Association of Pollinators of Different Species of Oil Palm with the Metabolic Profiling of Volatile Organic Compounds.

The development of studies on emissions of volatile organic compounds (VOCs) by inflorescence of oil palms deserves a special attention regarding the importance to reproduction success and for increase of production. This study aimed to evaluate metabolic profiling of VOCs expelled by male and female inflorescences of different oil palm species (African oil palm, Amazonian Caiaué and the interspecific hybrid BRS-Manicoré), associating the composition variability with main pollinators to improve the comprehension of the plant-insect relationship. The phenylpropanoids, terpenoids and the aliphatic hydrocarbons were predominant classes detected in inflorescences of oil palms and the major compound was estragole. This result may be correlated with attraction of Elaidobius pollinators, since these insects were not attracted by Caiaué, which emitted estragole only in trace amounts. However, Caiaué and the hybrid species were visited by other native species whose frequencies were low and their success as pollinators could not be expected.

Advancements in waste water characterization through NMR spectroscopy: review.

There are numerous organic pollutants that lead to several types of ecosystem damage and threaten human health. Wastewater treatment plants are responsible for the removal of natural and anthropogenic pollutants from the sewage, and because of this function, they play an important role in the protection of human health and the environment. Nuclear magnetic resonance (NMR) has proven to be a valuable analytical tool as a result of its versatility in characterizing both overall chemical composition as well as individual species in a wide range of mixtures. In addition, NMR can provide physical information (rigidity, dynamics, etc.) as well as permit in depth quantification. Hyphenation with other techniques such as liquid chromatography, solid phase extraction and mass spectrometry creates unprecedented capabilities for the identification of novel and unknown chemical species. Thus, NMR is widely used in the study of different components of wastewater, such as complex organic matter (fulvic and humic acids), sludge and wastewater. This review article summarizes the NMR spectroscopy methods applied in studies of organic pollutants from wastewater to provide an exhaustive review of the literature as well as a guide for readers interested in this topic.

Non-targeted analyses of organic compounds in urban wastewater.

A large number of organic pollutants that cause damage to the ecosystem and threaten human health are transported to wastewater treatment plants (WWTPs). The problems regarding water pollution in Latin America have been well documented, and there is no evidence of substantive efforts to change the situation. In the present work, two methods to study wastewater samples are employed: non-targeted 1D ((13)C and (1)H) and 2D NMR spectroscopic analysis to characterize the largest possible number of compounds from urban wastewater and analysis by HPLC-(UV/MS)-SPE-ASS-NMR to detect non-specific recalcitrant organic compounds in treated wastewater without the use of common standards. The set of data is composed of several compounds with the concentration ranging considerably with treatment and seasonality. An anomalous discharge, the influence of stormwater on the wastewater composition and the presence of recalcitrant compounds (linear alkylbenzene sulfonate surfactant homologs) in the effluent were further identified. The seasonal variations and abnormality in the composition of organic compounds in sewage indicated that the procedure that was employed can be useful in the identification of the pollution source and to enhance the effectiveness of WWTPs in designing preventive action to protect the equipment and preserve the environment.

Corrigendum to "Evaluation of freeze-dried phenolic extract from cashew apple by-product: Physical properties, in vitro gastric digestion and chemometric analysis of the powders" [Food Chemistry: Molecular Sciences 5 (2022) 100149].

[This corrects the article DOI: 10.1016/j.fochms.2022.100149.].

NMR-Based Metabolomic Approach for Evaluation of the Harvesting Time and Cooking Characteristics of Different Cassava Genotypes.

Cassava is an important staple food for low-income countries. However, its cooking characteristics are especially affected by genotype. In this study, two groups of genotypes, namely hard to cook (HTC) and easy to cook (ETC), were harvested at different times (9 and 15 months), and evaluated by NMR coupled to chemometrics. Additionally, lignin of these materials was studied by 1H-13C HSQC NMR. The carbohydrates were the most important class of compounds to differentiate the cassava genotypes. The correlation of NMR with cooking time and starch content showed that the higher content of primary metabolites, mostly glucose, can be associated with longer cooking times and reduction of starch, corroborating the metabolic pathways analysis. Furthermore, it was observed that the lignin from cell walls did not differentiate the cooking performance of the genotypes.

1H NMR and UPLC-HRMS-based metabolomic approach for evaluation of the grape maturity and maceration time of Touriga Nacional wines and their correlation with the chemical stability.

