Aroma ABT-285 Bedienungsanleitung

Diss. ETH No. 14862Investigation on aroma active photooxidative degradation products originating from dimethyl pentyl furan fatty acids in green tea a

IV

84 Conclusion and OutlookIn contrast to the model experiments, the investigations with the food samples werecomplicated by many factors that could not

Conclusion and Outlook 85compounds investigated should be considered together with all other aroma activevolatiles in the samples. AEDA in combination

86

876REFERENCESAaslyng, M.D., Elmore, J.S., Mottram, D.S. (1998). Comparison of the aromacharacteristics of acid-hydrolyzed and enzyme-hydrolyzed vegeta

88 ReferencesBailey, M.E., Gutheil, R.A., Hsieh, F.-H., Cheng, C.-W., Gerhardt, K.O. (1994a).Maillard reaction volatile compounds and color quality of

References 89Bolzoni, L., Careri, M., Mangia, A. (1990). Characterization of volatile componentsin apricot purées by gas chromatography-mass spectrome

90 ReferencesCiminiello, P., Fattorusso, E., Mango, S., Mangoni, A., Ialenti, A., Di Rossa, M.(1991). Furan fatty acid steryl esters from the marine s

References 91Fuchs, C.T., Spiteller, G. (1999). 9-(3,4-Dimethyl-5-pentyl-furan-2-yl)nonanoic acidand 9-(3,4-Dimethyl-5-propyl-furan-2-yl)nonanoic acid

92 ReferencesGrabic, R., Novák, J., Pacáková, V. (2000). Optimization of a GC-MS/MS method forthe analysis of PCDDs and PCDFs in human and fish tissue

References 93Guth, H., Grosch, W. (1990b). Deterioration of soya-bean oil: Quantification ofprimary flavour compounds using a stable isotope dilution

VIABBREVIATIONSAareaAEDA aroma extract dilution analysisASE accelerated solvent extractionBHT 2,6-di-tert-butyl-p-hydroxy-tolueneCHARM combined hedoni

94 ReferencesHasma, H., Subramaniam, A. (1978). The occurrence of furanoid fatty acid in Heveabrasiliensis latex. Lipids 13, 905-907.Hollnagel, A., Kr

References 95Ishii, K., Okajima, H., Okada, Y., Watanabe, H. (1989b). Effects ofphosphatidylcholines containing furan fatty acid on oxidation in multi

96 ReferencesKawakami, M., Kobayashi, A. (1991). Volatile constituents of green mate and roastedmate. J. Agric. Food Chem. 39, 1275-1279.Kawakami, M.,

References 97Lamikanra, V.T., Dupuy, H. (1990). Analysis of volatiles related to warmed overflavor of cooked chevon. J. Food Sci. 55, 861-862.Lardelli

98 ReferencesMatsui, K., Shibata, Y., Tateba, H., Akikazu, H., Kajiwara, T. (1997). Changes oflipoxygenase and fatty acid hydroperoxide lyase activiti

References 99Nijssen, L.M., Visscher, C.A., Maarse, H., Willemsens, L.C., Boelens, M.H. (1996).Volatile Compounds in Foods - Qualitative and Quantitat

100 ReferencesOta, T., Takagi, T. (1989b). Fatty acids of lipids from fish testes with particularreference to furan fatty acids. Bull. Fac. Fish. Hokk

References 101Pompizzi, R., Lamberti, M., Oechslin, R., Manzardo, G., Amadò, R. (1997).Identification of bovolides as degradation products of furan fa

102 ReferencesRubin, M.B. (1969). Photochemistry of σ-Quinones and α-Diketones. Fortschr. Chem.Forsch. 13, 251-306.Ruiz, J., Cava, R., Ventanas, J., J

References 103Schlüter, S., Steinhart, H., Schwarz, F.J., Kirchgessner, M. (1999). Changes in theodorants of boiled carp fillet (Cyprinus carpio L.) a

