Characterisation of cell wall polysaccharide profiles of apricots (Prunus armeniaca L.), peaches (Prunus persica L.), and pumpkins (Cucurbita sp.) for the evaluation of fruit product authenticity

Cell wall polysaccharides were investigated for their suitability as markers for quality and authenticity control of fruit products. For this purpose, the alcohol-insoluble residue (AIR) from several cultivars of apricots and peaches of different harvest seasons, provenances, and stages of ripeness was extracted and subsequently fractionated into acid- and EDTA/alkali-soluble pectins, hemicellulose, and cellulose. Each fraction was analysed for its neutral sugar composition by gas chromatography. In addition, analyses were also carried out on several cultivars of pumpkins because of their potential for use in fraudulent admixtures. Within the respective fruit species, characteristic neutral sugar profiles of the AIR and its fractions were observed, which were found to be independent of the cultivar, harvest season, and provenance. The fruit specific saccharide composition may be used for the differentiation of fruit products devoid of carbohydrate-based hydrocolloids. Furthermore, the isolated hemicellulose may also allow the detection of admixtures of non-specified fruit in complex fruit products, such as jams, spreads, and fruit preparations.     

Evaluation of fruit authenticity and determination of the fruit content of fruit products using FT-NIR spectroscopy of cell wall components

An analytical procedure using Fourier transform near infrared (FT-NIR) spectroscopy and chemometrics with multivariate techniques for the rapid determination of the fruit authenticity and for the quantification of the fruit content was developed, based on the cell wall constituents (alcohol-insoluble residue, AIR, and hemicellulose, HC). The contents of rhamnose, fucose, arabinose, xylose, mannose, galactose, and glucose in the hemicellulose fraction of apricots, peaches, and pumpkins determined by gas chromatography were used as references. Furthermore, spectral information was correlated with the fruit content and the gravimetric data obtained from sequential fractionation of the alcohol-insoluble residue. Samples of self-made and commercial apricot and peach fruit preparations, jams, and spreads were included in the investigations. Hemicellulose from 109 samples and AIR from 92 samples was recorded, and principal component regression was used to create calibration models relating chemical and gravimetrical reference values to spectral data. The calibration models provided a good predictability in comparison with the results obtained by reference methods. Good agreement was also obtained for the prediction of the neutral sugar composition of the HC and the fruit content from the AIR. FT-NIR spectroscopy allowed a rapid, accurate and non-destructive assignment of specified fruit from spectral data of the HC fraction and the AIR. Thus, FT-NIR could be applied for investigations on quality control complementing, or even replacing, gas chromatography as the most widespread method for the determination of neutral sugars. Furthermore, preliminary investigation on classification of fruit blends was performed. The probability of belonging to a specific fruit was significantly lowered or precluded for samples with fraudulent admixture like peach or pumpkin to apricot, or pumpkin to peach.     

The content of polyphenols and carotenoids in three apricot cultivars depending on stage of maturity and geographical region

During the ripening of three apricot cultivars (“Keckemetska ruza”, “Madjarska najbolja” and “Velika rana”) grown in two different geographical region of Croatia the changes of polyphenols and carotenoids were determined by using high-performance liquid chromatography (HPLC) with UV–Vis photo diode array detection. The content of individual polyphenols during ripening was quite similar, whereas their amount differed significantly. Immature fruits showed the highest level of polyphenols, which decreased at semi-mature fruits and did not change remarkably in commercial mature fruits. Among polyphenols, flavan-3-ols, chlorogenic acid and quercetin-3-rutinoside were dominant in all ripening stages of all apricot cultivars. The quantity of polyphenols during apricot fruits ripening depended on cultivars, while the region of cultivation did not have remarkable influence on polyphenols amount. During ripening carotenoids increased significantly especially β-carotene which represented 70–85% of the total carotenoid content. Besides β-carotene, in all apricot cultivars γ-carotene was found. α-Carotene, zeaxantin and lutein were found in cv. “Madjarska najbolja” and in cv. “Velika rana” α-carotene and lutein were determined. The region of cultivation and the cultivar were important factors, which influenced the carotenoid amount of apricot fruits, and this content was higher in cultivars grown in Mediterranean region.     

