Electronic Journal of Polish Agricultural Universities (EJPAU) founded by all Polish Agriculture Universities presents original papers and review articles relevant to all aspects of agricultural sciences. It is target for persons working both in science and industry,regulatory agencies or teaching in agricultural sector. Covered by IFIS Publishing (Food Science and Technology Abstracts), ELSEVIER Science - Food Science and Technology Program, CAS USA (Chemical Abstracts), CABI Publishing UK and ALPSP (Association of Learned and Professional Society Publisher - full membership). Presented in the Master List of Thomson ISI.
2008
Volume 11
Issue 1
Topic:
Food Science and Technology
ELECTRONIC
JOURNAL OF
POLISH
AGRICULTURAL
UNIVERSITIES
Bortnowska G. 2008. RELEASE OF CARVONE AND LIMONENE FROM OIL – POLYSACCHARIDE MIXTURES, EJPAU 11(1), #16.
Available Online: http://www.ejpau.media.pl/volume11/issue1/art-16.html

RELEASE OF CARVONE AND LIMONENE FROM OIL – POLYSACCHARIDE MIXTURES

Gra¿yna Bortnowska
Department of Food Technology, West Pomeranian University of Technology, Szczecin, Poland

 

ABSTRACT

Static headspace analysis of oil – polysaccharide mixtures flavoured with caraway shoved higher differences in release of carvone and limonene caused by an increase of fat component (oil and its replacer Frutafit®Tex – inulin) concentration than thickeners addition. The highest changes in retention of carvone and limonene were observed in oil – polysaccharide mixtures containing no more than 10% (w/w) of fat component especially with addition 0.11% (w/w) of xanthan gum. Sensory analysis of the caraway odour intensity of oil – polysaccharide mixtures confirmed results obtained from static headspace analysis and also shoved that with higher concentration of fat component slowly increased odour intensity reported by the assessors as oil odour and/or other (foreign) odour. These odours almost completely dominated caraway odour in samples containing 40% (w/w) of fat component.

Key words: carvone, limonene, Frutafit®Tex – inulin, xanthan gum, guar gum, static headspace analysis, odour intensity.

INTRODUCTION

Decrease of energy content in food products may be obtained, among other things, by reduction fat in their composition. This process very often is connected with increase of water quantity in the system, what causes large changes in rheological properties of new manufactured food products and also may affect qualitative and quantitative odour release [6, ]. However, consumers require that low – fat products will fulfil their traditional sensory expectations [16]. Ingredients commonly applied to manufacture low – fat food products are carbohydrate – based fat replacers which are very often a mixture mutually interacting hydrocolloids as regards physicochemical properties [22, 23]. Hydrocolloids may change odour release, because used in the appropriate amount, increase viscosity of systems and are showing physicochemical interactions with some of the odour molecules [8,24,26]. To the carbohydrate – based fat replacers belongs Frutafit®Tex – inulin, which also is used as an ingredient for developing texture in food products [7]. The use of Frutafit®Tex – inulin is however limited to the 15-20 g per day and advised in multiple doses [15], therefore low – fat systems containing large amount of water require addition of other thickeners. Moreover, it was reported that inulin, also Frutafit®Tex – inulin, did not increase retention of the studied aroma compounds in low – fat model systems and food products [9,25]. Relative good textural properties are shoving guar gum and xanthan gum, which applied in a very low concentration, markedly increase viscosity of the systems [12,13,18] and added as the mixture to the low – fat mayonnaise with Frutafit®Tex – inulin are developing physical and organoleptic properties similar to the traditional product [3]. Furthermore, xanthan gum and guar gum used as a stabilizers migrate slowly to the oil – water interfaces and exhibit some surface and interfacial activities [14], also interacting with aroma compounds affect odour release [28,5]. Although, González-Tomás et al. [11] reported that addition xanthan gum at any concentration did not modify the limonene odour intensity perceived by judges. In the available literature there is no papers dealing with the release of aroma compounds from systems containing mixtures with carbohydrate – based fat replacers and thickeners.

Therefore, the aim of this study was to investigate changes in retention of carvone and limonene, the main ingredients of caraway aroma, from Frutafit®Tex – inulin enriched mixtures depending on guar gum and/ or xanthan gum concentration.