VI AbbreviationsPE polyethylener correlation coefficientRFIDpeak area ratio, based on FID dataRI retention indexRMSpeak area ratio, based on MS dataR

104 ReferencesSiek, T.J., Albin, I.A, Sather, L.A., Lindsay, R.C. (1969). Taste thresholds of buttervolatiles in deodorized butteroil medium. J. Food

References 105Sutherland, M.M., Ames, J.M. (1995). The effect of castration on the headspacearoma components of cooked lamb. J. Sci. Food Agric. 69, 4

106 ReferencesTriqui, R., Reineccius, G.A. (1995b). Changes in flavor profiles with ripening ofanchovy (Engraulis encrasicholus). J. Agric. Food Chem.

References 107Wahl, H.G., Chrzanowski, A., Müller, C., Liebich, H.M., Hoffmann, A. (1995).Identification of furan fatty acids in human blood cells and

108 ReferencesYoshioka, M., Hashimoto, K., Fukuhara, T., Hasegawa, T. (1998). Reaction ofsinglet oxygen with enolic tautomers of 1-aryl-2-methyl 1,3-

CURRICULUM VITAE1971 Born on 07 April in Flüelen UR1978 - 1984 Primary school Flüelen UR1984 - 1991 Gymnasium Altdorf UR, Matura Type B1992 - 1998 Stu

VIIII SUMMARYIn the present work furan fatty acids (FFA) and their aroma active photooxidativedegradation products were investigated in dried green pl

VIII Summaryoxidation products derived from 2,3-octanedione. Based on the results of the modelexperiments, other pathways for the formation of FFA pho

IXIII ZUSAMMENFASSUNGIn der vorliegenden Arbeit wurden Furanfettsäuren (FFA) und deren aromaaktive,photooxidativ gebildete Abbauprodukte in grünem get

X Zusammenfassungund Hexansäure gehörten zu den aromaaktiven Oxidationsprodukten von 2,3-Octandion. Basierend auf den Resultaten aus diesen Modellexpe

11INTRODUCTIONFuran fatty acids (FFA) are minor components of the lipid fraction and occur widely indifferent plants, vegetable oils, seafood and mamm

2 IntroductionIn order to study the aroma active photooxidative degradation products of FFA it isnecessary to isolate the volatile substances from the

32LITERATURE REVIEW2.1 Furan fatty acids2.1.1 Structure and nomenclatureFuran fatty acids (FFA) (Fig. 1) are characterised by the presence of a di-, t

4 Literature Reviewby Rahn et al. (1981) will be used. Tab. 1 gives an overview of the nomenclature and theabbreviations of the most common FFA.In nat

Literature Review 52.1.2 OccurrenceThe analysis of different lipid fractions have revealed FFA to be constituents ofcholesteryl esters, triglycerides

6 Literature ReviewFFA have been identified as minor components in blood, liver, muscle and lipid tissueand in milk of rats (Gorst-Allman et al., 1988

Literature Review 7pentylMeF(3,5) crayfish Ishii et al. (1988a)MeF(5,5) butter and butter oil Guth and Grosch (1992)MeF(7,5) crayfish Ishii et al. (19

8 Literature Review2.1.3 RelevanceThe role of the FFA in biological systems remains more or less obscure. According toBatna and Spiteller (1994a, 1994

Literature Review 9FFA are considered as precursors of some potent aroma compounds. 3-Methyl-2,4-nonanedione (MND) was the first aroma compound that w

10 Literature ReviewBased on an aroma extract dilution analysis (AEDA), Guth and Grosch (1989, 1990a)identified MND as the most important odorant of s

Literature Review 111999b). Though MND showed a potent retronasal OAV, the compound had nooutstanding sensory characteristics in soybean lecithin. The

12 Literature Reviewcooked spinach leaves as a heavy, tenacious compound exhibiting a green, stalk, lovage-like note. Its structure is related to MND,

Literature Review 13 Figure 2: Proposed pathway for the photooxidative formation of MND(Guth and Grosch, 1991)Figure 3: Proposed pathway for the photo

Für meine ElternIn Liebe und Dankbarkeit

14 Literature Review2.2.2 2,3-Octanedione2,3-Octanedione is an aroma compound which odour has been described in manydifferent ways in the literature.