Touriga Nacional is a well-adapted Portuguese grape variety in São Francisco River Valley (northeastern Brazil). Nevertheless, it has only been indicated to short-term consumption because of the lack of chemical stability, which is attributed to low grape acidity and incomplete phenolic maturity. Therefore, we used Ultra-Performance Liquid Chromatography coupled High-resolution Mass Spectrometry, Nuclear Magnetic Resonance and chemometrics (PCA and PLS-DA) to evaluate the grape maturity and maceration time on chemical composition of wines from two harvest seasons. Moreover, we investigated how these experimental factors could affect their chemical stability. Grapes maturity showed to be the main effect. Overall, phenolic acids and short-chain organic acids were found to be at higher levels in wines produced with unripe grapes from February and shorter maceration time (p < 0.05). Proanthocyanidins and other flavonoids were increased in wines macerated for longer time using overripe grapes harvested in July. Furthermore, stable wines were made from overripe grapes, which contained more galacturonic acid.

Chemometric analysis of the volatile profile in peduncles of cashew clones and its correlation with sensory attributes.

Cashew apple, the hypertrophied peduncle of cashew nut, is a functional food with a high antioxidant activity and with good characteristics for juice industrialization and fresh consumption such as fleshy pulp, soft peel, without seeds, and exotic flavor. However, it is still poorly used or totally wasted. For this reason, the quality of cashew apples has received more attention from the Brazilian breeding program to maximize their uses. In this study, the volatile compound profiles of peduncles of seven cashew clones and their relation to the aroma and flavor differences were investigated. Nine trained panelists evaluated the cashew apples by descriptive analysis. After the standardization of headspace solid-phase microextraction (HS-SPME) extraction and chromatographic conditions, the volatile organic compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). A total of 48 compounds were identified with esters being the major chemical class, both in number of compounds and chromatographic peak area. The targeted and untargeted principal component analysis (PCA) analyses showed complementary and corroborative results from the cashew apple volatile composition based on genotype. The partial least squares (PLS) modeling revealed the high correlation of the unpleasant sensory attributes with the PRO805 and CAPI17 clones; sweet taste and sweet odor with the CCP76 clone; and cashew aroma/cashew flavor with the EMBRAPA51, HAC276, PRO555, and SLC12.20 clones. The correlation between the most relevant volatile organic compounds (VOC) for cashew apples and the sensory descriptors showed that the compounds methyl butanoate, methyl 3-methylbutanoate, ethyl 2-methylbutanoate, methyl 2-butenoate, methyl 3-methylpentanoate, 3-carene, methyl (E)-2-methyl-2-butenoate, ethyl 4-methylpentanoate, 2-hexenal, butyl 3-methylbutanoate, butyl pentanoate, and 3-methyl butanoic acid were important to explain differences in the characteristic fruit aroma and flavor of cashew apples among the studied clones. PRACTICAL APPLICATION: Cashew crops have been developed by using improved clones with increased nut productivity and resistance to diseases. The Brazilian genetic improvement program is also seeking to improve the quality of peduncles to maximize their use and prevent their destination as agricultural waste. In this study, the volatile profile of peduncles of seven cashew clones was determined and its correlation with the differences in their aroma and flavor attributes established. The results will provide important information about the potential of the new materials for fresh consumption and for the manufacturing of cashew juices, in addition to be used by breeders interested in improving the aroma of the fruit.

Untargeted GC/MS-based approach for identification of anti-inflammatory alkaloids from Hippeastrum elegans (Amaryllidaceae) using a human neutrophil model.

Hippeastrum elegans is an Amaryllidaceae species producing alkaloids with pharmaceutical potential including lycorine and galanthamine. Herein, we developed a non-targeted metabolomic study associated to chemometrics and biological evaluations to identify the H. elegans constituents that were able to reduce the human neutrophils proinflammatory mechanisms. The alkaloid fractions were extracted from bulbs cultivated for 15 months (m) and harvested in six harvest periods (5, 7, 9, 11, 13, and 15 m). The GC-MS analysis allowed the detection of 41 alkaloids being 31 identified. All alkaloid components varied over the cultivation and most of them were lycorine-type skeletons. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) distinguished three groups according to the chemical profile (group I: 5, 7, and 9 m; group II: 11 m and group III: 13 and 15 m). Therefore, the biological assays were only performed with one of the representative samples of each group: 7 m, 11 m and 15 m. None of them was toxic to human neutrophils by LDH activity and MTT test. The 7 m and 15 m-alkaloid fractions showed anti-inflammatory effects by reducing human neutrophil degranulation. However, the former one was more effective in inhibiting the cell activation based on the reduction of myeloperoxidase (MPO) release and reactive oxygen species (ROS) production. Afterwards, Partial Least Squares analysis (PLS) indicated lycorine and 11,12-dehydro-2-methoxy-assoanine as the compounds responsible for the anti-inflammatory activity of the bioactive fraction. Thus, the 7 m-alkaloid fraction of H. elegans seems to be a promising anti-inflammatory drug that deserves additional research.

