This study describes the validation of a headspace gas chromatography with flame ionization (HS-GC-FID) method for the determination of propanal, pentanal, hexanal, octanal, and trans-2-nonenal originated by lipid oxidation from cat food samples, as well as the evaluation of the matrix effect in the results. This method was applied to the analysis of commercial cat food and proved to be suitable for the determination of these volatile compounds in different samples. Mean recoveries between 88 and 109% were obtained and repeatability expressed as relative standard deviation was always lower than 6.95%. The intra- and inter-assay precisions ranged from 0.44 to 20.88% and from 0.45 to 20.52%, respectively. In addition, the matrix effect of cat food samples was determined by comparing the slopes of the standard addition method, and the external calibration curve and its influences were verified. These results highlight the high potential of this method, which allows the determination of lipid oxidation products in cat food samples directly, without requiring prior sample preparation techniques.

The objective of this study was to evaluate the effect of pasteurization, lyophilization and spray-drying on the lipid profile of donated human milk (DHM) at different lactation stages. Nine frozen samples of colostrum, transitional and raw mature human milk (HM) were collected from the Human Milk Bank (HMB) of the Hospital Universitário de Maringá (HUM). Samples were thawed and pooled according to lactation stage. Thereafter, it was submitted to pasteurization, lyophilization and spray-drying processes and later the fatty acid (FA) composition and the lipid profile analyses were performed. Gas chromatograph (GC) with flame ionization detector (FID) and electrospray ionization (ESI) mass spectrometer (MS) were used, respectively. In the FA composition analysis, it was observed that the same classes of saturated FA (SFA), monounsaturated FA (MUFA) and polyunsaturated FA (PUFA) were preserved throughout the process and in all lactation stages. The lipid profiles were also preserved after processing. Therefore, the lyophilization and spray-drying processes are promising techniques to preserve the DHM in the HMB, once the components evaluated were preserved, and both techniques facilitate the transport and storage, as the techniques reduce the sample volume.

A fast, sensitive, and selective direct injection electrospray tandem mass spectrometry (DI ESI MS/MS) method that is able to quantify ethyl carbamate in commercial sweetened sugar cane spirit is described. The preparation method uses a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) with potassium carbonate added to sweetened sugar cane spirit to separate the aqueous phase from the ethanol phase. The aqueous phase contains sucrose that suppresses electrospray ionization. Ethyl carbamate supernatant from the ethanol phase is transferred and enriched with 18-crown-6/trifluoroacetic acid additives. The additives sequester metal cations reducing the ionization of sodium and potassium, favoring the detection of ethyl carbamate as sole protonated cations. The method was successfully applied for the quantification of eleven real samples and certified sugar cane spirit demonstrating its applicability for quality control and regulatory analysis. The method showed reliable analytical parameters compared to conventional gas chromatography mass spectrometry (GC-MS) method commonly used for ethyl carbamate analysis. DI-ESI-MS/MS method requires just a fast step sample clean up and presents consistent values for the limit of detection (LOD 48.0 μg L-1) and limit of quantification (LOQ 160.0 μg L-1). Furthermore, the recoveries obtained were close to 100%, with relative standard deviations below 10% of sample certificates.

Dipteryx alata Vogel is a native fruit from Brazil, which has been poorly investigated concerning its phenolic composition and the biological effects of its pulp + peel. Thus, in this study we evaluated the antioxidant activity and total phenolic content of the D. alata pulp + peel extracts obtained with different solvents, as well as determined the phenolic compounds by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis. In addition, cytotoxic effects of D. alata pulp + peel extract on non-tumor and cancer cell lines were investigated for the first time. The results showed that phenolic compounds can be efficiently extracted from pulp + peel of D. alata by organic solvent-water mixtures as an extraction system. The developed UHPLC-MS/MS method allowed the quantification of eighteen phenolic compounds in D. alata pulp + peel extract for the first time, which luteolin and trans-cinnamic acid were predominant. In addition, D. alata pulp + peel extract exhibited better cytotoxity against SiHa and C33A cervical cancer cell lines, while weak cytotoxicity was noticed against non-tumor HaCaT and L929 cell lines, pointing out its safety and providing preliminary evidence of its anticancer potential. Our findings indicate that D. alata pulp + peel can be explored as a natural source of phenolic compounds with promising antioxidant and cytotoxic properties.