Xanthophyll esters are hydrolysed in the presence of recombinant human pancreatic lipase

Fruit-derived bioactive xanthophyll esters have to be cleaved in the human gastrointestinal tract before absorption of free xanthophylls is possible. One candidate for ester hydrolysis is human pancreatic lipase. For estimation of their activity, an in vitro assay using the recombinant enzyme human pancreatic lipase (rHPL) and porcine colipase was used. Extracts of fruits were incubated with rHPL/colipase for 21 h at 37 °C. Activity of rHPL was demonstrated by an increase of free xanthophylls formed during the incubation. An extremely low activity was detected with all substrates. HPLC–(APcI)MS studies proved that lutein diesters were preferentially cleaved at the β-ionone ring. This is the first report which shows that xanthophyll esters can be cleaved in the presence of rHPL, suggesting either an unexpected secondary ester bond hydrolysis occurring within rHPL active site or, more probably, a reaction induced by other amino acids of HPL such as observed earlier with p-nitrophenyl acetate.     

Identification and quantification of phenols, carotenoids, and vitamin C from papaya (Carica papaya L., cv. Maradol) fruit determined by HPLC-DAD-MS/MS-ESI

Recent studies have demonstrated that vitamin C, phenols, and carotenoids are bioactive compounds that protect the body from oxidative stress, reducing the risk of cardiovascular diseases and some types of cancer. Qualitative and quantitative analysis of the major phytochemicals found in papaya fruit flesh and skin (Carica papaya L., cv Maradol) was conducted in four stages of ripeness, using high-performance liquid chromatography mass spectrometry. Phenolic compounds identified in the fruit skin tended to decrease with ripening. The compounds identified were ferulic acid (277.49 to 186.63 mg/100 gDW), p-coumaric acid (229.59 to 135.64 mg/100 gDW), and caffeic acid (175.51 to 112.89 mg/100 gDW). The following carotenoids, along with vitamin C, increased in flesh with ripening; lycopene (0.36 to 3.40 mg/100 gDW), ??-criptoxanthin (0.28 to 1.06 mg/100 gDW), ??-carotene (0.23 to 0.50 mg/100 gDW), and vitamin C (25.07 to 58.59 mg/100 gDW). These results indicate that stage of ripeness significantly influences the contents of bioactive compounds in papaya fruit.     

Genistein and dicarboximide fungicides in infant formulae from the EU market

A method based on ultrasonic extraction and purification by solid phase extraction followed by LC–MS/MS and GC–MS analysis was developed for the determination of genistein, genistin, iprodione, vinclozolin and procymidone in infant powdered formulas. The method was tested for different formulations: milk, soy and hypoallergenic, and was applied to European pooled samples. Spike recoveries ranged from 53.1% to 91.5% and the relative standard deviation values for repeatability ranged from 9.6% to 17.7%, except for iprodione in milk formula (22.3%).     

Optimal conditions for the production of monoacylglycerol from crude palm oil by an enzymatic glycerolysis reaction and recovery of carotenoids from the reaction product

Monoacylglycerol (MAG) was produced from crude palm oil (CPO) by the enzymatic glycerolysis reaction in organic solvents. The optimal conditions for MAG production from CPO were: the use of a mixture of tert‐butanol and hexane (1:1) as the organic solvents; an immobilised lipase of 40%; a molar ratio of glycerol to CPO of 8:1 with 4% of water content in the glycerol; and an initial CPO concentration of 10%. A maximum yield of 74.3% MAG was obtained with an initial production rate of 42.3 mg MAG mL^?1 h^?1. By converting CPO to the more polar MAG, the efficiency of recovery of carotenoids by adsorption column chromatography was improved up to 75.7% from 55.1% when using unconverted CPO. This study provides information that will be useful for developing an efficient and cheaper industrialised process for the production of MAG from CPO and recovery of carotenoids from the reaction product.     

