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Tree nuts and oily fruits are used as a diet complement and are highly consumed worldwide. The production and consumption of these foods have been increasing, and an enormous global market value is forecasted for 2023. Besides their high nutritional value and lipid content, they provide health benefits to fat metabolism, heart, skin, and brain. The industrial by-products of these oily foods represent promising raw materials for many industries. However, the lipidomic analysis of nuts and oily fruits is still in its early stages. State-of-the-art analytical approaches for the lipid profiling and fingerprinting of nuts and oily fruits have been developed using high-performance liquid chromatography and high-resolution mass spectrometry for the accurate identification and structural characterization at the molecular species level. It is expected to bring a new understanding of these everyday foods' nutritional and functional value. This review comprises the oil content and lipid composition of various nuts and oily fruits, particularly those mostly consumed worldwide and having recognized beneficial health effects, biological activities associated with the lipids from different oily foodstuffs, analytical methodologies to analyze lipids in nuts and oily fruits, and the potential biotechnological applications of their industrial by-products for a lipid-based commercial valorization.

Modulation of lipid metabolism is a well-established cancer hallmark, and SCD1 has been recognized as a key enzyme in promoting cancer cell growth, including in glioblastoma (GBM), the deadliest brain tumor and a paradigm of cancer resistance. The central goal of this work was to identify, by MS, the phospholipidome alterations resulting from the silencing of SCD1 in human GBM cells, in order to implement an innovative therapy to fight GBM cell resistance. With this purpose, RNAi technology was employed, and low serum-containing medium was used to mimic nutrient deficiency conditions, at which SCD1 is overexpressed. Besides the expected increase in the saturated to unsaturated fatty acid ratio in SCD1 silenced-GBM cells, a striking increase in polyunsaturated chains, particularly in phosphatidylethanolamine and cardiolipin species, was noticed and tentatively correlated with an increase in autophagy (evidenced by the increase in LC3BII/I ratio). The contribution of autophagy to mitigate the impact of SCD1 silencing on GBM cell viability and growth, whose modest inhibition could be correlated with the maintenance of energetically associated mitochondria, was evidenced by using autophagy inhibitors. In conclusion, SCD1 silencing could constitute an important tool to halt GBM resistance to the available treatments, especially when coupled with a mitochondria disrupter chemotherapeutic.

Polychaetes can be successfully employed to recover otherwise wasted nutrients present in particulate organic matter (POM) of aquaculture effluents. The present study describes the fatty acid (FA) profile of four different polychaete species cultured in sand filters supplied with effluent water from a marine fish farm. The FA profile of cultured and wild Hediste diversicolor was compared and revealed a ≈ 24.2% dissimilarity, with cultured biomass displaying a higher content in two essential n-3 highly unsaturated FA (HUFA) (EPA [20:5 n-3] and DHA [22:6 n-3]-eicosapentaenoic and docosahexaenoic acid, respectively). The comparison of the FA profile of cultured H. diversicolor with that of other polychaete species whose larvae successfully settled on the sand filters (Diopatra neapolitana, Sabella cf. pavonina and Terebella lapidaria) revealed that their FA profile, which is here described for the first time, displayed high levels of EPA and DHA (≈ 1.5-4.8 and 1.0-1.1 µg mg -1 DW, respectively). The highest concentration of total FA per biomass of polychaete was recorded in H. diversicolor and T. lapidaria, with both species being the ones whose FA profiles revealed a lowest level of dissimilarity and more closely resembled that of the aquafeed used in the fish farm. In the present work it was demonstrated that it is possible to produce polychaetes biomass with high nutritional value through an eco-design concept such as integrated multi-trophic aquaculture (IMTA). Indeed, this framework promotes a cleaner production and, in this specific case, allowed to recover essential fatty acids that are commonly wasted in aquaculture effluents.

The structural diversity of the lipopolysaccharides (LPSs) from Helicobacter pylori poses a challenge to establish accurate and strain-specific structure-function relationships in interactions with the host. Here, LPS structural domains from five clinical isolates were obtained and compared with the reference strain 26695. This was achieved combining information from structural analysis (GC-MS and ESI-MS n ) with binding data after interrogation of a LPS-derived carbohydrate microarray with sequence-specific proteins. All LPSs expressed Lewis x/y and N-acetyllactosamine determinants. Ribans were also detected in LPSs from all clinical isolates, allowing their distinction from the 26695 LPS. There was evidence for 1,3-d-galactans and blood group H-type 2 sequences in two of the clinical isolates, the latter not yet described for H. pylori LPS. Furthermore, carbohydrate microarray analyses showed a strain-associated LPS recognition by the immune lectins DC-SIGN and galectin-3 and revealed distinctive LPS binding patterns by IgG antibodies in the serum from H. pylori-infected patients., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Marine aquaponics is a promising sustainable approach for the production of profitable crops such as halophytes. However, the effect of this culture approach on the lipid composition of halophytes remains unknown. In this work, we contrasted the polar lipidome of Salicornia ramosissima and Halimione portulacoides when produced in marine aquaponics (effluent from a super-intensive flatfish aquaculture production), with that of conspecifics from donor wild populations. Phospholipids and glycolipids were identified and quantified by LC-MS and MS/MS and their profile statistically analysed. Halophytes produced in aquaponics have higher levels of glycolipids with n-3 fatty acids (DGDG 36:3; SQDG 36:3; MGDG 36:6) compared with the donor wild populations. In the case of H. portulacoides, a significant increase of phospholipids bearing n-3 fatty acids (most in PC and PE) was also recorded. These lipids have potential applications in food, feed and pharmaceutical industries, contributing to the valorization of halophytes produced under sustainable aquaculture practices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Several species of sacoglossan sea slugs are able to sequester chloroplasts from algae and incorporate them into their cells. However, the ability to maintain functional "stolen" plastids (kleptoplasts) can vary significantly within the Sacoglossa, giving species different capacities to withstand periods of food shortage. The present study provides an insight on the comparative shifts experienced by the lipidome of two sacoglossan sea slug species, Elysia viridis (long-term retention of functional chloroplasts) and Placida dendritica (retention of non-functional chloroplasts). A hydrophilic interaction liquid chromatography-mass spectrometry approach was employed to screen the lipidome of specimens from both species feeding on the macroalga Codium tomentosum and after 1-week of starvation. The lipidome of E. viridis was generally unaffected by the absence of food, while that of P. dendritica varied significantly. The retention of functional chloroplasts by E. viridis cells allows this species to endure periods of food shortage, while in P. dendritica a significant reduction in the amount of main lipids was the consequence of the consumption of its own mass to endure starvation. The large proportion of ether phospholipids (plasmalogens) in both sea slug species suggests that these compounds may play a key role in chloroplast incorporation in sea slug cells and/or be involved in the reduction of the oxidative stress resulting from the presence of kleptoplasts., (© The Author(s) 2020. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology. All rights reserved. For permissions please email: journals.permissions@oup.com.)

