M S Simonetti

Università degli Studi di Perugia, Perugia, Umbria, Italy

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Publications (55)70.28 Total impact

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    ABSTRACT: Saffron's quality depends on the concentration of secondary metabolites, such as crocins, picrocrocin and safranal. The aim of this research was to evaluate the influence of drying conditions on the secondary metabolite contents of saffron produced in the area of Cascia, in central Italy. Different aliquots of the same saffron sample were subjected to various dehydration conditions and analysed by UV-Vis spectrophotometry to determine crocins, picrocrocin and safranal.. Safranal was also analysed by high resolution gas chromatography, while the crocins and picrocrocin were determined by high-performance liquid chromatography with diode array and mass spectrometric detectors. The results of chromatographic analyses showed that the samples dried in the milder conditions had the lowest content of secondary metabolites. Moreover the sample dried at 60°C for 55min presented the highest contents of trans-crocin-4 and picrocrocin, while safranal was most represented in saffron dried at 55°C for 95min.
    Food Chemistry 01/2014; 143:446-51. · 3.33 Impact Factor
  • L. Cossignani, L. Giua, M.S. Simonetti, F. Blasi
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    ABSTRACT: In this research, volatiles arising from heating of conjugated (CLA) and unconjugated (LA) linoleic acid, in different chemical forms (free acids, methyl esters and homogeneous triacylglycerols) have been studied. A solid phase micro-extraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used to analyze the volatile compounds produced during heating at 180°C for different times (15, 30, 45 and 60 min). Numerous types of volatiles have been identified such as aldehydes, furan fatty acids, alcohols, methyl esters and methyl-oxoacids. Results showed that aldehydes were the main volatile compounds both in CLA and LA, even if some differences were found between conjugated and unconjugated systems. In particular, heptanal and trans-2-octenal were detected mainly in CLA forms, while trans-2-heptenal in LA. Among furan fatty acids, 2-pentyl-furan content was higher in LA than in CLA at all treatment times, while 2-hexyl-furan was detected in free fatty acid and methyl ester forms of CLA and it was never detected in LA model systems. Among alcohols, 1-octen-3-ol was found only in LA forms. Methylated forms of CLA and LA provided high contents of methyl esters, among which methyl octanoate was the most represented. Therefore heptanal, trans-2-octenal, 2-hexyl-furan could be considered as characteristic compounds produced during CLA-rich sample oxidation.Practical applicationsNowadays CLA, known for its interesting beneficial health effects both on animals and humans, is widely used as functional component in numerous foods and nutritional supplements. Besides the more common triacylglycerol form, CLA is used also as free fatty acids and methyl esters. To date, studies on CLA oxidation are scarce and the results are sometimes contradictory. For these reason the comparison of the volatile compounds obtained from different model systems of CLA and LA could be useful to deepen knowledge on secondary oxidation products of some chemical forms of interest for pharmaceutical formulae and CLA-rich oils. In fact it is very important to know the secondary products typical of CLA- and LA-based matrices to identify characteristic oxidation compounds of CLA and LA products.
    European Journal of Lipid Science and Technology 12/2013; · 2.27 Impact Factor
  • L Giua, F Blasi, M S Simonetti, L Cossignani
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    ABSTRACT: The oxidative stability of conjugated linoleic (CLA) and linoleic (LA) acids in different chemical forms (free acids, methyl esters and homogeneous triacylglycerols) was compared. All model systems were heated at 180°C for different times (15, 30, 45 and 60min). The primary oxidation products were evaluated by spectrophometric analysis, while the volatile compounds were determined by solid phase micro-extraction (SPME), coupled with gas chromatography-mass spectrometry (HRGC-MS). The isomer profile modifications were investigated by silver-ion high performance liquid chromatography (Ag(+)-HPLC) equipped with an UV detector. Generally, peroxide values decreased during the heating time. Among the volatiles, saturated aldehydes were the most represented compounds. Isomerization of cis,trans and trans,cis CLA to trans,trans isomers was observed mainly for the methyl form of CLA. The three different chemical forms of LA never showed isomerization phenomena.