Atmospheric cold plasma frequency imparts changes on cashew apple juice composition and improves vitamin C bioaccessibility.

This study evaluated the atmospheric cold plasma (ACP) effect on cashew apple juice composition at different frequencies (200 and 700 Hz). The impact of this non-thermal technology on the organic juice compounds after the processing and along with the in vitro digestion carried out in a simulated digestion system at 37 °C/6 h was evaluated. The changes in the juice composition were determined by NMR spectroscopy and chemometric analyses. Vitamin C and total phenolic compounds were also quantified in processed and non-processed (control) juices and after each digestion phase. The results showed decreased glucose and fructose in samples treated by ACP and an increment in malic acid concentration for ACP700. ACP increased the amount of vitamin C in the juices and did not affect the total phenolic content. The gastric digestion highlighted the pronounced effect of plasma on the juice composition, increasing all of the components detected by NMR. Cashew apple juice processed by ACP700 presented a higher concentration of malic acid and phenylalanine. An increased bioaccessibility of vitamin C was also found for ACP700. Although ACP processing has decreased some compounds' concentration, this technology improved the bioaccessibility of vitamin C - the main bioactive compound of cashew apple juice.

Nopal cladode as a novel reinforcing and antioxidant agent for starch-based films: A comparison with lignin and propolis extract.

The potential use of nopal cladode flour (NC) as reinforcing/bioactive agent in cassava starch-based films was evaluated and compared with the use of propolis extract or lignin, which are commonly used for these purposes. Cassava starch-based films containing untreated NC (S-NC), NC treated at pH 12 (S-NC12), aqueous propolis extract at two different concentrations (SP1 or SP2), or lignin (S-L) were produced by the casting technique; glycerol was used as plasticizer. NC12 and NC affected the mechanical properties of the cassava starch-based film similarly as compared to propolis extract and lignin. Moreover, NC and NC12 had different performance as reinforcing and antioxidant agent in cassava starch-based film. Thus, S-NC12 film was more elongable (28.5 ± 6.5%), more hydrophobic (contact angle: 70.8° ± 0.1), less permeable to water vapor (0.8 ± 0.0 × 10-10 g·m-1·s-1·Pa-1) and had better antioxidant activity by ABTS•+ (44.70 ± 0.3 µM Trolox·g-1 of film) than the S-NC film. SEM and TGA analysis of films showed that NC12 was better incorporated into the cassava starch matrix than NC, lignin and propolis extract. Overall, nopal cladode flour has potential use in the production of active biodegradable packaging for the food preservation with high oxidation rate.

Green ultrasound-assisted extraction of chlorogenic acids from sweet potato peels and sonochemical hydrolysis of caffeoylquinic acids derivatives.

Sweet potato peels are rich in chlorogenic acids. In this work, we applied ultrasound technology to extract the main compounds from sweet potato peel and used multivariate analysis and principal component analysis (PCA) to evaluate the effects of different extraction conditions on the extraction of chlorogenic acids. The extraction was studied varying ultrasonic power density (20, 35 and 50 W/L) and processing time (5, 10, 20 and 40 min) using an ultrasonic bath operating at 25 kHz. The chemical analysis was carried out by UPLC-qTOF-MS, and the results were evaluated by PCA and PLS-DA chemometric analysis. Results show that both ultrasonic power density and processing time influences in the extraction of different chlorogenic acid, and that different extraction conditions can be used to selectively extract specific caffeoylquinic acids and feruloylquinic acids in higher amounts. Ultrasound promoted the hydrolysis of tricaffeoylquinic acid when subjected to ultrasonic waves (20-50 W/L), and of 3,4-caffeyolquinic acid at high ultrasonic power density (50 W/L).

Thermal and non-thermal processing effect on açai juice composition.

This study evaluated the effects of High-Temperature Short Time (HTST), Ultra High Temperature (UHT), and the non-thermal processes High Power Ultrasound (US), UV-pulsed-light and Low Pressure Plasma (LPP) on the composition, stability, and bioactive compounds bioaccessibility of açai juice. 1H NMR based approach, coupled to chemometrics, was applied to evaluate the changes in the juice composition. All the non-thermal processes increased the sugars content (glucose and fructose), and the amino acid betaine, except the combined processing of ultrasound followed by low-pressure plasma (US.LPP). HTST and UHT increased the fatty acids and phenolic compounds content in the açai juice. The bioaccessibility of phenolic compounds decreased due to the processing. After thermal sterilization (UHT), the anthocyanin bioaccessibility was 2-fold higher. The combined non-thermal treatment reduced the biocompounds bioaccessibility to 40% of the non-processed juice. However, the combined US.LPP improved the bioaccessibility of vitamin C by 8%. UHT increased the anthocyanin's bioaccessibility but sharply decreased vitamin C bioaccessibility. Higher impact of thermal processing on vitamin C, anthocyanins, total phenolics, PPO, POD, DPPH, ABTS, and FRAP was verified after 45 and 60 days of storage compared to the non-thermally processed samples.