The evaluation of encapsulation efficiency is a regulatory requirement for the characterization of drug delivery systems. However, the difficulties in efficiently separating nanomedicines from the free drug may compromise the achievement of accurate determinations. Herein, ultrafiltration was exploited as a separative strategy towards the evaluation of methotrexate (MTX) encapsulation efficiency in nanostructured lipid carriers and polymeric nanoparticles. The effect of experimental conditions such as pH and the amount of surfactant present in the ultrafiltration media was addressed aiming at the selection of suitable conditions for the effective purification of nanocarriers. MTX-loaded nanoparticles were then submitted to ultrafiltration and the portions remaining in the upper compartment of the filtering device and in the ultrafiltrate were collected and analyzed by HPLC-UV using a reversed-phase (C18) monolithic column. A short centrifugation time (5 min) was suitable for establishing the amount of encapsulated MTX in nanostructured lipid carriers, based on the assumption that the free MTX concentration was the same in the upper compartment and in the ultrafiltrate. The defined conditions allowed the efficient separation of nanocarriers from the free drug, with recoveries of >85% even when nanoparticles were present in cell culture media and in pig skin surrogate from permeation assays.

Cancer associated body wasting is the cause of physical disability, reduced tolerance to anticancer therapy and reduced survival of cancer patients and, similarly to cancer, its incidence is increasing. There is no cure for this clinical condition, and the pathophysiological process involved is largely unknown. Exercise training appears as the gold standard non-pharmacological therapy for the management of this wasting syndrome. Herein we used a lipidomics approach based on liquid chromatography coupled with high-resolution mass spectrometry (LC-HR-MS) to study the effect of exercise in the modulation of phospholipids profile of mitochondria isolated from gastrocnemius muscle of a pre-clinical model of urothelial carcinoma-related body wasting (BBN induced), submitted to 13 weeks of treadmill exercise after diagnosis. Multivariate analysis showed a close relationship between the BBN exercise group and both control groups (control sedentary and control exercise), while the BBN sedentary group was significantly separated from the control groups and the BBN exercise group. Univariate statistical analysis revealed differences mainly in phosphatidylserine (PS) and cardiolipin (CL), although some differences were also observed in phosphatidylinositol (PI, LPI) and phosphatidylcholine (PC) phospholipids. PS with shorter fatty acyl chains were up-regulated in the BBN sedentary group, while the other species of PS with longer FA and a higher degree of unsaturation were down-regulated, but the BBN exercise group was mostly similar to control groups. Remarkably, exercise training prevented these alterations and had a positive impact on the ability of mitochondria to produce ATP, restoring the healthy phospholipid profile. The remodelling of mitochondria phospholipid profile in rats with urothelial carcinoma allowed confirming the importance of the lipid metabolism in mitochondria dysfunction in cancer-induced skeletal muscle remodelling. The regulation of phospholipid biosynthetic pathways observed in the BBN exercise group supported the current perspective that exercise is an adequate therapeutic approach for the management of cancer-related muscle remodeling.

Recent evidence suggests that phosphatidylserine (PS) and its oxidized species drive the clearance of apoptotic cells by macrophages with putative immune response modulation. However, it is not clear whether PS and oxidized PS differentially modulate at molecular level the functional responses of macrophages. Therefore, we proposed in this work to explore this question by evaluating the influence of PS oxidation products on the macrophages inflammatory status. Thus, we determined the effects of oxidized 1-palmitoyl-2-linoleoyl-phosphatidylserine (oxPLPS) and PLPS on RAW 264.7 macrophages production of the pro-inflammatory mediator nitric oxide (NO) and on the levels of the inducible NO synthase (Nos2) and Il1β mRNA. The ability of PLPS and oxPLPS to modulate the lipopolysaccharide (LPS)-triggered macrophage activation was also analyzed. Finally, the effects of PLPS species over canonical inflammation-associated signaling pathways, such as nuclear factor (NF)-κB and mitogen-activated protein kinases (MAPKs) were also disclosed. The results obtained showed that both PLPS and oxPLPS species are deprived of intrinsic pro-inflammatory activity. Exquisitely, only oxPS were found to significantly inhibit NO production and iNos and IL1β genes transcription induced by LPS. At a molecular level, these effects were partially due to attenuation of LPS-induced c-Jun-N-terminal kinase (JNK) phosphorylation and p65 NF-κB nuclear translocation. Overall our data suggest that oxPLPS, but not native PLPS, mitigates pro-inflammatory signaling in macrophages, contributing to containment of inflammation during apoptotic cell engulfment., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The phenolic composition of hydroethanolic extracts of Mentha aquatica L., Lavandula dentata L. and Leonurus cardiaca L., obtained from plants grown under organic cultivation, was determined and their hepatoprotective effects were investigated in vitro. L. cardiaca extract was rich in phenylethenoid glycosides, especially lavandolifolioside (254 ± 36 μg/mg), whereas rosmarinic acid and eriodictyol- O -rutinoside were the major phenolic compounds of L. dentata and M. aquatica extracts, accounting for 68 ± 7 μg/mg and 145 ± 22 μg/mg, respectively. These differential phenolic components presumably account for their dissimilar antioxidant properties. While L. cardiaca extract showed moderate biological effects, M. aquatica extract displayed high antioxidant activity in chemical models, and that of L. dentata was effective in counteracting potassium dichromate-induced ROS generation in human hepatocarcinoma cells. Moreover, M. aquatica extract (50 μg/mL) and its mixture (50%/50%) with L. dentata extract displayed an effective cytoprotective effect.