Degradation compounds of carotenoids formed during heating of a simulated cashew apple juice

The influence of organic acid and heating treatments on carotenoid degradation on a simulated cashew apple juice was assessed by high performance liquid chromatography coupled with a photodiode array and mass spectrometry detectors. A total of nineteen carotenoids were separated in unheated simulated cashew apple juice, with all-trans-β-cryptoxanthin and all-trans-β-carotene as the major ones. As a consequence of heating, five xanthophylls disappeared, whereas two new cis isomers and five epoxide or furanoid-derivatives were formed and the levels of all cis isomers increased. In addition, 12′-apo-β-carotenal was formed at 90 °C. Two oxidation compounds (12′-apo-β-carotenal and 5,6-epoxy-β-cryptoxanthin) were formed after β-cryptoxanthin heating at 90 °C in an aqueous-based system. In all systems, the amounts of total carotenoids lost were not compensated by those formed. These facts indicated that isomerisation and oxidation to both coloured and non-coloured compounds were the main reactions occurring during heating of carotenoids in aqueous-based and juice systems.     

Determination of the melatonin content of different varieties of tomatoes (Lycopersicon esculentum) and strawberries (Fragariaananassa)

Melatonin has recently been detected in various plants and foods. However, data regarding the food composition of melatonin are too scarce to evaluate dietary intake. This paper aims to identify melatonin unequivocally using LC–MS in a wide set of varieties of tomatoes (Lycopersicon esculentum) and strawberry (Fragariaananassa). Furthermore, a validated LC fluorescence was developed.     

Identification of irradiated meats by determining o- and m-tyrosine as markers

To identify the irradiated meats, various parameters that affect extraction efficiency of tyrosine positional isomers were evaluated. The optimum procedure employed simple extraction by 0.1% formic acid and protein precipitation by acetone. Baseline separation for the extract was carried out on LC–fluorescence detection (FLD) and LC–tandem mass spectrometry (MS/MS). The LC–FLD and LC–MS/MS method had LOD of 1.7–2.1 and 0.3–0.5 ng/mL, respectively, and showed excellent linear correlation over three orders of magnitude, obtained ideal recoveries (78.68–88.90%) and RSD (≤ 8%). The methods were successfully applied in multiple samples. For o- and m-tyrosine, the order of descending trend was: chicken > beef > hairtail > pork and chicken > hairtail > beef > pork, respectively. The radiation dose could be quantitatively evaluated by the nonlinear correlation (y = A₀x² + A₁x + A₂) with coefficients of determination r² > 0.998 in individual meat samples.     

Antioxidant capacities,carotenoids and polyphenols evaluation of fresh and refrigerated peach and nectarine cultivars from Italy

Chemical–physical properties, colour parameters, antioxidant activities (AA), carotenoid and polyphenol levels (CL) in seven cultivars of yellow flesh peaches, five cultivars of yellow flesh nectarines and one cultivar of white flesh nectarines at harvest time and after 7 days of cold storage were evaluated. Peaches had major variability in flesh firmness (FF) and titratable acidity (TA) and lower soluble solid concentration (SSC) than nectarines. Evaluation of ground colour parameters, a*, b* and L*, showed that nectarines had a yellow-orange hue with high lightness, while peaches were darker, tending to red-green. Hydrophilic, lipophilic antioxidant activities of extracts (W-AA and L-AA), carotenoids and polyphenols levels (CL and PL) were evaluated and their relation with commercial maturation. The average of W-AA at harvest time was 11.0 TEAC, while the L-AA values at harvest time was on average higher in peaches (2.0 TEAC) than in nectarines (1.3 TEAC). The yellow flesh had higher amounts of total carotenoids (182.45 μg/100 g fw for peaches and 117.37 μg/100 g fw for yellow flesh nectarines). During cold storage, W-AA increased for nectarines (+22.9% in yellow flesh and +19.2% in white flesh) and peaches as well as polyphenolic compounds (+13.37%) while, contents of carotenoids decreased (−8.7%).     