Chemical composition of thermally processed coconut water evaluated by GC-MS, UPLC-HRMS, and NMR.

Thermally-processed coconut water often develop a commercially-undesirable pink color, thus, NMR, UPLC-HRMS, GC-MS analyses combined with chemometrics approach were applied to evaluate chemical variations in comparison to tender water (control) that could explain such color change. Chemometrics on negative ionization mode dataset showed trimeric and A-type dimeric procyanidins, and caffeoylshikimic acid as main identified secondary metabolites induced by processing, while, control water presented mainly cytokinin trans-zeatin riboside, procyanidin dimer, caffeoylshikimic acid and trihydroxy-octadecenoic acid. Processing increased long-chain saturated palmitic and stearic fatty acids contents, meanwhile NMR analysis showed a decline in primary metabolites content as sugars fructose and glucose, and short-chain organic acids. Among the results observed for thermally processed coconut water, the increase in oligomeric procyanidins as A-type dimer and trimer may be associated with pink color development as these are precursors of anthocyanin pigment and/or by enhancing color stability of anthocyanin solutions.

Ozone and plasma processing effect on green coconut water.

In this study, the effect of plasma and ozone processing on the quality of coconut water was evaluated. For ozone processing, the samples were submitted to different ozone loads and temperatures. For atmospheric cold plasma processing (ACP), samples were exposed to plasma under different frequencies and voltages. The coconut water pH, soluble solids, titratable acidity, color, total phenolic content, and enzymatic activity were determined before and after treatments. The main compounds were also determined by NMR spectroscopy and chemometric analysis. Both processes did not change the pH values, total soluble solids, titratable acidity, and color. Chemometrics analysis of 1H NMR dataset showed no relevant changes after the processing. All ozone treatments promoted complete inactivation of POD activity and did not affect the content of phenolic compounds. After ACP, the smallest POD residual activity was observed when higher frequencies were applied, and slight changes in phenolic compounds content were observed.

An integrated analytical approach based on NMR, LC-MS and GC-MS to evaluate thermal and non-thermal processing of cashew apple juice.

Innovative chemometric approaches by NMR and LC-MS data fusion (multiblock analysis) and decomposition of the GC-MS raw data by PARADISe were applied to evaluate the influence of thermal and non-thermal processing on the composition of cashew apple juices. Comparative investigations by Principal Component Analysis (PCA) highlighted pronounced effect of thermal processing on juice compared to non-thermal processing, as decreases of anacardic acids, sucrose, malic acid, tyrosine, phenylalanine, and important flavor compounds (esters, aldehydes, and ketones). Ultrasound presented relevant influence on increase of anacardic acids concentration. Non-thermal processing carried out at more intense conditions (10 min of ultrasound, 5 min of ozone, and pulsed light at 10 V) showed pronounced effect compared to other non-thermal processing. Although individual PCA enables to detect the influence of different processing technologies, data fusion and PARADISe presented advantages, since a more comprehensive understanding of the relationship among chemical changes from different analytical techniques were established.

NIR and 1H qNMR methods coupled to chemometrics discriminate the chemotypes of the gastroprotective herb Egletes viscosa.

Egletes viscosa is a Brazilian medicinal herb consumed as flower bud tea due to its gastroprotective properties. This plant possesses two essential oil-based chemical varieties: trans-pinocarveyl acetate-rich chemotype A and cis-isopinocarveyl acetate- rich chemotype B. Therefore, we developed two simple, fast and reliable methods for discrimination of E. viscosa chemotypes using NIR and 1H qNMR spectroscopies combined with the chemometrics tools (iPLS and PLS-DA). Both methods showed high sensitivity, precision and specificity in the cross-validation tests. The NIR method has the advantages of being non-destructive and analyzable by portable devices, enabling its application for field and industrial evaluations. Meanwhile, the 1H qNMR method allows the quantification of the bioactive components ternatin, tanabalin, and centipedic acid. These aforementioned compounds were found higher in the chemotype A. Accordingly, our methods showed to be complimentary approaches for authenticity and/or quality control of E. viscosa-derived raw materials and herbal products.