Obesity is a public health problem and a risk factor for pathologies such type 2 diabetes mellitus, cardiovascular diseases, and nonalcoholic fatty liver disease. Given these clinical implications, there is a growing interest to understand the pathophysiological mechanism of obesity. Changes in lipid metabolism have been associated with obesity and obesity-related complications. However, changes in the lipid profile of obese children have been overlooked. In the present work, we analyzed the serum phospholipidome of overweight and obese children by HILIC-MS/MS and GC-MS. Using this approach, we have identified 165 lipid species belonging to the classes PC, PE, PS, PG, PI, LPC, and SM. The phospholipidome of overweight (OW) and obese (OB) children was significantly different from normal-weight children (control). Main differences were observed in the PI class that was less abundant in OW and OB children and some PS, PE, SM, and PC lipid species are upregulated in obese and overweight children. Although further studies are needed to clarify some association between phospholipid alterations and metabolic changes, our results highlight the alteration that occurs in the serum phospholipid profile in obesity in children.

Olives ( Olea europaea L.) are classic ingredients in the Mediterranean diet with well-known health benefits, but their lipid composition has not been fully addressed. In this work, we characterised triacylglycerol (TAG) and polar lipid profiles of the olive pulp while using a complementary methodological approach that was based on solid-phase extraction to recover the neutral lipid (NL) and the polar lipid-rich fractions. The TAG profile was analysed in the NL-fraction by C 30 reversed-phase liquid chromatography (LC) and the polar lipid profile by normal-phase hydrophilic interaction liquid chromatography (HILIC), with both being coupled to electrospray ionization-mass spectrometry (ESI-MS) and ESI-MS/MS. This approach identified 71 TAG ions that were attributed to more than 350 molecular species, with fatty acyl chain lengths from C11:0 to C26:0, including different polyunsaturated acyl chains. The polar lipids included 107 molecular species that belonged to 11 lipid classes that comprised phospholipids, glyceroglycolipids, glycosphingolipids, and betaine lipids. In addition to polyunsaturated fatty acids, some of the phospholipids, glycolipids, and glycosphingolipids that were identified in the olive pulp have been described as biologically active molecules. Lipidomic phenotyping of the olive pulp has led to the discovery of compounds that will allow for a better assessment of its nutritional value and new applications of bioactive lipid components in this functional food.

Bacillus licheniformis I89 is a Gram-positive bacterium, a producer of the lantibiotic lichenicidin. No information is available on its fatty acid (FA) composition. Bacillus species are rich in branched FA (BrFA), claimed to be beneficial to human health and to treat diseases. Herein, the FA profile of B. licheniformis I89 was evaluated under different growth conditions: at two growth temperatures (37 and 50 °C) and at different growth phases (lag, exponential, and stationary), using gas chromatography-mass spectrometry. The FA profile revealed predominant BrFA of the iso-series and anteiso-series (i-15:0, ai-15:0, i-16:0, i-17:0, and ai-17:0) and low amounts of saturated FA (14:0, 16:0, and 18:0). Comparing the FA profiles at different temperatures, in the lag phase, at 50 °C, there was a decrease of ai-17:0 and a decrease of i-15:0 in the exponential phase, in comparison with 37 °C. In all growth phases, there was a decrease of ai-15:0 and an increase of i-17:0. From the lag to the stationary phase, at 50 °C, there was a decrease of ai-17:0 and i-16:0, whereas i-15:0 increased, while at 37 °C, there was an increase of i-15:0 and i-16:0, and a decrease in ai-15:0 and ai-17:0. B. licheniformis I89 can adapt its FA profile, at moderate temperatures, by changing the iso-FA and anteiso-FA composition and the iso/anteiso ratio. This nonpathogenic bacterium species can be used as a source of BrFA with putative beneficial health effects for gut protection and with reported antitumor properties, foreseeing its use for producing compounds with biotechnological applications., (© 2019 AOCS.)