MATERIALS AND METHODS

Raw materials
The study involved:

Model mixture

The model mixtures were produced by slowly mixing vegetable rapeseed oil and natural caraway flavouring (0,4% w/w) into the aqueous solutions of polysaccharides (Frutafit®Tex – inulin, guar gum and/or xanthan gum), then emulsifying the mixtures with an MPW 302 laboratory homogeniser (Mechanika Precyzyjna Warsaw) for 30 s at 15.000 rpm. The polysaccharides were dissolved in distilled water and heated to 80°C and then thoroughly mixed for 3 h [14]. Guar gum and xanthan gum mixed in proportion as 2: 1 (w/w). The model mixtures contained: 0.02, 0.06 and 0.11% (w/w) of guar gum and/or xanthan gum. The fat component (oil and its replacer Frutafit®Tex – inulin) was produced by substituting 4 g oil for 1 g Frutafit®Tex – inulin [8]. The final fat component concentration in the model mixtures was: 1, 3, 5, 10, 20 and 40% (w/w). For the comparison a blank sample, consisting of the caraway flavouring homogenised with water, was prepared each time.

Static headspace analysis
Equilibrium headspace aroma concentrations of carvone and limonene were determined with the use of Perkin – Elmer gas chromatograph interfaced with a mass spectrometer (electron ionization – EI) and autosampler. The flavoured mixtures (5 ml) were placed into 22.3 ml headspace sample vials, which were immediately sealed with butyl rubber caps.

An HS static headspace autosampler with 16 sample capacity was employed with the following conditions: oven temperature, 70°C; transfer line temperature, 70°C; needle temperature, 75°C; GC cycle time, 20.0 min; vial equilibration time, 15 min; pressurization time, 3.0 min; injection time, 0.04 min. The GC analysis used a capillary column PE-SMS 30 m × 0.25 mm i.d., 0.25 µm film thickness and helium as the carrier gas at a constant flow rate of 0.7 ml × min -1. The temperature program was as follows: initial temperature 50°C, program rate 10°C × min -1 and final temperature 150°C. Limonene and carvone peaks were identified by mass spectrometry and thereafter, by comparing them with a Wiley’s mass spectrum library and also by comparing the GC retention indices against known standards. The assays were run in duplicate, two measurements for each sample being taken. All data were expressed relative to water. The values lower than 100% indicated that limonene or carvone were retained by model mixtures [23].

Viscosity measurement
Viscosity of samples containing guar gum and/or xanthan gum was studied using a Rheotest (2 – 50 Hz), RV2 viscometer equipped with S/S1 cylinder. The measurements were carried out at 25 ± 0.5°C and constant shear rate 48.6 (s-1).

Sensory analysis
To the sensory analysis the model mixtures with: 1, 10, 40% (w/w) of fat component and 0.02, 0.06, 0.11% (w/w) of guar gum and/or xanthan gum were chosen. Sensory evaluation by quantitative descriptive analysis (QDA) was performed with a selected and trained panel consisting of 6 assessors.They were selected for their capacity to recognize, memorize, and discriminate odours of model mixtures (PN – ISO 5496). The evaluations were undertaken in a sensory laboratory equipped according to PN – ISO 8589. During training sessions the list of smell descriptors was developed and panelists were trained to evaluate orthonasally odour intensity using a scale 0 to 5. The odour intensity was scored 0-no intensity and 5-very strong intensity (PN – ISO 6564). Definition of smell descriptors were definied as follows: caraway odour-0.5% natural caraway flavouring; oil odour-vegetable rapeseed oil. For the sensory evaluation, samples (20 g) were serve at 37°C.

Statistical analysis
The standard error of the chromatographic areas was calculated for static headspace analysis and a one - way ANOVA, was applied at the error probability of p < 0.05 for sensory analysis. The analysis was run with Microsoft Excel 2000 software.