Sunflower oil has several properties that are valuable to the human skin and health; however, they are target of adulterations. In this study, in order to evaluate the authenticity of edible and cosmetics based on sunflower oils, the triacylglycerol (TAG) profiles using direct infusion electrospray ionization mass spectrometry (ESI-MS), the fatty acid (FA) composition by gas chromatography with flame ionization detection (GC-FID) and principal component analysis, of seven commercial samples were determined and the results obtained were compared with the pure sunflower and soybean oils. Of the seven brands analyzed, just one sample presented only sunflower oil in its composition; two stated in the label soybean addition; and four did not present the real composition of the product in the label. Therefore, GC-FID and ESI-MS analysis in conjunction with principal component analysis (PCA) demonstrated that they are complementary techniques and could be applied in food industries to assess the quality of vegetable oils, since results showed the need for stricter quality control for this product.

Acerola is a tropical fruit with a large industrial and commercial appeal due to its organoleptic qualities and bioactive compound-rich nature. Thus, as bioactive compounds (BC) stability is of great interest in the food industry, assessment of preserving techniques to prolong shelf life has become imperative. Hence, the purpose of this study was to evaluate how storage affects BC conservation in microencapsulated and lyophilized acerola pulps over 180 days. For this matter, antioxidant tests, physical-chemical analyzes, and vitamin C analysis by mass spectrometry were performed. Results indicated that microencapsulation better preserved the antioxidants in acerola pulp compared to the other preservation technologies employed. This is due to the greater BC concentration in the microencapsulated, as well as the pH reduction. Furthermore, over 180 days, microencapsulation better preserved the target compounds in acerola pulp compared to lyophilization, as evidenced by the superior content of BC in the former treatment, making it an appealing option for the food sector.

The present work intends to obtain and characterize a milk by-product: the human whey (HW), in order to avoid the excessive disposal of human milk (HM). The characterization was performed through analyzes of the chemical composition and fatty acids (FAs) and the triacylglycerol (TAG) lipid profile. The results indicated that the chemical composition altered significantly after the HW obtained, except for the percentage of ash and carbohydrates. About the FA composition, it was observed that strictly essential FA, essential FA and other FAs found in HM remained present in HW. For the nutritional lipids quality, the atherogenicity and the thrombogenicity indices presented desirable values, and the TAGs lipid profile revealed a variation in the analyzed samples. Therefore, it can be concluded that the characterized HW has potential for application in isolated form or to be used as an ingredient in other foods.

Considering the increasing number of low cost vegetable oil product adulterations, it is necessary to assess the authenticity of the lipid sources used in the dog food manufacture, consequently different brands and classifications of feed were analyzed to verify the product authenticity by gas chromatography (GC) with flame ionization detector (FID) and by electrospray ionization mass spectrometry (ESI-MS). Fatty acid (FA) composition analysis was performed to compare the FAs amount in samples with the respective guarantee levels stated by the manufacturers on its product label. Gas chromatography with flame ionization detector (GC-FID) results for omega-3 and 6 percentages are within the limits presented by each manufacturer, while the timnodonic + cervonic acids amount information presented on feed sample labels is not in accordance with GC-FID results. Consequently, the samples were analyzed by ESI-MS, the results exposed the chicken oil presence in the feed and eicosapentaenoic (EPA) + docosahexaenoic (DHA) acids absence, since no lipid profiles similar to fish oils or triacylglycerols (TAGs) containing these two FAs were found. Thus, the information presented on labels are in disagreement with the results obtained both by GC-FID FA composition analysis and by ESI-MS lipid profile analysis. Principal component analysis (PCA) confirmed that the main contribution was from FAs found by GC-FID.

Rosemary (Rosmarinus officinalis L.) is known for its bioactive compounds with high antioxidant potential and pharmacological properties, such as antibacterial, antidepressant and anti-inflammatory. These properties are attributed to the presence of (poly)phenolic compounds. In the literature there is no extraction of these compounds with a totally non-toxic solvent, capable of applying the extract directly to the food. This work aimed to optimize the extraction conditions of bioactive compounds from the rosemary leaves using water as solvent. According to the analysis of variance parameters, a cubic model of high order of significance was obtained with adjusted R2 (R squared) > 0.947. The optimal conditions of the antioxidant potential for conventional and ultrasonic agitation were: temperature 70 °C, 30 min of extraction and the solvent/solute ratio of 25, resulting in an antioxidant potential of 6861 and 7126 µmol L−1 Trolox, respectively. The electrospray ionization mass spectrometry (ESI(−)-MS/MS) analysis showed the presence of antioxidant compounds such as: carnosol (m/z 329.20), rosmanol (m/z 345.03) and rosmarinic (m/z359.14) acids. The response surface methodology evaluated the influence of the main parameters of the bioactive compounds extraction from rosemary using only water as solvent, in addition to the use of less time and sample mass, resulting in lower cost.