Bacillus licheniformis I89 is a non-pathogenic, Gram-positive bacterium, frequently found in soil. It has several biotechnological applications as producer of valuable compounds such as proteases, amylases, surfactants, and lantibiotics. Herein, it is reported the identification of the polar lipidome of B. licheniformis I89 during the different growth phases (lag, exponential and stationary) at 37 °C. The analytical approach relied on hydrophilic interaction liquid chromatography coupled to electrospray ionization mass spectrometry (HILIC-ESI-MS), accurate mass measurements and tandem mass spectrometry (MS/MS). In the lipidome of B. licheniformis I89 were identified four phospholipid classes: phosphatidylethanolamine, phosphatidylglycerol, lysyl-phosphatidylglycerol, and cardiolipin; two glycolipid classes: monoglycosyldiacylglycerol and diglycosyldiacylglycerol; and two phosphoglyceroglycolipid classes: mono-alanylated lipoteichoic acid primer and lipoteichoic acid primer. The same lipid species were identified at the different growth phases, but there were significant differences on the relative abundance of some molecular species. There was a significant increase in the 30:0 lipid species and a significant decrease in the 32:0 lipid species, between exponential and stationary phases, when compared to lag phase. No differences were observed between exponential and stationary phases. The lipidomic-based approach used herein is a very promising tool to be employed in the study of bacterial lipid composition, which is a requirement to understand its metabolism and response to growth conditions., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Endoplasmic reticulum-mitochondria contact sites have been a subject of increasing scientific interest since the discovery that these structures are disrupted in several pathologies. Due to the emerging data that correlate endoplasmic reticulum-mitochondria contact sites function with known events of the apoptotic program, we aimed to dissect this interplay using our well-established model of acetic acid-induced apoptosis in Saccharomyces cerevisiae. Until recently, the only known tethering complex between ER and mitochondria in this organism was the ER-mitochondria encounter structure (ERMES). Following our results from a screening designed to identify genes whose deletion rendered cells with an altered sensitivity to acetic acid, we hypothesized that the ERMES complex could be involved in cell death mediated by this stressor. Herein we demonstrate that single ablation of the ERMES components Mdm10p, Mdm12p and Mdm34p increases the resistance of S. cerevisiae to acetic acid-induced apoptosis, which is associated with a prominent delay in the appearance of several apoptotic markers. Moreover, abrogation of Mdm10p or Mdm34p abolished cytochrome c release from mitochondria. Since these two proteins are embedded in the mitochondrial outer membrane, we propose that the ERMES complex plays a part in cytochrome c release, a key event of the apoptotic cascade. In all, these findings will aid in targeted therapies for diseases where apoptosis is disrupted, as well as assist in the development of acetic acid-resistant strains for industrial processes., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

It is now well established that exogenous β-1,4-xylanases improve the nutritive value of wheat-based diets for poultry. Among other factors, the mechanism of action of exogenous enzymes may involve a microbial route resulting from the generation of prebiotic xylo-oligosaccharides (XOS) in the birds' gastro-intestinal (GI) tract. In a series of three experiments, the effect of XOS on the performance of broilers fed wheat or corn-based diets was investigated. In experiment 1, birds receiving diets supplemented with XOS displayed an increased weight gain (P = 0.08). The capacity of XOS to improve the performance of animals during a longer trial (42 d) was investigated (Experiment 2). The data revealed that diet supplementation with XOS, tested at two incorporation rates (0.1 and 1 g/kg), or with an exogenous β-1,4-xylanase resulted in an increased nutritive value of the wheat-based diet. An improvement in animal performance was accompanied by a shift in the microbial populations colonizing the upper portions of the GI tract. XOS were also able to improve the performance of broilers fed a corn-based diet, although the effects were not apparent at incorporation rates of 10 g/kg. Together these studies suggest that in some cases the capacity of β-1,4-xylanases to improve the nutritive value of wheat-based diets is more related to their ability to produce prebiotic XOS than to their ability to degrade arabinoxylans. The extremely low quantities of XOS used in this study also challenge the depiction of a prebiotic being a quantitatively fermented substrate. These data also bring into question the validity of the "cell wall" mechanism, as XOS elicited an effect with clearly no action on endosperm cell wall integrity and yet the performance effects noted were equivalent or superior to the added enzymes.