RESULTS AND DISCUSSION

Static headspace analysis applied to the oil – polysaccharide mixtures, with addition of natural caraway flavouring showed, bigger differences of carvone and limonene release to the headspace caused by an increase of fat component concentration than addition of thickeners. Relative release of the aroma compounds of caraway flavouring (limonene and carvone) decreased with increasing concentration of fat component and in samples with its addition of: 1, 3, 5, 10, 20 and 40% reached maximal values: 74.3, 47.1, 29.0, 14.2, 6.3 and 3.1% respectively (Figs. 1, 2). These results are in good agreement with those obtained by de Roos [6] who, showed that addition only 1% of oil to the model system containing carboxymethylcellulose rapidly decreased release rate, particularly lipophilic aroma compounds. Also other investigations confirmed that fat is a very good solvent, majority of the aroma compounds and significantly decreases quantity of volatile molecules released to the headspace at equilibrium [4,17,20]. The studies also showed that the biggest changes of carvone and limonene release from systems stabilized with addition of guar gum or xanthan gum were noticed in the samples containing no more than 10% of fat component. Increase concentration of Frutafit®Tex – inulin and oil in the system did not influence significantly retention of aroma compounds in evaluated mixtures, what also was stated earlier in samples without addition of thickeners [2]. Retention of carvone and limonene in oil – polysaccharide mixtures depended on concentration and sort of thickeners applied and was highest in samples with addition of xanthan gum, particularly those containing: 1, 3 and 5% of fat component. For example the relative release of aroma compounds of natural caraway flavouring decreased from model mixtures containing 1% of fat component stabilized with addition: 0.02, 0.06 and 0.11% of xanthan gum in comparison to the same samples thickened with guar gum by 13.7, 17.9, 9,8% and 13.5, 19.5, 14.9% for carvone and limonene respectively (Figs. 1, 2). These results can be partly related to the studies of Rankin and Bodyfelt [21] who reported that xanthan gum resulted in the greater decrease in headspace diacetyl than guar gum after correction for viscosity. Instead, addition of guar gum and/or xanthan gum to the oil-polysaccharide mixtures with 10, 20 and 40% of fat component, did not influence significantly release of carvone and limonene, regardless of sort and concentration of thickeners applied. Stabilization of model systems by addition mixtures containing guar gum and xanthan gum, caused in most cases increase of carvone and limonene retention, in comparison to the samples with addition of guar gum and decrease it in relation to the samples containing xanthan gum, irrespective of thickeners and fat component concentration (Figs. 1, 2). The observed differences of carvone and limonene release from oil-polysaccharide mixtures could be affected by viscosity which increased with higher concentration of thickeners, mostly in samples stabilized with addition of xanthan gum (Fig. 3). Also, Secuard et al. [24] reported that limonene release, from polysaccharide matrices, was depressed with increasing concentration of xanthan gum particularly in the range of 0.04 to 0.1%. Otherwise, small quantity of proteins found in gums may interact with limonene and carvone and affect their different release from oil-polysaccharide mixtures [14]. Sensory analysis of the oil-polysaccharide mixtures containing: 1, 10 and 40% of fat component confirmed results obtained from static headspace analysis.

Fig. 1. Comparison of relative carvone release from caraway flavoured oil – polysaccharide mixtures in relation to the concentration of guar gum (G) and/or xanthan gum (X) and quantity of fat component: (a) – 1% (w/w), (b) – 3% (w/w), (c) – 5% (w/w), (d) – 10% (w/w), (e) – 20% (w/w), (f) – 40% (w/w)

Fig. 2. Comparison of relative limonene release from caraway flavoured oil – polysaccharide mixtures in relation to the concentration of guar gum (G) and/or xanthan gum (X) and quantity of fat component: (a) – 1% (w/w), (b) – 3% (w/w), (c) – 5% (w/w), (d) – 10% (w/w), (e) – 20% (w/w), (f) – 40% (w/w)

Fig. 3. Viscosity of water solutions with addition of guar gum (G) and/or xanthan gum (X) depending on their concentration of: 0.02, 0.06 and 0.11% (w/w)

Fig. 3. Comparison of odour intensity profiles of caraway flavoured oil - polysaccharide mixtures in relation to the concentration of guar gum (G) and/or xanthan gum (X) and quantity of fat component: (a) – 1% (w/w), (d) – 10% (w/w), (f) – 40% (w/w)

Table 1. Significance of differences between intensities of selected odour profiles of caraway flavoured oil – polysaccharide mixtures depending on concentration: 0.02, 0.06, 0.11% (w/w) of guar gum (G) and/or xanthan gum (X) and quantity of fat component: (a) – 1% (w/w), (d) – 10% (w/w) and (f) – 40% (w/w)

Samples compared

Significance of differences

Caraway odour

Oil odour

Other (foreign) odour

(a)

(d)

(f)

(a)

(d)

(f)

(a)

(d)

(f)