Literature Review 15yeast extract 2,3-octanedione has been stated as an aroma compound (Ames and Elmore,1992). Recently, 2,3-octanedione was detected

16 Literature Review(Lamikanra and Dupuy, 1990), beef patties stored under vacuum (Spanier et al., 1992a,1992b) and freeze-dried lean beef (Thongwong

Literature Review 17However, a strong correlation between the formation of 2,3-octanedione and of hexanalwas observed. This findings led the authors t

18 Literature ReviewReaction of the epoxide moiety with water leads to the dihydroxy compound which thenis oxidised to the corresponding diones. React

Literature Review 19neutral fraction derived from Burley and Virginia tobacco (Forsblom et al., 1990).The odour of bovolide is described as celery-lik

20 Literature Reviewcompound 2,3-dimethylhept-2-en-4-olide was also identified beside the dihydro-bovolide (Yajima et al., 1983).Both bovolides have b

Literature Review 21Some years later, Pompizzi et al. (2000) confirmed the oxidative formation of bovolidesfrom pentyl DiMeF in model experiments and

22 Literature Review Figure 6: Proposed pathway for the autoxidative formation of bovolide (Pompizzi et al., 1997)OR1R2R1 = (CH2)3CH3R2 = (CH2)7COOCH

Literature Review 23 Figure 7: Proposed pathway for the photooxidative formation of bovolide (Pompizzi et al., 2000)Figure 8: Hypothetical photooxidat

Neue Ideen sind nur durch ihreUngewohnheit schwer verständlich.Franz Marc, dt. Maler

24 Literature Review2.2.4 PentanalAccording to the general description the odour of pentanal is pungent and almond-like(e.g. Schnabel et al., 1988).

Literature Review 25flavour. The fat from animals finished on grain exhibited a significantly less lambyflavour compared to fat from animals finished

26 Literature Reviewdiacetyl could not be explained for all food products. For example the origin of 2,3-butanedione as potent odorant in boiled trout

273EXPERIMENTAL PART3.1 Material3.1.1 Sample materialDried samples of tarragon (Artemisia dracunculus), basil (Ocimum basilicum), savory(Satureja hort

28 Experimental Partdiluting 1 ml of the stock solution to 10 ml with diethyl ether. In Tab. 5 the exactconcentrations of the components of the stock

Experimental Part 29(Fluka 67690), isolute HM-N (Separtis 9800-0060), isopropanol (Riedel-de Haën27225), magnesium sulfate anhydrous (Fluka 63136), me

30 Experimental Part3.2.2 2,3-OctanedioneAccording to Zibuck and Seebach (1988), 39.8 g (186.1 mmol) sodium periodate wasadded to a mixture of 5 g (45

Experimental Part 313.3.2 Capillary gas chromatography-mass spectrometry (GC-MS)GC-MS was performed using the OC injection technique on a GC 8065 gasc

32 Experimental Part(2.8 m, 530 µm ID, J & W Scientific) was used. Data processing was achieved with theICIS 2 version 8 software (Finnigan). Tab

Experimental Part 333.3.3 Capillary gas chromatography-ion trap mass spectrometry (GC-MS/MS)GC-MS/MS was performed either on a Trace GC 2000 series ga

DANKSAGUNGAn der erfolgreichen Durchführung der Dissertation sind immer mehrere Personenbeteiligt. Ich danke ganz herzlich... Prof. Dr. Renato Amad

34 Experimental PartData processing was achieved with the XCalibur version 1.1 software (ThermoQuestFinnigan) or with the Saturn View (TM) version 5.4

Experimental Part 353.3.5 Capillary gas chromatography-olfactometry (GC-O)For sniffing experiments, a GC-FID system of the type HP GC 5890 series II (

36 Experimental Part3.4 Extraction methods3.4.1 Simultaneous distillation solvent extraction (SDE)The extraction of the volatile compounds was perform

Experimental Part 37(ISTD 3) were added and the extract dried (MgSO4). The samples were analysed withGC-FID (Tab. 6) and/or GC-MS (Tab. 7, method A).

