HPLC-DAD-ESI-QTOF-MS and HPLC-FLD-MS as valuable tools for the determination of phenolic and other polar compounds in the edible part and by-products of avocado

Avocado is a tropical fruit increasingly cultivated around the world due to global interest and rising consumption. Thus, there is also a surge in avocado by-products that needs assessment. The aim of this work is to compare the phenolic profile of avocado pulp, peel and seed when the fruit is at optimal ripeness for consumption and when overripe. Two analytical techniques were used: (1) HPLC-DAD-ESI-QTOF-MS was used for the first time to determine phenolic and other polar compounds in avocado peel and seed. Phenolic compounds quantified with these methods were in higher concentration in overripe than in pulp and seed of optimally ripe fruit. (2) HPLC-FLD-MS was used to specifically determine flavan-3-ols. Procyanidins to degree of polymerization 13 have been quantified singularly here for the first time. In addition, A- and B-type procyanidins from the degree of polymerization 2 to 6 were differentiated and quantified. The procyanidin concentration increased after ripening probably due to the release of tannins linked to cell-wall structures. Because of this situation and the presence of A-type procyanidins, avocado peel and seed from overripe fruit, the main by-products of avocado processing, hold interest for developing functional foods, nutraceuticals and cosmetics

Bioactive lipids in butter chain production from the Parmigiano Reggiano cheese area

Introduction. Bovine milk contains hundreds of diverse components. Particularly, the complex composition of milk lipids and their specific structural organisation in the form of fat globules of various sizes need to be further investigated to take advantage of their properties for nutritional and health applications. The lipidic composition has been influenced by different variables such as: breed, feed and technological processing. To this end the fatty acid and phospholipid composition of different typology of samples were determined. Material and methods. All the samples were collected in the protected designation of origin Parmigiano Reggiano cheese area. Cream, butter and buttermilk from two different farms were analyzed. The raw material was represented by cream samples obtained by outcrop natural creaming. The first group of samples (IS) was recovered in a farm where the cows were raised with a mix of unifeed and forage and the butter was produced with industrial Fritz method; the other group of samples (TS) were obtained from Reggiana cows breeding, raised only with forage and the butter was obtained with a traditional churn. The fatty acids methyl esters and phospholipids were determined in the cream, butter and buttermilk samples. Results. The results about fatty acid composition showed that all the TS samples reported a higher content of MUFA and PUFA and, consequently, a lower SFA/UFA ratio. The CLA content in cream, butter and buttermilk of TS samples was about 30 % higher than IS samples. As reported for CLA, also the omega-3 fatty acids content was significantly higher in Reggiana cow\u2019s samples; consequently, the n6/n3 ratio was higher in the IS samples. The phospholipids composition varied between IS and TS. PE was the first phospholipid in IS-cream, IS-butter and IS-buttermilk samples, instead PE was the first phospholipid in TS-cream and TS-buttermilk, but PC was the first phospholipid in TS-butter. It can be due to the different churning process that causes a different membrane disruption. The total phospholipid content was higher in TS samples. TS-butter phospholipid content was 33 % higher than IS-butter. Conclusions. The sampling represents the two typologies of products that are present in the Parmigiano Reggiano cheese area. The industrial samples are produced in higher quantities compared to the Reggiana derived products. Effectively, the Reggiana cow milk production is lower compared to other breeds. Moreover, the traditional churn process is time consuming and economically disadvantageous. However, its products contain more bioactive lipids than others obtained from different breeds and industrial process

FROM WASTES TO ADDED VALUE BY-PRODUCTS: AN OVERVIEW ON CHEMICAL COMPOSITION AND HEALTHY PROPERTIES OF BIOACTIVE COMPOUNDS OF OLIVE OIL CHAIN BY-PRODUCTS

The production of olive oil originates a huge amount of residues like aqueous waste (50%) called olive mill wastewater and olive leaves that represent up to 10% of the weight of olive oil extraction and olive pomace. Moreover, other wastes were generated during the filtration processes and during the storage time when suspended solids tend to migrate at the bottom of the tanks originating sediments. However, it has been demonstrated that these wastes are rich in bioactive compounds and, thus, they can be considered as useful by-products for the recovering of these compounds to further uses. The olive oil mill wastewater is a problematic and polluting effluent which may degrade the soil and water quality, with critical negative impacts on ecosystems functions and services provided. Nevertheless, literature highlights its high concentration of antioxidants, especially phenolic compounds. However, the qualitative phenolic profiles of olive oil mill wastewater differ depending on the technological process of production of olive oil and the time of storage. Because of that, it is very important to evaluate the technological processes and the shelf life of olive oil mill wastewater to obtain a good source of bioactive compounds. In fact, the biological activities of phenolic compounds from olive mill wastewater have been studied, and they show a spectrum of highly interesting bioactivities. Olive leaves also represent a significant by-product of the cultivation and harvesting of olive. Historically, olive leaf has also been used as a folk remedy for combating fevers and other diseases, such as malaria. Several pharmacological reports have shown that olive leaf extracts have the property to lower blood pressure, increase blood flow in the coronary arteries, and exhibit a wide antiviral activity including anti-HIV activity, or have been cited for their antitumor activity, particularly against different types of breast cancer. Olive pomace can reach up to 30% of olive oil manufacturing, depending on the milling process which, after oil extraction, is generally distributed by means of controlled spreading on agricultural soil. However, a large quantity of olive mill solid residue remains without actual application because only small amounts are used as natural fertilizers, combustible biomass and additives in animal feeding and activated carbon. But theses residues are a valuable starting material for the production of phenol extracts that could be used in the industries. Because of that, research for valorization of olive pomaces has so far been mainly focused on panels or target known compounds considered of interest