Production of bacterial lipid-based biofuels using inexpensive substrates, as wastes, is an emerging approach. In this work, a selective process using carbon feast-famine cycles was applied to obtain an indigenous microbial community of hydrocarbon-degrading and lipid-accumulating bacteria, using a real lubricant-based wastewater as carbon source. In the conditions applied, the enriched bacterial community, dominated by members of the genus Rhodococcus, Pseudomonas and Acinetobacter, was able to degrade almost all hydrocarbons present in the wastewater within 24 h' incubation and to accumulate, although in low levels, triacylglycerol (TAG) (<5% of cell dry weight (CDW)) and polyhydroxyalkanoates (PHA) (3.8% ± 1.1% of the CDW) as well as an unknown lipid (29% ± 6% of CDW), presumably a wax ester-like compound. The influence of culture conditions, namely carbon and nitrogen concentrations (and C/N ratio) and cultivation time, on the amount and profile of produced storage compounds was further assessed using a statistical approach based on a central composite circumscribed design and surface response methodology. The regression analysis of the experimental design revealed that only nitrogen concentration and C/N ratio are significant for neutral lipid biosynthesis (p < 0.05). Maximum neutral lipid content, i.e. 33% (CDW basis), was achieved for the lowest carbon and nitrogen concentrations evaluated (10 g COD L -1 and 0.02 g N L -1 ). PHA accounted for less than 5% of CDW. In these conditions, neutral lipid content was mainly composed by TAG, about 70% (w/w). TAG precursors, namely monoacylglycerols (MAG), diacylglycerols (DAG) and fatty acids (FA), accounted for 22% of total neutral lipids and WE for about 7%. Nevertheless, according to the applied response surface model, further improvement of neutral lipids content is still possible if even lower nitrogen concentrations are used. The fatty acids detected in TAG extracts ranged from myristic acid (C14:0) to linoleic acid (C18:2), being the most abundant palmitic acid (C16:0), stearic acid (C18:0) and oleic acid (C18:1). This study shows the feasibility of combining treatment of hydrocarbon contaminated wastewater, herein demonstrated for lubricant-based wastewater, with the production of bacterial neutral lipids using open mixed bacterial communities. This approach can decrease the costs associated to both processes and contribute to a more sustainable waste management and production of lipid-based biofuels., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Some halophytes are currently used as gourmet plant ingredients for human consumption. The polar lipidome of the succulent organs of Salicornia ramosissima (fresh branch tips) and Halimione portulacoides (leaves) were characterized in-depth, with more than two hundred lipid species being identified in both halophytes. The lipid species identified were distributed over five classes of phospholipids, three classes of glycolipids and one class of glycosphingolipids. Despite the existence of some species-specific differences between the polar lipidome, phospholipids and glycolipids show a high content of n-3 fatty acids in both S. ramosissima and H. portulacoides. These results highlights the advantage of employing mass spectrometry based lipidomic platform towards the valorization of halophytes as a source of valuable nutrients and bioactives, fostering potential applications in the fields of healthy and functional food products, and for nutraceutical and pharmaceutical uses., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The occurrence of protein synthesis errors (mistranslation) above the typical mean mistranslation level of 10-4 is mostly deleterious to yeast, zebrafish and mammal cells. Previous yeast studies have shown that mistranslation affects fitness and deregulates genes related to lipid metabolism, but there is no experimental proof that such errors alter yeast lipid profiles. We engineered yeast strains to misincorporate serine at alanine and glycine sites on a global scale and evaluated the putative effects on the lipidome. Lipids from whole cells were extracted and analysed by thin layer chromatography (TLC), liquid chromatography-mass spectrometry(LC-MS) and gas chromatography (GC). Oxidative damage, fatty acid desaturation and membrane fluidity changes were screened to identify putative alterations in lipid profiles in both logarithmic (fermentative) and post-diauxic shift (respiratory) phases. There were alterations in several lipid classes, namely lyso-phosphatidylcholine, phosphatidic acid, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, and triglyceride, and in the fatty acid profiles, namely C16:1, C16:0, C18:1 and C18:0. Overall, the relative content of lipid species with saturated FA increased in detriment of those with unsaturated fatty acids. The expression of the OLE1 mRNA was deregulated, but phospholipid fluidity changes were not observed. These data expand current knowledge of mistranslation biology and highlight its putative roles in human diseases., Competing Interests: The authors have declared that no competing interests exist.

Polar lipids are minor components of olives and olive oil and include a myriad of molecules such as phospholipids and glycolipids. Even though sensitive and high-resolution analytical approaches have been used to unveil the polar lipidome of these matrices, new insights on their composition are needed. In this review, we will describe the findings on the identification and characterization of polar lipids from olives and olive oil and the underlying analytical challenges. The significance of polar lipids will also be discussed as potential markers of identity and traceability of olives and olive oil and in detecting adulteration of olive oil. Their potential impact on nutrition and health will be presented as a valuable source of bioactive compounds and as promising ingredients for different uses from olive-derived industrial by-products.

Collision induced dissociation of triple quadrupole mass spectrometer (CID-QqQ) and high-energy collision dissociation (HCD) of Orbitrap were compared for four neuropeptides Y Y1 (NPY Y1) receptor antagonists and showed similar qualitative fragmentation and structural information. Orbitrap high resolution and high mass accuracy HCD fragmentation spectra allowed unambiguous identification of product ions in the range 0.04-4.25 ppm. Orbitrap mass spectrometry showed abundant analyte-specific product ions also observed on CID-QqQ. These results show the suitability of these product ions for use in quantitative analysis by MRM mode. In addition, it was found that all compounds could be determined at levels >1 μg L -1 using the QqQ instrument and that the detection limits for this analyzer ranged from 0.02 to 0.6 μg L -1 . Overall, the results obtained from experiments acquired in QqQ show a good agreement with those acquired from the Orbitrap instrument allowing the use of this relatively inexpensive technique (QqQ) for accurate quantification of these compounds in clinical and academic applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Nitro-fatty acids (NO 2 -FA) have been widely studied with regard to their identification, structural characterization, and biological actions. NO 2 -FA could also be present endogenously esterified to phospholipids (PL), and NO 2 -PL were already detected in cardiac mitochondria from diabetic rats and cardiomyoblasts subjected to starvation. However, the biological actions of NO 2 -PL have been overlooked. In this study, we evaluate the antioxidant and anti-inflammatory potential of the nitrated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) formed in vitro by incubation with NO 2 BF 4 , in a well-recognized mimetic model of nitroxidative stress. Nitrated POPC showed anti-radical ability to reduce both 2,2-diphenyl-1-picrylhydrazyl radical (DPPH • ) (IC 20 = 225 ± 4 μg/mL; Trolox equivalent (TE) = 86 ± 6 μmol Trolox/g lipid) and 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid radical cation (ABTS •+ ) (IC 50 = 124 ± 2 μg/mL; TE = 152 ± 9 μmol Trolox/g lipid). Also, higher lag times were achieved in oxygen radical absorbance capacity (ORAC) assay for nitrated POPC, indicating a faster reaction with oxygen-derived radicals (TE = 1.03 ± 0.22 and TE = 1.30 ± 0.16 mmol Trolox/g lipid for nonmodified and nitrated POPC, respectively). Nitrated POPC showed the ability to inhibit lipid oxidation induced by the hydroxyl radical generated under Fenton reaction conditions, monitored by electrospray ionization (ESI) mass spectrometry (MS) using phosphatidylcholine (PtdCho) liposomes as a model of cell membrane. Nitrated POPC showed anti-inflammatory potential, as assessed by the inhibition of inducible nitric oxide synthase (iNOS) expression in RAW 264.7 macrophages activated by the Toll-like receptor 4 (TLR4) agonist lipopolysaccharide (LPS) in a well-described in vitro model of inflammation. Altogether, this study provides new clues regarding the antioxidant and anti-inflammatory potential of nitrated POPC, which should be explored in depth., (© 2018 AOCS.)