38 Experimental Part3.5 Light exposure experiments3.5.1 Sample preparationThe dried samples were packed under air or oxygen atmosphere in transparent

Experimental Part 39ensured a constant illuminance during the exposure period. 3.5.3 Light exposure model system IIThe experiments were carried out in

40 Experimental Part3.6 Oxidation experimentsThe experiments were performed under photooxidative conditions at 4 °C in twodifferent organic solvents a

Experimental Part 413.6.1 Conditions in hexaneIn 200 ml hexane, 20 mg meso-tetraphenyl porphyrine was dissolved with the aid of anultrasonic bath and

42

434RESULTS AND DISCUSSION4.1 Analysis of furan fatty acids4.1.1 Development of a method using ion trap gas chromato-graphy-mass spectrometryIn order t

Part of this work has been published:• Sigrist, I.A., Wunderli, B., Pompizzi, R., Manzardo, G.G.G., Amadò, R. (2000). Influence ofdimethyl furan fatty

44 Results and Discussion As an example for the efficiency of the method, the ion trap GC-MS chromatograms ofthe fatty acid methyl ester extract of ch

Results and Discussion 45Grabic et al. (2000) stated that at a constant isolation time and excitation time the yieldof product ions from an MS/MS expe

46 Results and DiscussionTable 13: Intensity of the diagnostic ion for pentyl DiMeF at varying collision energyexcitation voltage [V]peak area diagno

Results and Discussion 47The highest intensity of the target product ions was obtained at an excitation voltage of1.2 V for both the pentyl DiMeF and

48 Results and Discussion In the samples, DiMeF(9,5) and DiMeF(11,5) as well as DiMeF(11,3) were quantifiedwith the internal standard method. DiMeF(8,

Results and Discussion 49Figure 14: Calibration graphs for quantification of different furan fatty acids (n=2)A: DiMeF(9,5)B: DiMeF(11,3)C: DiMeF(11,5

50 Results and DiscussionSeveral methods for the quantitative determination of FFA have been published. In thesemethods the lipids have to be pre-frac

Results and Discussion 51Table 15: Concentrations of furan fatty acids in green tea, different herbs and vegetablessample DiMeF(11,3)1MeF(9,5) MeF(11

52 Results and DiscussionDiMeF(11,5) was found in all samples, whereas DiMeF(9,5) could not be detected insavory, basil, leek and onion. Chervil and t

Results and Discussion 534.2 Isolation of furan fatty acid photooxidative degra-dation products by using micro simultaneous distillation solvent extra

ITABLE OF CONTENTSIABBREVIATIONS VII SUMMARY VIIIII ZUSAMMENFASSUNG IX1INTRODUCTION 12LITERATURE REVIEW 32.1 Furan fatty acids 32.1.1 Structure and no

54 Results and Discussionan aqueous mixture and from a green tea matrix. In Tab. 16 the RV of the analytes andof the ethyl decanoate (ISTD 1) and the

Results and Discussion 55butanedione (83.6 %) was expected because of the relatively high volatility of thiscompound compared to the other analytes. I

56 Results and Discussiondecanoate (ISTD 1) was shown to be suitable for both sample preparation and GCanalysis. However, it must be taken into accoun

Results and Discussion 57The calculated RMS values for ISTD 1/ISTD 3 and ISTD 2/ISTD 3 showed good RSDfrom 2.8 % to 7.6 % and from 4.8 % to 6.7 %, res