Improvement of the bioaccessibility of bioactive compounds from Amazon fruits treated using high energy ultrasound.

The aim of this paper was to evaluate the effect of high energy ultrasound on the bioaccessibility of bioactive compounds from açaí (Euterpe precatoria) and buriti (Mauritia flexuosa) juices. Five levels of energy density (0, 0.9, 1.8, 2.7 and 3.6 J.cm-3), as well as their effects on the bioactive compounds were evaluated. Ultrasound did not significantly influence pH, titratable acidity and soluble solids. However, it affected the color attributes of juices by increasing brightness and color variation. The concentration of bioactive compounds (anthocyanins and carotenoids) and antioxidants increased with increasing ultrasound energy density, which was confirmed by Principal Component Analysis (PCA). Fatty acids increased up to 2.7 J.cm-3 and were reduced when higher energy was employed on the ultrasound process. Ultrasound allowed the release of new aromatic substances. For this reason, the ultrasound technology can be considered an alternative pre-treatment for fruit juices, improving the bioaccessibility and concentration of bioactive compounds.

Cold plasma processing effect on cashew nuts composition and allergenicity.

The study investigated the influence of atmospheric plasma processing on cashew nut composition as well as on its allergenicity. The cashew nuts were processed by low-pressure plasma, using glow discharge plasma (80 W and 50 kHz power supply). Anacardic acids and allergens were quantified by HPLC and immunoassay, respectively. Additionally, the overall composition was evaluated by 1H qNMR. Increases in amounts of anacardic acids (15:1, 15:2, and 15:3) and fatty acids (oleic, linoleic, palmitic and stearic) were detected after all process conditions, with 70.92% of total variance captured using 2 LVs. The total amount of anacardic acids increased from 0.7 to 1.2 µg·mg-1 of nut. The major change was observed for anacardic acid (C15:3) with an increase from 0.2 to 0.55 µg/mg of nut for the samples treated with a flow of 10 mL·min-1 and 30 min of processing. On the other hand, the amount of sucrose decreased, from 33 to 18 mg·g-1 of nut, after all processing conditions. Plasma processing of cashew nuts did not affect binding of either the rabbit anti-cashew or human cashew allergic IgE binding. Among the treatments, 10 min of plasma processing at flow rate of 30 mL·min-1 of synthetic air followed by 20 min at flow rate 5.8 mL·min-1 had the least effect on nut composition as a whole.

1H NMR and LC-MS-based metabolomic approach for evaluation of the seasonality and viticultural practices in wines from São Francisco River Valley, a Brazilian semi-arid region.

São Francisco River Valley (SFRV) is a wine-producing semi-arid region in Brazil. Therefore, we used a 1H NMR and UPLC-MS-based metabolomic approach coupled to chemometrics to evaluate the variability in Chenin Blanc and Syrah wines for two harvest seasons, two vine training system and six rootstocks. Overall, the secondary metabolites were influenced by the three factors studied, whereas the primary metabolites were only by the seasonality. Chenin Blanc wines made in December presented higher content of an unidentified carbohydrate. In Syrah wines, glycerol, tartaric acid, succinic acid and 2,3-butanediol were greater in December, while proline and lactic acid were more abundant in July. For training system, caffeic acid derivatives were increased in wines produced from espalier. Lyre system increased phenolic compounds, organic acids and apocarotenoids. The effect of the rootstocks was less pronounced, affecting basically caffeic acid derivatives. Thus, we expect that our results may assist the winemakers to improve the SFRV wine quality.

Qualitative and quantitative control of pediatric syrups using Nuclear Magnetic Resonance and chemometrics.

Several flavoring and sweetening agents added to excipient of pediatric syrups are not declared in the package leaflet. Therefore, the aim of this study was to develop a non-target, simple, and precise method for qualitative and quantitative evaluation of pediatric syrups using NMR spectroscopy combined with chemometrics. This approach allowed the identification of several added compounds as citric acid, cyclamate, ethanol, glycerol, propylene glycol, saccharin, sorbitol, fructose, glucose, and sucrose. Among the sugared syrups, sucrose was the main carbohydrate with approximately 59.1%, and for sweetened syrups, glycerol with 25.5%. The ethanol was found with highest concentration of 4.0%, approximately. In addition, some syrups presented both sugar and sweetener, which is inconsistent according to the purpose of the addition. Consequently, institutional structures of countries as Brazil that are in charge of public health should put additional compliance pressure on pharmaceutical companies to clearly declare in package leaflet the presence and exact amount of the main compounds (at least) existent in the pediatric excipients.