Chemical profile of the organic residue from ancient amphora found in the Adriatic Sea determined by direct GC and GC-MS analysis

An ancient organic residue was collected from the bottom of a Greco-Italian amphora found in the Adriatic Sea and investigated by direct GC and GC- MS analysis. The headspace composition was determined by HS-SPME using: (1) DVB/CAR/PDMS and (2) PDMS/DVB fibres. Higher percentages of benzene derivatives, monoterpenes and other low- molecular aliphatic compounds were obtained by method (1) in contrast to higher percentage of naphthalene and phenanthrene derivatives found by method (2). In comparison with the composition of pine resin, it is more likely that the found low- molecular aliphatic alcohols, acids, esters and carbonyls with 2-phenylethanol were trapped and preserved within the organic residue from stored wine – the amphora’s originally content. Semi- volatile diterpenes methyl dehydroabietate (33.6%) and retene (24.1%) were dominant in the residue CH2Cl2 solution. Other abundant compounds were 1, 4-dimethoxyphenanthrene (6.8%) as well as other naphthalene and/or phenanthrene derivatives [7-(1- methylethyl)-1, 4a-dimethyl-1, 2, 3, 4, 4a, 9, 10, 10a- octahydronaphthalene, 7-(1-methylethyl)-1, 4a- dimethyl-2, 3, 4, 4a, 9, 10-hexahydrophenanthrene, 7- (1-methylethyl)-1, 4a-dimethyl-1, 2, 3, 4, 4a, 9, 10, 10a- octahydro-phenanthrene, 3, 6-dimethylphenanthrene and 2, 3, 5-trimethylphenanthrene]. Possible sources and formation pathways of the major compounds in the residue were discussed

Primjena mikroekstrakcije vršnih para na čvrstoj fazi kao preparativni pristup za plinsku kromatografiju sa spektrometrijom masa

Reviewed in brief are the selected results of the application of headspace solid-phase microextraction as a preparative approach for gas chromatography – mass spectrometry (HS-SPME/GC-MS) for natural organic compounds research at the University of Split, Faculty of Chemistry and Technology. A wide variety of headspace compounds from different natural sources has been identified: lower aliphatic compounds (e.g., C5- and C6-compounds), aromatic compounds, monoterpenes (e.g., linalool derivatives (oxides, anhydro-oxides, epoxides), hotrienol), sesquiterpenes (e.g., eudesmol isomers, hydrocarbons), and C9- and C13-norisoprenoids (e.g., 3,4-dihydro-3-oxoedulan, 4-oxoisophorone, trans-β-damascenone). These compounds are important phytochemicals as flavour/fragrance compounds, chemical markers of the botanical origin or others (e.g., allelochemicals, pheromones, or acaricide residue). This work is licensed under a Creative Commons Attribution 4.0 International License.Ukratko su prikazani odabrani rezultati primjene mikroekstrakcije vršnih para na čvrstoj fazi kao preparativnog pristupa plinskoj kromatografiji – spektrometriji masa (HS-SPME/GC-MS) za istraživanje prirodnih spojeva, koje je provedeno na Kemijsko-tehnološkom fakultetu Sveučilištu u Splitu. Velika raznolikost spojeva vršnih para istražena je iz različitih prirodnih izvora: niži alifatski spojevi (npr. C5- i C6-spojevi), aromatski spojevi, monoterpeni (npr. derivati linaloola (oksidi, anhidro-oksidi, epoksidi), hotrienol), seskviterpeni (npr. eudezmol izomeri, ugljikovodici) te C9- i C13-norizoprenoidi (npr. 3,4-dihidro-3-oksoedulan, 4-oksoisoforon, trans-β-damascenon). Ti su spojevi važne fitokemikalije kao spojevi aroma/mirisa, kemijski marker botaničkog podrijetla ili drugo (npr. aleokemikalije, feromoni ili ostatci akaricida). Ovo djelo je dano na korištenje pod licencom Creative Commons Imenovanje 4.0 međunarodna

GC-MS Fingerprints and Other Physico-chemical Characteristics of Rare Unifloral Prunus cerasus L. Honey