58 Results and DiscussionTable 18: Main products derived from MND under different reaction conditions in hexane, expressed as peak area ratio to thein

Results and Discussion 59Table 19: Main products derived from MND under different reaction conditions in methanol, expressed as peak area ratio to the

60 Results and DiscussionOnly products with an RMS of > 0.1 (based on TIC) were considered. MND showed tobe stable under oxidative conditions in th

Results and Discussion 61 The main oxidation product of MND was 3-hydroxy-3-methyl-2,4-nonanedione(HMND). This substance was shown to be aroma active

62 Results and DiscussionThe infrared spectra of HMND and of MND are shown in Fig. 18. According to J.H. vander Maas (2002, personal communication) th

Results and Discussion 63stretching. Therefore MND and HMND exhibit the C=O stretching peak in the sameregion. Figure 18: GC-IR spectra of MND (A) an

II Table of Contents3EXPERIMENTAL PART 273.1 Material 273.1.1 Sample material 273.1.2 Reference aroma compounds 273.1.3 Model mixture of reference aro

64 Results and DiscussionIn MND, keto-enol tautomerism may occur. The broad band at 1608 cm-1 in the spec-trum of MND (Fig. 18 A) could be due to this

Results and Discussion 65Some of the products formed under the different experimental conditions have not beenidentified yet. The mass spectral charac

66 Results and DiscussionMND can not play the role of a sensitiser. Its absorbance maximum is at 287 nm and thelamps used for the experiments under ph

Results and Discussion 67 Based on the results obtained in the present study the formation of 2,3-octanedione cannot only be explained by the pathway

68 Results and DiscussionTable 21: Main products derived from 2,3-octanedione under different reaction conditions in hexane, expressed as peak area r

Results and Discussion 69Table 22: Main products derived from 2,3-octanedione under different reaction conditions in methanol, expressed as peak arear

70 Results and Discussion Figure 20: GC-MS chromatogram of products derived from 2,3-octanedione under photooxidative conditions in hexane (see Tab.

Results and Discussion 71As in the experiments with MND (chapter 4.3.1), only few products were formed andthe solvent had little influence on the prod

72 Results and DiscussionIn the photochemical experiment, the same compounds, except pentanal, were detectedas in the unsensitised oxidation. Accordin

Results and Discussion 734.4 Formation of furan fatty acid photooxidative degradation products in green teaThe formation rate of the aroma compounds p

Table of Contents III3.6 Oxidation experiments 403.6.1 Conditions in hexane 413.6.2 Conditions in methanol 414RESULTS AND DISCUSSION 434.1 Analysis of

74 Results and Discussion Figure 23: Formation of pentanal (A), bovolide (B) and dihydrobovolide (C) in green tea under photooxidative conditions

Results and Discussion 75 Figure 24: Formation of the diones MND (A), HMND (B), 2,3-octanedione (C) and 2,3-butanedione (D) in green tea under photoox

76 Results and DiscussionAn increase in the illumination from 3’200 lx to 40‘000 lx - all other experimentalconditions were kept constant - did not re

Results and Discussion 77As discussed in chapter 4.3.1, 2,3-butanedione, 2,3-octanedione and HMND are pro-ducts obtained from MND by a photooxidative

78 Results and Discussion The differences between the results obtained with green tea and those with other plantand animal materials as well as pure F

Results and Discussion 79thresholds in water of the aroma compounds formed by photooxidation of FFA in greentea.The thresholds vary in a broad range f

80 Results and DiscussionOnce MND has been formed in green tea, further influence of light is not expected tocause relevant changes in the flavour by

Results and Discussion 81Table 25: Relative concentrations of aroma compounds (expressed as RMS) in different herbs and vegetables before and afterlig

82 Results and DiscussionIn addition to the FFA, other constituents have to be taken into account by interpretingthe different behaviour of the invest

835CONCLUSION AND OUTLOOKIn previously performed model experiments DiMeF were identified as precursors of thearoma compounds pentanal, 2,3-butanedione