Sacoglossan sea slugs, also known as crawling leaves due to their photosynthetic activity, are highly selective feeders that incorporate chloroplasts from specific macroalgae. These "stolen" plastids - kleptoplasts - are kept functional inside animal cells and likely provide an alternative source of energy to their host. The mechanisms supporting the retention and functionality of kleptoplasts remain unknown. A lipidomic mass spectrometry-based analysis was performed to study kleptoplasty of the sacoglossan sea slug Elysia viridis fed with Codium tomentosum. Total lipid extract of both organisms was fractionated. The fraction rich in glycolipids, exclusive lipids from chloroplasts, and the fraction rich in betaine lipids, characteristic of algae, were analysed using hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-LC-MS). This approach allowed the identification of 81 molecular species, namely galactolipids (8 in both organisms), sulfolipids (17 in C. tomentosum and 13 in E. viridis) and betaine lipids (51 in C. tomentosum and 41 in E. viridis). These lipid classes presented similar lipidomic profiles in C. tomentosum and E. viridis, indicating that the necessary mechanisms to perform photosynthesis are preserved during the process of endosymbiosis. The present study shows that there are no major shifts in the lipidome of C. tomentosum chloroplasts sequestered by E. viridis.

The data presented here are related to the research paper entitled "Transglycosylation reactions, a main mechanism of phenolics incorporation in coffee melanoidins: inhibition by Maillard reaction" (Moreira et al., 2017) [1]. Methanolysis was applied in coffee fractions to quantify glycosidically-linked phenolics in melanoidins. Moreover, model mixtures mimicking coffee beans composition were roasted and analyzed using mass spectrometry-based approaches to disclose the regulatory role of proteins in transglycosylation reactions extension. This article reports the detailed chemical composition of coffee beans and derived fractions. In addition, it provides gas chromatography-mass spectrometry (GC-MS) chromatograms and respective GC-MS spectra of silylated methanolysis products obtained from phenolic compounds standards, as well as the detailed identification of all compounds observed by electrospray mass spectrometry (ESI-MS) analysis of roasted model mixtures, paving the way for the identification of the same type of compounds in other samples.

Under nitroxidative stress conditions, lipids are prone to be modified by reaction with reactive nitrogen species (RNS) and different modifications were reported to occur in fatty acids. However, in the case of phospholipids (PL) studied under nitroxidative stress conditions, only nitroalkene derivatives of phosphatidylcholine (PC) and phosphatidylethanolamine (PE), were reported when using both in vitro biomimetic conditions and in vivo model system of type 1 diabetes mellitus. Therefore, in order to further explore other nitroxidative modifications of PL, a biomimetic model of nitroxidation combined with liquid chromatography mass spectrometry (MS) and MS/MS approaches were used to characterize the nitrated and nitroxidized derivatives of PCs and PEs. Single and multiple nitrated derivatives of phospholipids (PLs) such as nitroso and dinitroso, nitro, dinitro, and nitronitroso derivatives, together with nitroxidized derivatives were identified. Further, the specific MS/MS fragmentation pathways of these products were studied. Product ions arising from loss of HNO and HNO 2 , from the combined loss of HNO (or HNO 2 ) and polar head groups, [NO n -FA+O n +H] + and [NO n -FA+O n -H] - (n=1-2) product ions corresponding to the modified fatty acyl chains were observed, depending on each modification. The knowledge obtained from the study of the MS/MS fragmentation pattern has allowed us to identify nitrated PCs, including NO 2 -PC, (NO 2 ) 2 -PCs, (NO 2 )(NO)-PC, NO-PC; nitrated PEs, NO 2 -PEs; and nitroxidized PCs, (NO 2 )(2O)-PC in H9c2 cells under starvation, but not under ischemia or control conditions. The physiological relevance of this nitrated and nitroxidized PCs and PEs species observed exclusively in cardiomyoblast cells (H9c2) under starvation is still unknown but deserves to be explored., (Copyright © 2017. Published by Elsevier Inc.)