GC-MS fingerprints of unifloral sour cherry ( Prunus cerasus L.) honey were investigated for the first time by GC-FID and GC-MS {after headspace solid phase microextraction (HS-SPME) and ultrasonic solvent extraction (USE)}. Additionally, other physico-chemical characteristics of the samples were determined (total phenolic content, antioxidant activity and CIE L*a*b*C*h chromatic coordinates). The principal volatile components of the honey headspace were lilac aldehydes (46.0; 50.6%) along with benzaldehyde (18.0; 19.4%). The dominant component of the dichloromethane USE extract was vomifoliol (39.6; 44.9%). The abundant identified compounds may only serve as non-specific markers of the honey's botanical origin since they also occur in other honey types. The honey contained low-moderate amount of polyphenols (209.0 - 309.5 mg GAE/kg) and exhibited moderate antioxidant activity (0.4 - 0.6 mmol TEAC/kg; 1.6 - 1.9 mmol Fe2+/kg)

Virgin olive oil and nutrition

Numerous medical studies (a study in seven countries, Monika study, Dart studies, etc. ) have shown that olive oil is one of the most important ingredient of "Mediterranean diet" associated with a reduction in cardiovascular disease and certain types of cancerous diseases. Nutritional and health value of virgin olive oil is attributed to the large proportion of monounsaturated fatty acids (mainly oleic, 55-83 %), and precious unsaponifiable ingredients that include aliphatic and triterpene alcohols, sterols (mainly β-sitosterol), hydrocarbons (squalene), volatile compounds, tocopherols (preferably α-tocopherol), pigments (chlorophylls and carotenoids) and antioxidants. Oleic acid is the most abundant fatty acid in olive oil that is claimed to affect the increase in level of high density lipoprotein (HDL) and reducing levels of low-density lipoprotein (LDL) in the blood plasma. For this reason it is considered that oleic acid could prevent the occurrence of certain cardiovascular diseases which are still one of the major causes of death. Besides the already mentioned high level of oleic acid, virgin olive oil is characterized by a highly valuable unsaponifiable ingredients which are attributed to exceptional biological value as virgin olive oil is classified as functional food

Physico-chemical, colour and textural properties of Croatian traditional dry sausage (Slavonian Kulen)

U ovom istraživanju određivana su fizikalno-kemijska svojstva, instrumentalna boja i tekstura deset različitih uzoraka tradicionalne hrvatske trajne kobasice - slavonskog kulena. Osnovni kemijski sastav pokazao je velike razlike (p < 0,05) u masenom udjelu vode, proteina, masti, te osobito kolagena. Na temelju tih rezultata se može zaključiti da proizvođači koriste različite recepture u proizvodnji i da svi uzorci nisu bili u istoj fazi zrenja. Instrumentalni parametri boje L* i a* slavonskog kulena bili su slični dok je parametar b* značajno varirao (p < 0,05) između uzoraka, što se može biti posljedica različitog masenog udjela i botaničkog podrijetla začina paprike u uzorcima. Parametri profila teksture slavonskog kulena bili su dosta ujednačeni. Vrijednosti parametra profila teksture (čvrstoće, elastičnosti i otpora žvakanju) pokazali su statistički značajnu korelaciju (p < 0,05) s masenim udjelima soli u uzorcima.A study of physico-chemical properties, the instrumental measurement of colour and texture was carried out on ten different brands of traditional Croatian dry fermented sausage known as Slavonian Kulen. Basic physico-chemical properties showed large variability (p < 0.05), especially the collagen content. This can be related to different recipes used by different producers, and different stages of maturation in the samples. Parameters related to colour showed significant variability (p < 0.05), especially the b* values. The higher variability of b* could be related to the amount and botanical origin of paprika spice used in the recipe. The textural properties of examined brands were quite similar. Some differences in hardness, springiness and chewiness were significantly correlated to salt content (p < 0.05)

Characterization of Summer Savory (Satureja hortensis L.) Honey by Physico-Chemical Parameters and Chromatographic / Spectroscopic Techniques (GC-FID/MS, HPLC-DAD, UV/VIS and FTIR-ATR)