This paper describes the monitoring of ethyl carbamate concentration in sugar cane spirit from industrial distilleries in Brazil. In total, 18 distilleries from Minas Gerais and São Paulo states were evaluated, with, a total of 336 samples from August 2017 to August 2019. The ethyl carbamate was analyzed using a previously validated mass spectrometric method. Analytical curves presented coefficient of determination (R2) values higher than 0.99, and quality control samples showed a relative standard deviation (RSD) below 9%. Concentrations of ethyl carbamate ranged from not detected to 1608 µg L-1, with mean values of 294.2, 280.7 and 230.0 µg L-1 in 2017, 2018, and 2019, respectively. On average, 46, 44 and 69% of samples presented levels of ethyl carbamate below 210 µg L-1. A variety of factors may have led to distillery A having a low level (ca. 115 µg L-1) of ethyl carbamate, including controlled temperature, yeast strain, post-harvesting quality, sugar cane variety choice, and the treatment process on the sugar cane juice, which goes towards the addition of Ca(OH)2, heating and freezing. These results showed the importance of internal quality control, and that sugar cane juice treatment may be a way to decrease ethyl carbamate in the distilleries.

In order to provide an effective and environmentally correct alternative for oil extraction, subcritical n-propane was used under different temperature and pressure conditions to obtain Brazil nut oil. The composition of the oil was determined and compared to the oils obtained by conventional methods. The result of the extraction yield obtained using subcritical fluid extraction (SFE) at 60 ºC, 6 MPa and granulometry < 1.40 mm (63.13%) presented minor differences to the yield obtained by Soxhlet extraction (SE) (68.44%) and Bligh and Dyer extraction (BD) (59.54%). The composition in fatty acids was similar regardless of the method of extraction used. Oxidized triacylglycerols (TAGs) were found in the oils extracted by SE and BD while they were not detected in the oils extracted by SFE. The quantity of bioactive compounds was higher in the oils obtained by SFE. Thus, the SFE using n-propane preserves the nutritional characteristics and lipophilic components of the oil, besides improving the availability of bioactive compounds from an effective “green extraction” without the use of toxic solvents.

This work reports the theoretical and experimental study of fragmentation reactions in the gas phase of five phenolic acids using triple quadrupole mass spectrometry by electrospray ionization in negative ionic mode, as well as the isotope exchange experiments. MS/MS spectra were analyzed to suggest the fragmentation mechanisms, while theoretical calculations at the theory level B3LYP/6-311+G** were performed to expose the proposed mechanisms viability for this class of compounds. As expected, compounds with aromatic methoxy substitution presented •CH3 radical elimination as the principal fragmentation pathway, forming dystonic ions. Compounds without methoxy substituents dissociate with higher energies losing the CO2, CO and H2O. The isotopic marking experiments indicated the exchange of hydrogens by deuterases in the hydroxyl protons, which corroborates with the proposed mechanisms.

Human milk (HM) lipids provide about 50% energy and facilitate the transport and absorption of fat-soluble vitamins for infants, but their composition should be studied when the milk is processed. This study evaluated the lipid quality of lyophilized and vacuum-packed colostrum (C), transitional (T), and mature (M) HM for a period of 1, 30, 60, 90, 120, 150, and 180 days of storage at –18 ºC. From the acidity (ºDornic), lipid content, and fatty acid (FA) composition results, no significant differences in the analyzed period were observed. The relative percentage of major triacylglycerols (TAG) of the HM was not altered, showing that the lyophilization process in HM is a good alternative that could be applied in human milk banks (HMB), increasing HM preservation and facilitating its transport and storage.

Coconut oil has several domestic uses and health benefits, which can be used in food, pharmaceuticals and cosmetics products. However, it has been the target of adulteration with lower price oils and fats, such as soybean oil. In this study, a fast, easy and simple methodology was used to detect low quantities of intentionally adulterated coconut oil with soybean oil by direct infusion electrospray ionization mass spectrometry (ESI-MS) at different levels (0, 2, 5, 10, 15, 20, 30, 50, 70 and 100%). In the oil industry, intentional adulterations usually occur with the addition of low quantities of soybean oil to coconut oil. Therefore, the suggested ESI-MS method is promising for routine analysis to guarantee the quality control of coconut oil since it is possible to detect adulteration with a minimal of 2% soybean oil addition.

The developed method (DM) allows to perform experiments in shorter time with reduced amount of sample and reagent for fatty acids (FA) determination in fermented milk samples. Design Expert software was employed to discover the greatest sonication time (7 and 20 min) and concentration for alkaline and acidic reactions (0.70 and 1.5 mol L-1). Validation procedures were applied in yogurt samples with diverse fat content, ranging from 1.22 to 2.83%, being in agreement with acceptable values. Besides, the intraday relative standard deviation (RSD) (1.86%) and interday RSD (4.23%) values confirmed the good accuracy of the proposed method for FA derivatization.