Metoprolol is a β-blocker highly prescribed for the treatment of heart diseases. It is not efficiently removed in wastewater treatment plants and it has been detected not only in the treated effluents, but also in natural waters. Thus, the knowledge of its fate in the environment is an important issue, and photodegradation is an important degradation pathway. While direct photodegradation of metoprolol by solar light is not relevant, there is evidence in the literature that it suffers indirect photodegradation and a few studies have been published showing the important role of dissolved humic matter as photo-sensitizer. However, the identification of the photoproducts formed in the presence of humic matter is very poor, since only 2 photoproducts had been identified. This study investigated the degradation of metoprolol under simulated solar radiation and in the presence of fulvic acids (FA) extracted from a river. During the photodegradation experiments we observed the formation of new compounds which were separated and tentatively identified by HPLC-UV-ESI-MS n . At least 16 compounds were tentatively identified, including the 2 compounds previously identified in the literature and 4 new compounds which had not been detected by other authors as degradation products of metoprolol, even when submitted to artificial degradation processes., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In the aquatic environment, pharmaceutical drugs are submitted to degradation processes, where photodegradation is one of the most important mechanisms affecting the fate, persistence and toxicity of the compounds. Carbamazepine, a widely used antiepileptic, is known to suffer photodegradation in water bodies and generate photoproducts, some of them with higher potential toxicity than the parent compound. Therefore, to evaluate the toxic effects of CBZ when combined with its photoproducts, an acute exposure (96h) with the edible clam Scrobicularia plana was performed using environmental concentrations of CBZ (0.00-9.00μg/L) irradiated (and non-irradiated) with simulated solar radiation. The analysis of the irradiated CBZ solutions by mass spectrometry revealed the formation of 5 photoproducts, including acridine (a compound known to be carcinogenic). Oxidative stress results showed that the exposure to CBZ photoproducts did not increase the toxicity to clams, by comparison with the parent compound. Lipid peroxidation levels, catalase and superoxide dismutase activities were the most responsive parameters to these stressors and lipid peroxidation results appeared to show the presence of an antagonistic effect resulting from the mixture of CBZ and its photoproducts., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Eggs are one of the main foods eaten worldwide. Nutritionally they are one of the main sources of dietary lipids, impacting human health. Egg yolk lipid composition changes depending on different conditions associated with hens raising. Therefore, the purpose of our work was to use a lipidomic approach as a tool to evaluate if different diets (vegetable versus animal) and raising environments (free range versus indoor) interfere in the triacylglycerol (TAG) and phospholipid (PL) profiles of eggs' yolks and to use such differences to differentiate eggs according to their origin. To achieve that goal, total lipid extracts were obtained and then fractionated by solid-phase chromatography. TAGs fraction was analysed by ESI-MS and PLs fraction by HILIC-LC-MS/MS. TAG and five PL classes were identified, namely PC, LPC, PE, LPE and SM. Fatty acids (FA) esterified to the glycerol backbone of PL ranged between C16:0 and C22:6. On the other hand, FA esterified to TAG ranged from C14:0 to C20:0. Major differences on the PL profile were observed regarding eggs from free-range hens and fed with vegetable origin food and eggs from the remaining conditions, once the former presented higher levels of PC (O-34:0), PC (34:1) and PE (34:1). Eggs from hens fed with animal origin food contained PL and TAG molecular species richer in n-6 FA, according to GC-MS and to LC-MS/MS data. The lipidomic approach used herein proved to be promising in differentiating eggs from hens with different raising conditions., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Cinnamylideneacetophenones (CA) are an important group of α,β,γ,δ-diunsaturated ketones that have been widely used in a variety of synthetic transformations. Biological studies concerning these compounds are scarce and refer mainly to antiviral and antibacterial evaluations. Curcumin (CR), a natural polyphenol, is a yellow pigment extracted from the plant Curcuma longa, which is one of the major spices used in the Indian culinary. It has been reported that CR has cancer chemopreventive properties in a range of animal models of chemical carcinogenesis, along with antioxidative and anti-inflammatory properties. Inspired by the biological activity shown by CR and their structural resemblance with CA, it was considered to study the ability of the latter molecules to inhibit lipid oxidation induced by the hydroxyl radical (Fenton reaction) by electrospray ionization (ESI) mass spectrometry (MS) using phosphatidylcholine (PC) liposomes as a model of cell membrane. Compound 4, holding a methylated hydroxy group in the position R(2), and CR showed similar effects in inhibiting lipid peroxidation. In the presence of 7, the extension of oxidation was higher than the one verified in all other compounds. Other methodologies, namely DPPH radical scavenging and oxygen radical absorption capacity (ORAC) assays, were performed to complement and clarify the results attained by oxidation of PC monitored by ESI-MS and to evaluate the antioxidant profile of compounds. For both assays, compound 7 showed to be rather efficient due to its specific structure. This derivative can form a quite stable allylic radical by abstraction of a hydrogen atom which accounts for these results., (Copyright © 2016 Elsevier Masson SAS. All rights reserved.)

Dendritic cells' (DC) activation is considered a key event in the adverse outcome pathway for skin sensitization elicited by covalent binding of chemicals to proteins. The mechanisms underlying DC activation by contact sensitizers are not completely understood. However, several "danger signals" are pointed as relevant effectors. Among these extra-cellular early danger signals, purines may be crucial for the development of xenoinflammation and several reports indicate their involvement in contact allergic reactions. In the present work we used the DC-surrogate monocytic cell line THP-1, cultured alone or co-cultured with the human keratinocyte cell line HaCaT, to explore the contribution of extracellular adenine nucleotides to THP-1 maturation triggered by the extreme contact sensitizer, 1-fluoro-2,4-dinitrobenzene (DNFB). We found that THP-1 maturation induced by DNFB is impaired after purinergic signaling inhibition, and that the transcription of the purinergic metabotropic receptors P2Y2 and P2Y11 is modulated by the sensitizer. We also detected that THP-1 cells only partially hydrolyse extracellular adenosine triphosphate, leading to accumulation of the mono-phosphate derivative, AMP. We detected different and non-overlapping activation patterns of mitogen activated protein kinases by DNFB and extracellular nucleotides. Overall, our results indicate that THP-1 maturation induced by DNFB is strongly modulated by extracellular adenine nucleotides through metabotropic purinergic receptors. This knowledge unveils a molecular toxicity pathway evoked by sensitizers and involved in THP-1 maturation, a DC-surrogate cell line thoroughly used in in vitro tests for the identification of skin allergens.