A spectroscopic and chemometric study of virgin olive oils subjected to thermal stress

The paper describes a study of thermal stress of three different samples of virgin olive oil in terms of oxidative stability. Fatty acid composition, evaluation of oxidative stability under forced conditions (OSI), determination of UV-spectrophotometric oxidation indexes (k232 and k270) and spectral properties were explored along the thermal treatment. The samples were subjected to heating treatment at 180\ub0C and evaluated after 0, 30, 60, 90, 120, 150 and 180 min. Middle infrared (MIR) and visible\u2013near infrared (Vis\u2013NIR) spectra were elaborated by partial least squares modelling to individualise regions and bands where critical variations were present. Two bands were found as principal influential ones (1245\u20131180 cm-1 and 1150\u20131030 cm-1) on MIR while one primary region was identified on Vis\u2013NIR (2200\u20131325 cm-1)

Development of a rapid method to determine phenolic and other polar compounds in walnut by capillary electrophoresis\u2013electrospray ionization time-of-flight mass spectrometry

The aim of this work was to develop a capillary electrophoresis\u2013mass spectrometry (CE\u2013MS) method to identify and quantify phenolic and other related polar compounds in walnut samples. The extraction capacity of several solvent mixtures of phenolic compounds from walnut by conventional solid\u2013liquid extractions was tested, and CE and electrospray ionization MS parameters were optimized. The finalized procedure is able to determine many well-known phenolic compounds present in walnuts and provide relevant information about the presence of minor polar compounds. A new compound in walnut ((2E,4E)-8-hydroxy-2,7-dimethyl-2,4-decadiene-1,10-dioic acid 6-O-beta-d-glucopiranosyl ester, [M−H]− 403.161m/z) with a structure similar to glansregininswas also identified. Phenolic compounds correspond to 14\u201328% of total polar compounds quantified. Aglycone and glycosylated ellagic acid represent the principalcomponents and account for 64\u201375% of total phenols inwalnuts.However, thesumof glansregininsA, B and (2E,4E)-8-hydroxy-2,7-dimethyl-2,4-decadiene-1,10-dioic acid 6-O--d-glucopiranosyl ester was in the range of 72\u201386% of total quantified compounds. In addition, this is the first time that separation by CE with detection by electrospray ionization time-of-flightMShas been applied to the analysis of phenolic and other polar compounds in walnut samples, providing results in less than 15 min

Determination of the Major Phenolic Compounds in Pomegranate Juices by HPLC\u2013DAD\u2013ESI-MS

Traditionally, pomegranate (Punica granatum L.) has been consumed as fresh fruit or as pomegranate juice. In this study, the main phenolic compounds of 12 pomegranate varieties and 5 pomegranate clones were determined by HPLC-DAD-ESI-MS. Two chromatographic methods with a fused-core C18 column and a classical HPLC system were developed. Thirteen anthocyanins and fourteen other phenolic compounds were determined in the pomegranate juices. As far as we are concerned, a new flavonol-glycoside, phellatin or its isomer amurensin, has been tentatively identified for the first time in pomegranate juices. Total phenolic content ranged from 580.8 to 2551.3 mg/L of pomegranate juice. Anthocyanins varied between 20 to 82% of total phenolic content. Flavonoids were 1.6-23.6% of total phenolic compounds, while phenolic acids and ellagitannins were in the range 16.4-65.8%. The five clones reported a phenolic content comparable with that of the other pomegranate samples