G/0.02 → X/0.02

G/0.02 → G/X/0.02

G/X/0.02 → X/0.02

G/0.06 → X/0.06

G/0.06 → G/X/0.06

G/X/0.06 → X/0.06

G/0.11 → X/0.11

G/0.11 → G/X/0.11

G/X/0.11 → X/0.11

*

–

*

*

*

–

*

–

*

*

–

–

*

*

*

*

*

–

–

–

–

*

*

–

–

–

–

–

–

–

–

–

–

*

*

–

–

*

*

–

–

–

–

–

–

–

–

–

*

–

*

–

–

*

*

*

–

–

*

–

–

–

–

–

–

*

*

–

–

–

*

*

–

*

–

*

*

–

–

*

*

G/0.02 → G/0.06

G/0.02 → G/0.11

G/0.06 → G/0.11

X/0.02 → X/0.06

X/0.02 → X/0.11

X/0.06 → X/0.11

G/X/0.02 → G/X/0.06

G/X/0.02 → G/X/0.11

G/X/0.06 → G/X/0.11

–

*

*

–

*

*

*

*

–

–

*

*

–

–

–

*

*

*

*

–

–

–

–

–

–

–

–

–

*

*

–

–

–

–

–

–

*

*

–

*

*

–

–

–

–

–

–

–

*

*

–

–

–

–

–

–

*

–

–

–

–

–

–

*

–

–

*

*

–

–

*

*

–

–

–

*

–

*

*

–

–

(*) differences significant (p<0.05).
(–) differences non-significant (p<0.05).

The most intensive caraway odour, assessors reported evaluating oil-polysaccharide mixtures with 1% of fat component, also it was possible to notice that in these samples the odour intensity depended on thickeners applied (Fig. 4). The perceived intensity of caraway odour from model oil-polysaccharide mixtures was mostly decreased by addition of xanthan gum and in comparison to the samples stabilized with the use of guar gum or mixtures of guar and xanthan gum these changes were in most cases statistically significant (Fig. 4, Table 1). Increase concentration of fat component to 10%, lowered odour release of caraway from model samples on average about by 60%, additional increase of fat component to 40% caused that some of the assessors did not perceive odour of caraway flavouring, regardless of guar gum, xanthan gum or their mixtures applied (Fig. 4). Similar relation confirming that fat is the most influencing parameter of odour perception was reported by Miettinen et al. [19] who studied orthonasally odour intensity of linalool from milk. These changes in odour release may be explained as the higher resistance to mass transfer for aroma compounds in samples with increasing fat concentration [7]. Sensory evaluations also shoved that with the progressive decrease in perception of caraway odour, appeared small increase of odour reported by the assessors as oil odour and/ or other (foreign) odour, which in samples containing 40% of fat component, completely dominated caraway odour (Fig. 4). Other (foreign) odour could come from the polysaccharides applied similar as it was reported by Wendin and Hall [27] who, added thickeners (guar gum and xanthan gum) to the salad dressings.

CONCLUSIONS

  1. Release of carvone and limonene, the most important aromatic ingredients of caraway flavouring, from oil-polysaccharide mixtures, depended more on concentration of fat component than concentration of guar gum and/or xanthan gum.

  2. Addition of thickeners, particularly xanthan gum at concentration of 0.11%, to the samples containing no more than 10% fat component decreased release of carvone and limonene from oil – polysaccharide mixtures.

  3. Stabilization of oil-polysaccharide mixtures containing 20 and 40% of fat component, by addition guar gum and/or xanthan gum did not influence statistically significant carvone and limonene retention.

  4. Differentiated release of carvone and limonene from oil-polysaccharide mixtures confirmed sensory analysis concerning intensity of caraway odour which also shoved changes of profile odour, intensified by increase of oil concentration as well as addition of polysaccharides.


REFERENCES

  1. Akoh C. C., 1998. Fat replacers. Food Technol. 52, 3, 47–53.

  2. Bortnowska G., 2005. Influence of oil substitution by inulin on the headspace concentration of carvone and limonene released from caraway preparations. EJPAU 8(4), #80.

  3. Bortnowska G., Makiewicz A., 2006. Technological utility of guar gum and xantan in the manufacture of low- fat inulin enriched mayonnaise. Acta Sci. Pol. Technol. Aliment. 5 (2).

  4. Brauss M. S., Linforth R. S. T., Cayeux I., Harvey B., Taylor A. J., 1999. Altering the fat content affects flavour release in a model yogurt system. J. Agric. Food Chem. 47, 2055-2059.

  5. Charles M., Rosselin V., Beck L., Sauvageot F., Guichard E., 2000. Flavor release from salad dressings: sensory and physicochemical approaches in relation with the structure. J. Agric.Food Chem. 48, 1810-1816.