Satureja hortensis L. unifloral honey was characterized by pollen analysis, electrical conductivity, pH and extensively by chromatographic and spectroscopic techniques. UV / VIS spectro-scopy measurements revealed total phenol content of 682.1 mg GAE / kg by Folin-Ciocalteu assay, antiox-idant capacity by DPPH assay of 1.7 mmol TEAC / kg and by FRAP assay of 4.3 mmol Fe2+ / kg as well as CIE L*a*b*Cab*h°ab chromaticity coordinates. GC-MS after headspace solid-phase microextraction (HS-SPME) revealed hotrienol (22.8 %) along with other linalool derivatives, benzaldehyde (6.1 %), phenylacetaldehyde (4.9 %) and few norisoprenoids (safranal (7.6 %) as the major). Ultrasonic solvent ex-traction (USE) followed by GC-MS allowed identification of methyl syringate (54.7 %) as predominant compound along with other benzene derivatives. HPLC-DAD analysis determined tyrosine (382.0 mg kg−1), phenylalanine (140.4 mg kg−1) and methyl syringate (39.32 mg kg−1). Methyl syringate and hotrienol can be considered non-specific chemical markers of S. hortensis honey. FTIR-ATR spectral characteristics of S. hortensis honey in fingerprinting region were not significantly different from other honey types, but the integrated intensity of the region was smaller than in other unifloral honeys

BioProspecting of the Adriatic Sea: A Review of Recent Studies of Volatile Organic Compounds

Istraživanja predstavljena u ovom preglednom radu doprinose poznavanju isparljivih organskih spojeva iz morskih organizama, posebno iz makroalgi Jadranskog mora. Za izolaciju isparljivih spojeva iz svježih i/ili na zraku osušenih uzoraka primijenjene su komplementarne metode: mikroekstrakcija vršnih para na čvrstoj fazi (HS-SPME) i/ili hidrodestilacija (HD). Dobiveni izolati analizirani su vezanim sustavom plinske kromatografije-spektrometrije masa (GC-MS). U vršnim parama i isparljivim uljima makroalgi Halopteris filicina, Flabellia petiolata, Dictyota dichotoma, Taonia atomaria, Padina pavonica, Codium bursa i morskoj cvjetnici Posidonia oceanica pronađeno je mnoštvo različitih spojeva, uglavnom seskviterpena, diterpena i alifatskih spojeva. Alifatski spojevi male molekulske mase, poput dimetil-sulfida (DMS), tribrommetana, 1-jodpentana, 3-metilbut-2-enala, heksanala i pent-1-en-3-ona, nađeni su u kemijskim profilima vršnih para. Također su identificirani i alifatski C8- i C11-spojevi (npr. oktan-l-ol, oktanal, okt-1-en-3-ol, 6-metilhept-5-en-2-on, fukoseraten i diktioptereni). Zajedno s višim acikličkim ugljikovodicima, također pronađenim u vršnim parama (npr. heptadekan), u ispitivanim isparljivim uljima identificirani su i viši alifatski alkoholi (npr. (Z)-oktadec-9-en-1-ol, heksadekan-1-ol, (Z,Z)-oktadeka-3,13-dien-1-ol) i esteri (npr. diizooktil-ftalat, dibutil-ftalat). Fenilpropanski derivati (npr. benzaldehid, benzil-alkohol) i C13-norizporenoidi (npr. α-jonon i β-jonon) također su pronađeni u isparljivim profilima, kao i mnoštvo seskviterpena (npr. germakren D, biciklogermakren, δ-kadinen, epizonaren, epibicikloseskvifelandren, β-kubeben, gleenol, (E)-β-farnezen). Isparljivi organski spojevi identificirani u morskim algama mogu poslužiti u kemotaksonomskim istraživanjima. Ovo djelo je dano na korištenje pod licencom Creative Commons Imenovanje 4.0 međunarodna.Studies presented in this review contribute to the knowledge of volatile organic compounds (VOCs) from marine organisms, especially macrolgae from the Adriatic Sea. Complementary methods were used for the isolation of VOCs from fresh and/or air-dried samples: headspace solid-phase microextraction (HS-SPME) and/or hydrodistillation (HD). The isolates were analysed by gas chromatography and mass spectrometry (GC-MS). A variety of different volatile compounds, mainly sesquiterpenes, diterpenes and aliphatic compounds were found in headspace and volatile oils of macroalgae Halopteris filicina, Flabellia petiolata, Dictyota dichotoma, Taonia atomaria, Padina pavonica, Codium bursa, and one seagrass Posidonia oceanica. Low molecular aliphatic compounds were found in the chemical profiles of headspace, such as dimethyl sulphide (DMS), tribromomethane, 1-iodopentane, 3-methylbut-2-enal, hexanal and pent-1-en-3-one. Aliphatic C8- and C11-compounds (e.g., octan-1-ol, octanal, oct-1-en-3-ol, 6-methylhept-5-en-2-on, fucoserratene and dictyopterenes) were also identified. Along with higher acyclic hydrocarbons, which are also found in headspace (e.g. heptadecane), in the investigated volatile oils higher aliphatics alcohols (e.g., (Z)-oktadec-9-en-1-ol, hexadecan-1-ol, (Z,Z)-oktadeca-3,13-dien-1-ol) and esters (e.g., diisooctyl phthalate, dibutyl phthalate) were found. Phenylpropane derivatives (e.g., benzaldehyde, benzyl alcohol) and C13-norisporenoids (e.g., α-ionone and β-ionone) were also identified in the volatile profiles, as well as an array of sesquiterpenes (e.g., germacrene D, bicyclogermacrene, δ-cadinene, epizonarene, epi-bicyclosesquiphellandrene, β-cubebene, gleenol, (E)-β-farnesene). VOCs, identified in marine algae, could be useful for chemotaxonomic studies. This work is licensed under a Creative Commons Attribution 4.0 International License

