial samples. Strong evidence of commercial Brazil nut oil adulteration was confirmed using a spiking procedure. Our findings show that NMR and chemometrics are successful tools for correlating fatty acid profile with botanical origin, which can be suitable for detecting sample adulteration.

NMR-based approach reveals seasonal metabolic changes in mate (Ilex paraguariensis A. St.-Hil.).

Ilex paraguariensis (mate) is a species native to South America and is widely consumed in countries such Argentina, Uruguay, Paraguay, and Brazil. Mate consumption is associated with several phytotherapeutic functions, in addition to its cultural and regional importance. However, the harvest period can affect the properties of the mate, due to variations in the constituent proportions, as a consequence of seasonal changes. In this work, we employed nuclear magnetic resonance and chemometrics to evaluate the chemical variations in leaf extracts of I. paraguariensis over the four seasons of the year. We found significant changes in the levels of glucose, myo-inositol, caffeine, theobromine, and fatty acids. These changes can be related to resource allocation for the flowering period, or to responses to environmental stresses, such as temperature.

Metabolic Study of Dioecy in Mauritia flexuosa: NMR-based and Chemometric Approaches.

INTRODUCTION: Mauritia flexuosa is a dioecious species native to the Amazon, and the gender identification can currently be determined through the differentiation between female and male flowers in the first flowering. OBJECTIVES: To identify variations in the metabolome profiles of pooled and individual samples of leaves from female and male plants of M. flexuosa in reproductive phase, and the plant in its vegetative phase, using two extraction systems. MATERIAL AND METHODS: Extractions of leaves were separately conducted using deuterated water and methanol. The extracts were evaluated by NMR spectroscopy and chemometric methods. RESULTS: Different NMR spectroscopic profiles were observed for females, males, and plants in the vegetative phase. Significant variations were found in the carbohydrate and fatty acid contents for the aqueous and methanolic extracts, respectively. Although principal component analysis (PCA) has not been efficient to distinguish the genders, orthogonal signal correction/partial least squares-discriminant analysis (OPLS-DA) was able to successfully differentiate male and female plants in the reproductive phase, independently on the sampling approach. For plants in the vegetative phase, OPLS-DA method from aqueous extracts of M. flexuosa leaves also distinguished female samples from the others and showed a small overlap between male and young plants, while the classification model was not able to be used for prediction. CONCLUSIONS: NMR spectroscopy and chemometric-based approach was demonstrated to be useful in the metabolic study of dioecy in M. flexuosa. The extracts of the leaves allowed for differentiation between male and female plants; however, for plants in the vegetative phase, the identification of the gender was not effective. Copyright © 2018 John Wiley & Sons, Ltd.

Ethanol determination in frozen fruit pulps: an application of quantitative nuclear magnetic resonance.

This study reports the chemical composition of five types of industrial frozen fruit pulps (acerola, cashew, grape, passion fruit and pineapple fruit pulps) and compares them with homemade pulps at two different stages of ripening. The fruit pulps were characterized by analyzing their metabolic profiles and determining their ethanol content using quantitative Nuclear Magnetic Resonance (qNMR). In addition, principal component analysis (PCA) was applied to extract more information from the NMR data. We detected ethanol in all industrial and homemade pulps; and acetic acid in cashew, grape and passion fruit industrial and homemade pulps. The ethanol content in some industrial pulps is above the level recommended by regulatory agencies and is near the levels of some post-ripened homemade pulps. This study demonstrates that qNMR can be used to rapidly detect ethanol content in frozen fruit pulps and food derivatives. Copyright © 2015 John Wiley & Sons, Ltd.

NMR-Based Metabolomic Analysis of Huanglongbing-Asymptomatic and -Symptomatic Citrus Trees.

Huanglongbing (HLB) is one of the most severe diseases that affects citrus trees worldwide and is associated with the yet uncultured bacteria Candidatus Liberibacter spp. To assess the metabolomic differences between HLB-asymptomatic and -symptomatic tissues, extracts from leaf and root samples taken from a uniform 6-year-old commercial orchard of Valencia trees were subjected to nuclear magnetic resonance (NMR) and chemometrics. The results show that the symptomatic trees had higher sucrose content in their leaves and no variation in their roots. In addition, proline betaine and malate were detected in smaller amounts in the HLB-affected symptomatic leaves. The changes in metabolic processes of the plant in response to HLB are corroborated by the relationship between the bacterial levels and the metabolic profiles.