Pesticide residue analysis by RPLC–GC in lycopene and other carotenoids obtained from tomatoes by supercritical fluid extraction

In the present work supercritical fluid extraction (SFE) is used to obtain carotenoids from tomatoes which were previously treated with pesticides. A procedure to determine pesticides in the extracts by RPLC–GC using the TOTAD interface is proposed. Tomatoes growing in an experimental plot were treated with different pesticides, and after picking, pesticide residues in the tomatoes were analysed and the tomatoes were used to obtain carotenoids by SFE. The carotenoid extracts were analysed using the above mentioned method. The data obtained indicated that trace amounts of the pesticides were extracted together with the carotenoids by SFE. The concentration of pesticide obtained in the second separation vessel was higher than that obtained in the first separation vessel. We conclude that only pesticide-free tomatoes should be used to extract carotenoids for applications as a nutritional supplement or in the cosmetic and pharmaceutical industries.     

Monitoring of perfluorinated compounds in edible fish from the Mediterranean Sea

Perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS) are environmental contaminants belonging to a chemical group known as perfluorinated compounds (PCFs). The United States Environmental Protection Agency (US EPA) considers both compounds to be carcinogenic. The goal of the present study was to evaluate the contamination levels of PFOS and PFOA in edible fish of the Mediterranean Sea. Twenty six fish muscles, 17 fish livers, five series of cephalopods (each composed of ten specimens) and thirteen series of bivalves (each composed of about 50 specimens) were used for the investigation. A fast sample treatment, followed by an LC–ESI–MS/MS method is described for the identification, and quantification of PFOA and PFOS in fish. The method was in-house-validated through the determination of precision, accuracy, specificity, calibration curve, decision limit (CCα), and detection capability (CCβ). The results showed PFOA and PFOS levels in fishes and molluscs lower than those reported for analogue matrices in different geographic areas. Therefore, our biomonitoring results did not show that the Mediterranean Sea had any particularly alarming pollution by PFCs, although it is located in a semi-closed basin with scarce water change. Nonetheless, a worrying element is that a few fish showed extremely high contamination by PFOA and PFOS. This finding needs further clarification in order to assess whether such unusual contamination is linked to “dot-like” pollutant release, which could explain the anomaly.     

Content,composition, and stereochemical characterisation of lignans in berries and seeds

In seed extracts of five oilseed species, in bran extracts of three cereal species, and in seed and/or whole berry extracts of 10 berry species, the concentrations of a large number of lignans and the enantiomeric composition of selected lignans were determined. In the case of sesame and hemp seeds, the lignan content and composition of the whole seeds was compared to that of the hulled seeds. The results showed that cloudberry seeds are the third most lignan-rich food source after linseeds and whole sesame seeds, and that most of the berry species analysed were more lignan-rich than the cereal brans. The lignans are concentrated in the hull of the oilseeds and in the seeds of the berries. In most samples, secoisolarici-, pino-, medio-, and syringaresinol were present as a mixture of two enantiomers.     

Chemical characterization and antioxidant evaluation of muscadine grape pomace extract