    Food Chemistry 10/2013; 140(4):680-5. · 3.33 Impact Factor
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    ABSTRACT: Product authenticity is an important topic in dairy sector. Dairy products sold for public consumption must be accurately labelled in accordance with the contained milk species. Linear discriminant analysis (LDA), a common chemometric procedure, has been applied to fatty acid% composition to classify pure milk samples (cow, ewe, buffalo, donkey, goat). All original grouped cases were correctly classified, while 90% of cross-validated grouped cases were correctly classified. Another objective of this research was the characterisation of cow-ewe milk mixtures in order to reveal a common fraud in dairy field, that is the addition of cow to ewe milk. Stereospecific analysis of triacylglycerols (TAG), a method based on chemical-enzymatic procedures coupled with chromatographic techniques, has been carried out to detect fraudulent milk additions, in particular 1, 3, 5% cow milk added to ewe milk. When only TAG composition data were used for the elaboration, 75% of original grouped cases were correctly classified, while totally correct classified samples were obtained when both total and intrapositional TAG data were used. Also the results of cross validation were better when TAG stereospecific analysis data were considered as LDA variables. In particular, 100% of cross-validated grouped cases were obtained when 5% cow milk mixtures were considered.
    Journal of Dairy Research 11/2012; · 1.34 Impact Factor
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    ABSTRACT: Rabbit meat has excellent nutritive properties. The purpose of this study was to characterize rabbit meat and offal; in particular, the lipid fraction was studied in order to evaluate total and positional fatty acid (FA) compositions of triacylglycerol (TAG) and phosphatidylcholine (PC) fractions. Eight samples of weaned and eight of fattened rabbits were considered. Fattened rabbit meat contained slightly higher protein percentage content (P < 0.05) in comparison to weaned (20.1% versus 18.0%). Calcium content was higher in meat than in offal, unlike sodium, iron, zinc, manganese and copper. The cholesterol content in offal was much higher than in meat. FA profiles of total lipid showed a high percentage of unsaturated fatty acids and an n-6/n-3 ratio of 10.3 for fattened rabbit meat. Stereospecific analysis of TAG and PC was carried out on an eight-sample pool of each meat and offal from weaned and fattened rabbits. In all samples the sn-2-position was prevalently esterified with oleic and linoleic acids in TAG, with polyunsaturated fatty acids in PC. Lipids from rabbit meat presented higher content of monounsaturated FA and lower n-6/n-3 ratio in comparison to offal, which was characterized by higher cholesterol and mineral levels.
    Journal of the Science of Food and Agriculture 03/2012; 92(4):952-9. · 1.76 Impact Factor
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    ABSTRACT: Recently CLA isomers have received considerable attention as potential anti-cancer agents. The aim of the study was to assess the genotoxicity/antigenotoxicity in vitro of linoleic acid (LA, c,c-C18:2, Δ-9), CLA isomer mixtures and homogeneous CLA TAGs (TriCLA) using the comet assay, to evaluate the effects on the extent of DNA injury in human hepatoma (HepG2) cells. The study was carried out both on commercial CLA (CLAc) and on CLA synthesized from grapestone oil (CLAg). The CLA isomer mixtures had different isomer profiles, determined by silver-ion HPLC (Ag+-HPLC), in particular CLAc was characterized by four main isomers (t8,c10; c9,t11; t10,c12; c11,t13), while CLAg showed two main isomers (c9,t11; t10,c12). As regards antigenotoxicity testing, LA, TriCLAg, and above all TriCLAc were effective antigenotoxic compounds against ethylmethanesulfonate (EMS) induced genotoxicity, while LA and CLAg were almost equally effective against 4-nitroquinoline N-oxide (4NQO) induced DNA damage. Both TriCLAc and TriCLAg showed an increased antigenotoxic activity toward EMS and a lower antigenotoxic activity toward 4NQO, with respect to both CLAc and CLAg. The higher capability of CLAg with respect to CLAc in counteracting the genotoxicity of 4NQO could be due to the different CLA isomer composition. Practical applications: CLA isomers have shown many beneficial health effects both on animals and humans. They are widely used in nutritional supplements, as CLA improves body composition by reducing fat storage. In this regard it is very important to know, besides the chemical and analytical aspects, also genotoxic and antigenotoxic effects of different CLA mixtures. To our best knowledge, few results have been reported on CLA antigenotoxic properties by the comet assay, and no data could be retrieved in the literature for TriCLA antigenotoxicity testing. The obtained results are interesting in that they can increase the knowledge on particular fatty acids used in commercial supplements.