Polycyclic aromatic hydrocarbon concentrations in gas and particle phases and source determination in atmospheric samples from a semiurban area of Dourados, Brazil.

A headspace solid-phase microextraction (HS-SPME) procedure that employs a PDMS/DVB fiber was developed for the analysis of gas-phase polycyclic aromatic hydrocarbons (PAHs) collected in polyurethane foam (PUF) by gas chromatography (GC) mass spectrometry. The method exhibited good linearity (R (2) > 0.99) and repeatability (4.9-25 %) as well as an impressive detection limit that ranged from 1.1 to 3.3 ng. Twenty-two air samples were collected by high-volume samplers from January to November 2007 in a semiurban area of Dourados (Brazil) and were analyzed for their content of total suspended particulates and PAHs. The PAHs were extracted from the PUF samples using the developed procedure (HS-SPME), and PAHs adsorbed on particulate matter were extracted with dichloromethane/methanol (4:1 [v/v]) in an ultrasonic bath. The values of the total daily concentrations of 16 PAHs determined in the samples ranged from 0.375 to 8.407 ng m(-3). In addition, diagnostic ratios were calculated, showing that the PAHs in the atmosphere at the sampling site originated predominantly from vehicle emissions and the combustion of grass and wood. Hierarchical cluster analysis and principal component analysis were performed as well, the results of which indicated (1) the same sources of PAH identified by the diagnostic ratios and (2) that the sampling days could be categorized into three groups depending on the atmospheric conditions. GC retention indices were also used to identify PAHs, biphenyl (phenylbenzene), and heterocyclic organic compounds (benzofurans) in some of the samples.

Increment of antimycobaterial activity on lichexanthone derivatives.

A new dihydropyranexanthone derived from the natural xanthone lichexanthone (1) was synthesised and, together with other 18 derivatives including ω-bromo and ω-aminoalkoxylxanthones (containing methyl, ethyl, propyl, tertbutylamino and piperidinyl moieties), were tested against Mycobacterium tuberculosis. Nine ω-aminoalkoxylxanthones showed good antimycobacterial activity, and their in vitro cytotoxicity was determined using VERO cells in order to calculate the selectivity index (SI). One of these nitrogenated xanthone derivatives showed very promising results, with MIC of 2.6 µM and SI of 48. This MIC is comparable to values found in "first and second line" drugs commonly used to treat TB. In order to understand better about this compound, it was evaluated together with two other ones that showed good SI, against resistant clinical strains of M. tuberculosis to verify the existence of cross-resistance. A chemometrical approach was useful to establish a pattern of antitubercular activity among the group of ω-aminoalkoxylxanthones, according to some structural and chemical features.

Cytotoxic evaluation of phenolic compounds from lichens against melanoma cells.

Atranorin, lichexanthone, and the (+)-usnic, diffractaic, divaricatic, perlatolic, psoromic, protocetraric, and norstictic acids isolated from the lichens Parmotrema dilatatum (VAIN.) HALE, Usnea subcavata MOTYKA, Usnea sp., Ramalina sp., Cladina confusa (SANT.) FOLMM. & AHTI, Dirinaria aspera HÄSÄNEN, and Parmotrema lichexanthonicum ELIASARO & ADLER were evaluated against UACC-62 and B16-F10 melanoma cells and 3T3 normal cells. Sulforhodamine B assay revealed significant cytotoxic activity in protocetraric, divaricatic, and perlatolic acids on UACC-62 cells (50% growth inhibitory concentration (GI(50)) 0.52, 2.7, and 3.3 µg/mL, respectively). Divaricatic and perlatolic acids proved the most active on B16-F10 cells (GI(50) 4.4, 18.0 µg/mL, respectively) and the most cytotoxic to 3T3 normal cells. Diffractaic, usnic, norstictic, and psoromic acids were cytotoxic to UACC-62 cells in the 24.7 to 36.6 µg/mL range, as were protocetraric and diffractaic acids to B16-F10 cells (GI(50) 24.0, 25.4 µg/mL, respectively). Protocetraric acid was highly selective (selectivity index (SI*) 93.3) against UACC-62 cells, followed by norstictic, perlatolic, psoromic, and divaricatic acids, while norstictic and divaricatic acids were more selective against B16-F10 cells. The high SI* value obtained for protocetraric acid on UACC-62 cells makes it a potential candidate for the study of melanomas in experimental models. Chemometric analysis was performed to evaluate the general behavior of the compounds against the cell lines tested.