Concentrated muscadine pomace extract was chromatographically analyzed for its individual phenolic, flavonoid, and anthocyanidin compounds. This extract was also characterized regarding its total phenolic content (TPC), total flavonoid content (TFC), antioxidative activities in terms of scavenging DPPH free radicals, reducing ferric, and chelating Fe²⁺. The TPC of this product was 34.1 ± 1.8 mg of gallic acid equivalents(GAE)/g of extract, and TFC was 3.0 ± 0.3 mg of quercetin equivalents/g of extract. Some phenolic compounds including ellagic acid, gallic acid, (−)-epicatechin, (−)-epigallocatechin, catechin, myricetin, quercetin, and kaempferol were identified. Some anthocyanidins including delphinidin, cyanidin, petunidin, peonidin, and malvidin were also identified in the extract by using a combination of retention and spectral properties on a reverse-phase HPLC–PDA. In addition, 3,3′,4,4′5,5′-hexahydroxystilbene-a resveratrol analogue present in the extract was identified for the first time by LC–MS. The results from this study demonstrate that the muscadine pomace extract is rich of natural antioxidants such as phenolics, flavonoids and anthocyanins, and possesses strong antioxidant properties. Besides, the developed methods can be used for routine quality control of the muscadine products for manufacturing efficiency and consistency.     

Process optimisation for recovery of carotenoids from tomato waste

Carotenoids constitute an important component of waste originating from tomato processing plants. Studies were carried out to assess the extraction yield of tomato waste carotenoids in different solvents and solvent mixtures and to optimise the extraction conditions for maximum recovery. A mixture of ethyl acetate and hexane gave the highest carotenoid extraction yield among the others examined. Extraction conditions, such as percentage of hexane in the solvent mixture of ethyl acetate and hexane, ratio of solvent to waste and particle size were optimised using a statistically designed experiment. A regression equation for predicting the carotenoid yield as a function of three extraction variables was derived by statistical analysis and a model with predictive ability of 0.97 was obtained. The optimised conditions for maximum carotenoid yield (37.5 mg kg⁻¹ dry waste) were 45% hexane in solvent mixture, solvent mixture to waste ratio of 9.1:1 (v/w) and particle size 0.56 mm.     

金盏菊花类胡萝卜素提取最佳条件的研究

在不同溶剂、提取时间、温度、料液比和次数等条件下,通过正交实验,对金盏菊花类胡萝卜素提取最佳条件进行了研究。结果表明：最佳提取工艺条件是用石油醚－丙酮（１：１,Ｖ／Ｖ）混合溶剂浸提,料液比为１：２５（ｇ／ｍｌ）,在４５℃浸提１ｈ,反复４次,浸提率可达９３．５％。     

Phytochemical flavonols,carotenoids and the antioxidant properties of a wide selection of Fijian fruit,vegetables and other readily available foods

Frequent consumption of fruits and vegetables is associated with a lowered risk of cancer, heart disease, hypertension and stroke. This has been attributed to the presence of various forms of phytochemicals and antioxidants present in the foods, e.g. carotenoids and polyphenol compounds including flavonoids and anthocyanins. Seventy Fiji grown fruits and vegetables, and some other commonly consumed products, were analysed for their total antioxidant capacity (TAC), total polyphenol content (TPP), total anthocyanin content (TAT) as well as the major flavonol and carotenoid profiles. These data will be used to estimate the phytochemical and antioxidant intake of the Fijian population and will be a useful tool in future clinical trials.     

Development and validation of a liquid chromatographic-tandem mass spectrometric method for determination of eleven coccidiostats in milk

A reversed phase liquid chromatographic–tandem mass spectrometric method with simple solvent extraction and purification by solid phase extraction (SPE) has been developed for the determination of coccidiostats in milk. For sample preparation matrix solid phase dispersion, extraction by organic solvent and SPE with different cartridges were also tested. The compounds determined include lasalocid, narasin, salinomycin, monensin, semduramicin, maduramicin, robenidine, decoquinate, halofuginone, nicarbazin and diclazuril. Main steps of the method are addition of acetonitrile to the milk samples, centrifugation, removal of matrix by SPE, concentration by evaporation and LC–MS–MS determination. During a 15 min time segmented chromatographic run compounds are ionised either positively or negatively. Calculated recoveries range between 77.1% and 118.2%. Maximum levels are in the range of 1–20 μg/kg. The developed method was validated in line with the requirements of Commission Decision 2002/657/EC (2002). It is applicable for control of coccidiostat residues in milk as indicated in Regulation 124/2009/EC (2009).