    European Journal of Lipid Science and Technology 01/2012; · 2.27 Impact Factor
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    ABSTRACT: It is known that conjugated linoleic acid (CLA) isomers have different beneficial health effects, and it has been demonstrated that the effects of CLA may be isomer dependent. For this reason, CLA isomer fractionation is a very important topic, and recently, various enzymatic methods for the fractionation of CLA isomers have been studied. In this paper, a commercial CLA standard including four isomers (c11,t13-, t10,c12-, c9,t11- and t8,c10-CLA) were subjected to enzymatic esterification with L-menthol in order to examine the ability of Candida rugosa lipase to discriminate among the isomers. The lipase was incubated at 30 �C for different reaction times, and subsequently, the degree of enzymatic esterification was established by high-performance liquid chromatography (HPLC) with light scattering detection. Moreover, in this study, a silver–ion HPLC analysis was developed to determine the isomer profile of L-menthyl-CLA. Since the t8,c10- and c11,t13-CLA isomers are not commercially available, they were obtained by sigmatropic rearrangement of c9,t11- and t10,c12-CLA, respectively. The highest selectivity for the c9,t11-CLA isomer was obtained when enzymatic esterification was carried out for 8 h. This study demonstrated that C. rugosa lipase has a higher selectivity for cis,trans isomers, than for trans,cis isomers; in particular, it has a higher selectivity for c9,t11- than for c11,t13-CLA.
    European Food Research and Technology 01/2012; 235:53. · 1.44 Impact Factor
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    ABSTRACT: Stereospecific analysis is an important tool for the characterization of lipid fraction of food matrices, and also of milk samples. The results of a chemical-enzymatic-chromatographic analytical method were elaborated by chemometric procedures such as linear discriminant analysis (LDA) and artificial neural network (ANN). According to the total composition and intrapositional fatty acid distribution in the triacylglycerol (TAG) backbone, the obtained results were able to characterize pure milk samples and milk mixtures with 1, 3, 5% cow milk added to donkey milk. The resulting score was very satisfactory. Totally correct classified samples were obtained when the TAG stereospecific results of all the considered milk mixtures (donkey-cow) were elaborated by LDA and ANN chemometric procedures.
    Journal of Dairy Research 08/2011; 78(3):335-42. · 1.34 Impact Factor
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    ABSTRACT: This paper reports the separation of four isomers of conjugated linoleic acid (CLA), c,t/t,c-8,10; c,t/t,c-9,11; c,t/t,c-10,12; c,t/t,c-11,13, after reaction of esterification with aliphatic alcohols of different chain length and adduct formation with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD). The high resolution gas chromatographic analyses were carried out using a simple 50-m cyanopropyl polysiloxane capillary column both with a flame ionization detector and a mass spectrometer. The resolution between the two pair of isomers: c,t/t,c-9,11 and c,t/t,c-10,12 and between c,t/t,c-10,12 and c,t/t,c-11,13 isomers were good for all the investigated alkyl esters and increased with the chain length of alcohol esterified to carboxylic moiety of CLA isomers. The most interesting result was relative to the c,t/t,c-8,10 and c,t/t,c-9,11 isomers, critical pair of isomers also when analyzed with a 120-m cyanopropyl polysiloxane capillary column; their resolution also increased from methyl to hexyl esters of CLA isomers and reached an acceptable value (0.8) in the case of hexyl esters. The best resolutions of the four considered CLA isomers were obtained with the hexyl esters of MTAD adducts of the isomers, without excessive analysis time. This method was useful and simple to evaluate the profile of the four main c,t isomers in commercial CLA samples.
    Journal of chromatographic science 05/2011; 49(5):379-83. · 0.79 Impact Factor
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    ABSTRACT: BACKGROUND: Structured lipids containing medium-chain fatty acids have interesting applications as reduced-calorie fats; moreover, conjugated linoleic acid (CLA) isomers have shown interesting biological properties. The aim of this study was to synthesize triacylglycerols (TAGs) containing capric acid in the sn-1- and sn-3- positions and CLA isomers in the sn-2- position, using different commercial available lipases.RESULTS: The homogeneous CLA-TAGs (Tri-CLA) were chemically synthesized starting from glycerol and CLA isomers, 9-cis,11-trans and 10-trans,12-cis CLA. The acidolysis reactions of Tri-CLA with capric acid were carried out at 55 °C for different times in hexane; after 96 h the acidolysis average yield was 65%. The best capric acid incorporation in total TAGs was obtained after 96 h with Lipozyme IM (56.6%). The results of structural analysis carried out on the obtained TAGs showed that both Novozyme 435 and anhydrous Lipozyme IM gave the best incorporation of capric acid in sn-1(3)- positions (61.8%). However, anhydrous Lipozyme IM gave also the highest CLA percent content in sn-2- position (73.2%).CONCLUSION: Anhydrous Lipozyme IM appears to be the more effective enzyme in acidolysis reactions to obtain structured TAGs containing CLA isomers in the central position and capric acid at external positions. Copyright © 2009 Society of Chemical Industry