Kemijska analiza hlapljivih spojeva tradicionalne rakije Anižete s otoka Korčule – Republika Hrvatska

Anižeta je prirodno jako alkoholno piće koje se proizvodi aromatiziranjem rakije lozovače prirodnim ekstraktima zvjezdastog anisa (llicium verum Hook.), anisa (Pimpinella anisum L.), koromača (Foeniculum vulgare Mill.) ili drugog bilja koje sadržava jednake glavne aromatične sastojke. U brojnim zemljama mediteranskog područja rakije aromatizirane anisom imaju dugu tradiciju proizvodnje. U našoj zemlji Anižeta je tradicionalno jako alkoholno piće koje se najvećim dijelom proizvodi na otoku Korčuli. Tijekom proizvodnje rakije nastaju brojne hlapljive tvari čiji udjel i sastav određuje kvalitetu gotovog proizvoda. Cilj ovog rada je utvrditi profil hlapljivih sastojaka rakije Anižete. Za izolaciju hlapljivih spojeva korištena je tehnika mikroekstrakcije vršnih para na krutoj fazi (HS-SPME). Analiza izoliranih hlapljivih spojeva provedena je primjenom plinske kromatografije udružene s spektrometrijom masa (GC-MS). Identificirano je ukupno 26 hlapljivih spojeva koji pripadaju sljedećim kemijskim skupinama: esteri, viši alkoholi, terpeni, fenilpropani i norizoprenoidni derivati. Brojčano su najzastupljeniji esteri, a fenilpropani cis-anetol (17,88 %) i trans-anetol (31,62 %) su prisutni u najvišem relativnom udjelu te doprinose slatkastoj, specifičnoj aromi Anižete. Dobiveni rezultati su uspoređeni sa literaturnim podacima sličnih alkoholnih pića u drugim zemljama

With food to health : proceedings of 11th International symposium

Proceedings contains 13 original scientific papers, 10 professional papers and 2 review papers which were presented at "10th International Scientific and Professional Conference WITH FOOD TO HEALTH", organised in following sections: Nutrition, Dietetics and diet therapy, Functional food and food supplemnents, Food safety, Food analysis, Production of safe food and food with added nutritional value