A previous work showed that the night period is important for the occurrence of Fenton-like oxidation of small aromatic acids from biomass burning in atmospheric waters, which originate new chromophoric compounds apparently more complex than the precursors, although the chemical transformations involved in the process are still unknown. In this work were identified by gas chromatography-mass spectrometry (GC-MS) and by electrospray mass spectrometry (ESI-MS) the organic intermediate compounds formed during the Fenton-like oxidation of three aromatic acids from biomass burning (benzoic, 4-hydroxybenzoic and 3,5-dihydroxybenzoic acids), the same compounds evaluated in the previous study, in water and in the absence of light, which in turns allows to disclose the chemical reaction pathways involved. The oxidation intermediate compounds found for benzoic acid were 2-hydroxybenzoic, 3-hydroxybenzoic, 4-hydroxybenzoic, 2,3-dihydroxybenzoic, 2,5-dihydroxybenzoic, 2,6-dihydroxybenzoic and 3,4-dihydroxybenzoic acids. The oxidation intermediates for 4-hydroxybenzoic acid were 3,4-hydroxybenzoic acid and hydroquinone, while for 3,5-dihydroxybenzoic acid were 2,4,6-trihydroxybenzoic and 3,4,5-trihydroxybenzoic acids, and tetrahydroxybenzene. The results suggested that the hydroxylation of the three small aromatic acids is the main step of Fenton-like oxidation in atmospheric waters during the night, and that the occurrence of decarboxylation is also an important step during the oxidation of the 4-dihydroxybenzoic and 3,5-dihydroxybenzoic acids. In addition, it is important to highlight that the compounds produced are also small aromatic compounds with potential adverse effects on the environment, besides becoming available for further chemical reactions in atmospheric waters., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The characterization of several commercial dextrins and the analysis of the potential of dextrin derived hydrogels for biomedical applications were performed in this work. The structural characterization of dextrins allowed the determination of the polymerization and branching degrees, which ranged from 6 to 17 glucose residues and 2 to 13%, respectively. Tackidex, a medical grade dextrin was choosen for further characterization. The combination of hydrogel with a dextrin nanogel and urinary bladder matrix was achieved without compromising the mechanical properties or microstructure. The encapsulation of cells, preserving its viability, confirms the biocompatibility of the injectable hydrogels, which have therefore great potential for biomedical applications., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this review, we provide a comprehensive bibliographic overview of the role of mass spectrometry and the recent technical developments in the detection of post-translational modifications (PTMs). We briefly describe the principles of mass spectrometry for detecting PTMs and the protein and peptide enrichment strategies for PTM analysis, including phosphorylation, acetylation and oxidation. This review presents a bibliographic overview of the scientific achievements and the recent technical development in the detection of PTMs is provided. In order to ascertain the state of the art in mass spectrometry and proteomics methodologies for the study of PTMs, we analyzed all the PTM data introduced in the Universal Protein Resource (UniProt) and the literature published in the last three years. The evolution of curated data in UniProt for proteins annotated as being post-translationally modified is also analyzed. Additionally, we have undertaken a careful analysis of the research articles published in the years 2010 to 2012 reporting the detection of PTMs in biological samples by mass spectrometry., (© 2013 Elsevier Inc. All rights reserved.)

The study carried out in this work concerns the structural characterization of pectic polysaccharides from plum (Prunus domestica L.) and pear (Pyrus communis L.) cell walls and commercial pectic polysaccharides, obtained from Citrus. The α-(1→4)-d-galacturonic acid backbone was submitted to a selective hydrolysis with endo-polygalacturonase (EPG) and the fractions with low molecular weight (<1kDa) obtained by size-exclusion chromatography were analysed by mass spectrometry using electrospray ionisation (ESI-MS). The ESI-MS spectra obtained revealed the presence of several [M+Na] + ions of pectic oligosaccharides identified as belonging to different series, including oligosaccharides constituted only by galacturonic acid residues (GalA n , n=1-5) and galacturonic acid residues substituted by pentose residues (GalA 3 Pent n , n=1-2). Surprisingly, it was also observed the occurrence of galacturonic acid residues substituted by hexose residues (GalA n Hex m , n=2-4, m=1-2). The fragmentation of the observed [M+Na] + ions, obtained under ESI-MS/MS and MS n allowed to confirm the proposed structures constituent of these pectic oligosaccharides. Furthermore, the ESI-MS n spectra of the ions that could be identified as GalA n Hex m (n=2-4, m=1-2) confirmed the presence of Hex or Hex 2 residues linked to a GalA residue. Methylation analysis showed the presence, in all EPG treated samples, of terminally linked arabinose, terminally and 4-linked xylose, and terminally and 4-linked glucose. The occurrence of GalA substituted by Glc, and Glc-β-(1→4)-Glc are structural features that, as far as we know, have never been reported to occur in pectic polysaccharides., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Olive mill wastewaters (OMW) are a potential source of biophenols, but they have a complex composition with many unknown phenolics. The analysis of purified methanol extracts from two Portuguese OMW by electrospray mass spectrometry in the negative mode showed [M-H] - ions at m/z 539 and m/z 523, corresponding respectively to oleuropein and ligstroside isomers which contain the glucose unit linked to its aromatic moiety. Also, the fragmentation pathway of the [M-H] - ions at m/z 863, 685 and 847 indicated the presence of a diglucoside derivative of the oleuropein isomer and of mono- and diglucosides of the ligstroside isomer, respectively. Moreover, the two OMW samples contained an elenoic derivative of the ion at m/z 685 and a degradation product (m/z 453) of the [M-H] - ion at m/z 523. Future studies focusing on the abundance of these compounds on OMW, as well as their bioactivities, will determine their possible industrial exploitation., (Copyright © 2011 Elsevier Ltd. All rights reserved.)