    Journal of the Science of Food and Agriculture 10/2009; 89(15):2595 - 2600. · 1.76 Impact Factor
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    ABSTRACT: The synthesis of structured triacylglycerols (TAG) by the enzymatic reaction between sn-1,3-diacylglycerols (sn-1,3-DAG) and conjugated linoleic acid (CLA) isomers was studied. Both the substrates of the reaction were produced from vegetable oils, the sn-1,3-DAG from extra virgin olive oil and the CLA isomers from sunflower oil. The enzymatic reactions between these substrates were catalyzed for 96h by an immobilized lipase from Rhizomucor miehei (Lipozyme IM) and the reactions carried out in solvent were monitored every 24h by using high-performance liquid chromatography-evaporative light scattering detector (HPLC-ELSD). The enzymatic reactions were carried out in different reaction media (hexane, isooctane and solvent free) and with different CLA/sn-1,3-DAG ratios. Total % acidic composition and structural analysis data were evaluated to verify the presence of CLA isomers in sn-2- position of synthesized TAG. The results showed good levels of CLA incorporation in sn-1,3-DAG, from 19.2% of TAG synthesized in solvent free conditions with a 0.5:1 substrate ratio, to 47.5% of TAG synthesized in isooctane with a 2:1 substrate ratio. It was observed that for all the reaction media, the best sn-2- acylic specificity was obtained with a 0.5:1 substrate ratio.
    Journal of Oil & Fat Industries 01/2009; 86(2):127-133. · 1.59 Impact Factor
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    ABSTRACT: The present research deals with the chemical esterification of the sn-2- position of sn-1,3-diacylglycerol (sn-1,3-DAG) with 9cis,11trans (c9,t11) and 10trans,12cis (t10,c12) conjugated linoleic acid (CLA) isomers to obtain structured triacylglycerols (TAG); the sn-1,3-DAG substrates were produced from extra virgin olive oil by means of enzymatic reactions while CLA isomers were obtained using a three-step procedure based on alkaline hydrolysis of sunflower oil, urea purification of linoleic acid (LA) and alkaline isomerization of LA. The results showed good levels of CLA incorporation in structured TAG at the tested temperatures: 37.5% at 4°C and 39.1% at 14°C. To evaluate the incorporation of CLA isomers in sn-2- position of sn-1,3-DAG structural analysis of the newly synthesized TAG was carried out using an enzymatic and a chemical method. The results of the structural analysis also showed up the occurrence of acyl migration. The pancreatic lipase method allowed the direct determination of the fatty acid composition of TAG sn-2- position but this enzymatic method showed different results (p<0.05) in respect to the chemical one; this occurrence could be due to an acylic specificity of the lipase. High incorporation of CLA isomers in sn-2- position of TAG was observed, 77.0% at 4°C and 81.5% at 14°C, considering the results of the chemical procedure.
    Journal of Oil & Fat Industries 06/2008; 85(7):613-619. · 1.59 Impact Factor
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    ABSTRACT: Export Date: 25 October 2012, Source: Scopus
    Italian Journal of Food Science 01/2008; 20(2):263-271. · 0.44 Impact Factor
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    ABSTRACT: Arbutus unedo L. (fam: Ericaceae), a typical plant of the Mediterranean woods, produces many reddish berries with small seeds. This study was carried out to characterize the triacylglyeerol (TAG) fraction of the oil extracted from the seeds of A. unedo berries by stereospecific analysis and by a procedure based on hyphenated techniques (silver ion high-performance liquid chromatography -Ag+-HPLC- and stereospecific analysis of some sub-fractions). A. unedo lipids have a notable amount of essential fatty acids (EFA) and low levels of saturated fatty acids; furthermore there is a marked asymmetry in the FA positional distribution on the TAG glycerol backbone.
    Italian Journal of Food Science 01/2008; 20(1):49-56. · 0.44 Impact Factor
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    ABSTRACT: In the present research article, donkey milk samples were studied and the results were compared with those obtained from other mammalian species such as cow, ewe, goat and buffalo. Stereospecific analysis of triacylglycerols (TAG) was carried out to determine the intrapositional % fatty acid (FA) compositions and then the interpositional FA distribution in the sn-positions of TAG glycerol backbone. Buffalo milk showed the highest lipid content (9.6%) and donkey milk the lowest (0.3%). The FA distribution among the three sn-positions of the glycerol backbone was non-random; in all the considered milk samples, saturated FA (SFA) were prevalently esterified in sn-3-position, while monounsaturated FA (MUFA) in sn-2-, with some exceptions. Donkey milk represents an important dietary source of essential FA (EFA), about 40mg/100g milk; in particular, the linoleic acid is 2.5 times higher than in cow milk (15mg/100g versus 6mg/100g); moreover, these are esterified in high percentages in sn-2-position, so this milk appears interesting for its potential pharmaceutical and nutritional properties.