DETERMINATION OF DIFFERENT PHENOLIC COMPOUND CLASSES IN POMEGRANATE JUICES BY HPLC-DAD-ESI-QTOF-MS

Background and objectives: Traditionally, pomegranate (Punica granatum L.) has been consumed as fresh fruit or as pomegranate juice and it has been described as a rich source of phenolic compounds. Several recent studies have shown that drinking pomegranate juice contributes to significant potential health benefits, and, today, it is known, that the positive health properties of pomegranate are due to the presence of bioactive compounds like, flavonoids, phenolic acids and tannins contained in it. Therefore, in this work, the main phenolic compounds of 17 pomegranate varieties were determined by HPLC-DAD-ESI-qTOF-MS. Methods: A new chromatographic HPLC-DAD-ESI-qTOFMS method, using a C18 fused-core column, was established and the analyses were performed in less than 20 minutes. Results: Eight anthocyanins and fourteen other phenolic compounds were tentatively identified and quantified in the pomegranate juices. As far we are concerned, a new flavonolglycoside has been tentatively identified for the first time in pomegranate juices. Total phenolic content ranged from 573.6 to 2519.8 mg/mL. Anthocyanins varied between 110.9 to 1925.5 mg/mL and they represented the 17-86 % of total phenolic content.Flavonoids were the 1.6-24.4 % of total phenolic compounds. Phenolic acid and ellagitannins were in the range of 300.9-810.2 mg/mL. Conclusions: The results confirmed, as reported in literature, that the pomegranate variety influences substantially the phenolic composition. It is important to highlight that, as far we are concerned, a new flavonol-glycoside has been tentatively identified for the first time in pomegranate juices thanks to this method

Solid Phase Extraction for the Direct Extraction of Phospholipids in Virgin Olive Oil and their Determination by Hydrophilic Interaction Liquid Chromatography Coupled to Mass Spectrometry

Phospholipids (PLs) are the most important class of polar lipids in foods because they are the major components of cell membranes in animal and plant tissues. Recent studies have shown that PLs can have a positive nutritional effect on human health, such as reducing the risk of cardiovascular disease, reducing blood cholesterol levels and enhancing brain function [ ]. As an integral component of cell membranes, they are involved in cell signalling and, therefore, they are indispensable for the communication and interaction between body cells [ - ]. Although some influences of phospholipids on health are controversial, overall dietary phospholipids are most likely to have a positive effect on health [ ]. Nevertheless, phospholipids are poorly investigated as minor compounds in olive oil and in literature the phospholipids extraction has been essentially developed by liquid-liquid extraction (LLE). The aim of this work was to compare the effectiveness of a previous LLE extraction method with a direct separation and purification of olive oil phospholipids with two different SPE sorbents (silica and diol). As far we are concerned this is the first application of SPE for the direct extraction of phospholipids in virgin olive oil. Furthermore, the extracts were analyzed by HPLC-ESI-qTOF-MS to obtain basic information useful for a possible identification of the single components. To this aim, a new separation method was established using an hydrophilic fused core liquid chromatography column (HILIC). The HILIC chromatography is readily compatible with electrospray ionization and results in higher sensitivity and improved peak shapes. The SPE diol extraction and HPLC-ESI-TOF-MS methodology have demonstrated to be very useful to determine the phospholipids in not filtered virgin olive oil and also in a veiled virgin olive oil subjected to a glyceridic crystallization due to a temperature decrease. In fact, it could be observed that crystallization caused a significant decrease in the phospholipids fraction

Evaluating the incidence of pathological complete response in current international rectal cancer practice: the barriers to widespread safe deferral of surgery

This is the peer reviewed version of the following article: , which has been published in final form at https://doi.org/10.1111/codi.14361. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions."Colorectal Disease © 2018 The Association of Coloproctology of Great Britain and Ireland Introduction: The mainstay of management for locally advanced rectal cancer is chemoradiotherapy followed by surgical resection. Following chemoradiotherapy, a complete response may be detected clinically and radiologically (cCR) prior to surgery or pathologically after surgery (pCR). We aim to report the overall complete pathological response (pCR) rate and the reliability of detecting a cCR by conventional pre-operative imaging. Methods: A pre-planned analysis of the European Society of Coloproctology (ESCP) 2017 audit was performed. Patients treated by elective rectal resection were included. A pCR was defined as a ypT0 N0 EMVI negative primary tumour; a partial response represented any regression from baseline staging following chemoradiotherapy. The primary endpoint was the pCR rate. The secondary endpoint was agreement between post-treatment MRI restaging (yMRI) and final pathological staging. Results: Of 2572 patients undergoing rectal cancer surgery in 277 participating centres across 44 countries, 673 (26.2%) underwent chemoradiotherapy and surgery. The pCR rate was 10.3% (67/649), with a partial response in 35.9% (233/649) patients. Comparison of AJCC stage determined by post-treatment yMRI with final pathology showed understaging in 13% (55/429) and overstaging in 34% (148/429). Agreement between yMRI and final pathology for T-stage, N-stage, or AJCC status were each graded as ‘fair’ only (n = 429, Kappa 0.25, 0.26 and 0.35 respectively). Conclusion: The reported pCR rate of 10% highlights the potential for non-operative management in selected cases. The limited strength of agreement between basic conventional post-chemoradiotherapy imaging assessment techniques and pathology suggest alternative markers of response should be considered, in the context of controlled clinical trials