    Journal of Food Composition and Analysis - J FOOD COMPOS ANAL. 01/2008; 21(1):1-7.
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    ABSTRACT: Cited By (since 1996): 2, Export Date: 25 October 2012, Source: Scopus
    Italian Journal of Food Science 01/2008; 20(1):49-56. · 0.44 Impact Factor
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    ABSTRACT: Many researchers have studied the biological effects of carotenoids and the more appropriate procedure for extracting them from vegetable sources. In this work we propose a rapid and low-cost procedure to extract lycopene from tomato in order to by-pass the problems related to the high cost of this molecule. Following this procedure we have obtained over 95% pure all-trans-lycopene checked by DAD-HPLC coupled with mass-spectrometer equipped with APCI source and by UV–Vis spectroscopy. Moreover, in order to evaluate the effectiveness of this procedure, we have assayed the capacity of the extracted lycopene to inhibit proliferation in T-lymphocyte jurkat J32 cells in comparison with authentic standard all-trans-lycopene. On this cellular line both standard lycopene and extracted lycopene tended to be dose-dependent but this latter seems to be more active even at lowest concentration.
    European Food Research and Technology 01/2008; 226(3):327-335. · 1.44 Impact Factor
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    ABSTRACT: The fatty acid compositions and the positional distributions of fatty acid in triacylglycerol (TAGs) and phospholipid (PLs) fractions of four cultured freshwater fish species (Salmo trutta, Ictalurus punctatus, Ictalurus melas and Micropterus salmoides) were investigated. As regards the TAGs fraction, the S. trutta (trout) and I. punctatus (channel catfish) species had the highest % content in n3 polyunsaturated fatty acids (PUFAs) and the lowest n6/n3 ratio; this ratio resulted always lower than 1 in all the considered fish species. The PLs fraction of the considered fish was very interesting because of the high percentage of PUFAs, both in phosphatidylcholines and in phosphatidylethanolamines. The fatty acid distribution among the three sn-positions of the glycerol backbone was non-random; generally, both n6 and n3 PUFAs were mainly distributed between sn-2- and sn-3-positions of TAGs while the contents in sn-1-position were generally lower; in PLs fraction these fatty acids preferred the sn-2-position.
    Food Chemistry - FOOD CHEM. 01/2008; 110(1):199-206.
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    ABSTRACT: In this study, sn-1,2-, sn-2,3-, and sn-1,3-diacylglycerols were isolated from olive oil, and their urethane derivatives (urethanes) were prepared. Normal-phase high-performance liquid chromatography (NP-HPLC) separation of the urethane isomers was performed and the separate classes were studied by nuclear magnetic resonance (NMR). The use of 1H NMR and homo- and heteronuclear 2D techniques provided a great amount of information in a very short time, particularly when a high-field NMR instrument (700 MHz) was used. Particularly diagnostic for this kind of compound was the glyceridic moiety that presents typical chemical shifts both for carbon and hydrogen. These studies show the usefulness of NMR spectroscopy to recognize clearly the sn-1,3- and, moreover, sn-1,2- with respect to sn-2,3-diacylglycerols, although very minor differences occur between them.
    Journal of Agricultural and Food Chemistry 02/2007; 55(2):191-6. · 2.91 Impact Factor
  • F. Blasi, L. Cossignani, M. S. Simonetti, P. Damiani
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    ABSTRACT: Enzymatic synthesis of sn-1,3-diacylglycerols (sn-1,3-DAG) in two steps without isolation of the intermediates was investigated. Firstly ethanolysis of extra virgin olive oil (EVO) using immobilized non-regiospecific lipase from Candida antarctica (Novozym 435) was carried out to obtain glycerol (Gly) and fatty acid ethyl esters (FAEE). In the second step the ethanolysis products have been re-esterificated testing different sn-1,3-regiospecific lipases, both immobilized and non-immobilized, in different reaction media, that is in the presence of solvents or in a solvent-free system, for different times, at different temperatures (12, 25 and 40°C). The lipase from Rhizomucor miehei (Lipozyme IM) has been the most effective among the sn-1,3-specific lipases screened.
    Enzyme and Microbial Technology - ENZYME MICROB TECHNOL. 01/2007; 41(6):727-732.