  6. De Roos K. B., 1997. How lipids influence food flavor. Food Technol. 51, 1, 60-62.

  7. Devereux H. M., Jones G. P., McCormack L., Hunter W. C., 2003. Consumer acceptability of low fat foods containing inulin and oligofructose. J. Food Sci. 68, 5, 1850-1854.

  8. Encyklopedia dodatków do ¿ywno¶ci [Encyclopaedia of ford additives], 2003. www.hotrimex.com.pl [in Polish].

  9. Gijs L., Piraprez G. M Perpéte P., Spinnler E., Collin S., 2000. Retention of sulfur flavours by food matrix and determination of sensorial data independent of the medium composition. Food Chem. 69, 319-330.

  10. Godshall M. A., 1997. How carbohydrates influence food flavor. Food Technol. 51, 1, 63-67.

  11. González-Tomás L., Carbonell I., Costell E., 2004. Influence of type, concentration and flow behaviour of hydrocolloid solutions on aroma perception. Eur. Food Res. Technol. 218, 248-252.

  12. Hennock M., Rahalkar R. R., Richmond P., 1984. Effect of xantan gum upon the rheology and stability of oil – water emulsions. J. Food Sci. 49, 1271-1274.

  13. Hemar Y., Tamehana M., Munro P., Singh H., 2001. Influence of xantan gum on the formation and stability of sodium caseinate oil – in – water emulsions. Food Hydrocoll. 15, 513-519.

  14. Huang X., Kakuda Y., Cui W., 2001. Hydrocolloids in emulsions: particle size distribution and interfacial activity. Food Hydrocoll.15, 533-542.

  15. Human tolerance towards indigestible carbohydrates, 2001. www.sensus.nl.

  16. Katz F., 1998. Fat-free reduced-fat reach maturity. Food Technol.52, 3, 54-56.

  17. Leland J. V., 1997. Flavor interactions: the greater whole. Food Techno.51, 1, 75-80.

  18. Mandala I. G., Savvas T. P., Kostaropulos A. E., 2004. Xantan and locust bean gum influence on the rheology and structure of white model-sauce. J. Food Eng. 64, 335-342.

  19. Miettinen S. M., Hyvönen L., Tuorila H., 2003. Timing of intensity perception of a polar vs nonpolar aroma compound in the presence of added vegetable fat in milk. J. Agric. Food Chem. 51, 5347-5443.

  20. Nongonierma A. B., Springett M., Quéré J. L. L., Cayot P., Voilley A., 2006. Flavour release at gas/matrix interfaces of stirred yoghurt models. Int. Dairy J. 16, 102-110.

  21. Rankin A. S., Bodyfelt F. W., 1996. Headspace diacetyl as affected by stabilizers and emulsifies in model dairy system. J. Food Sci. 61, 5, 921-923.

  22. Schirle-Keller J. P., Chang H. H., Reineccius G. A, 1992. Interaction of flavour compounds with microparticulated proteins. J. Food Sci. 57, 6, 1448-1451.

  23. Schirle-Keller J. P., Reineccius G. A., Hatchwell L. C., 1994. Flavor interactions with fat replacers: effect of oil level. J. of Food Sci. 59, 4, 813-815, 875.

  24. Secouard S., Malhiac C., Grisel M., Decroix B., 2003. Release of limonene from polysaccharide matrices: viscosity and synergy effect. Food Chem. 82, 227-234.

  25. Tárrega A., Costell E., 2006. Effect of inulin addition on rheological and sensory properties of fat – free starch – based dairy desserts. Int. Dairy J. 16, 1104-1112.

  26. Voragen A. G. J., 1998. Technological aspects of functional food-related carbohydrates. Trends Food Sci. Technol. 9, 328-335.

  27. Wendin K., Hall G., 2001. Influences of fat, thickener and emulsifier contents on salad dressing: static and dynamic sensory and rheological analyses. Lebensm.-Wiss. u -Technol. 34, 222-233.

  28. Yven C., Guichard E., Giboreau A., Roberts D. D., 1998. Assessment of interactions between hydrocolloids and flavor compounds by sensory, headspace, and binding methodologies. J. Agric. Food Chem. 46, 1510-1514.

 

Accepted for print: 22.02.2008

Gra¿yna Bortnowska
Department of Food Technology,
West Pomeranian University of Technology, Szczecin, Poland
Papie¿a Paw³a VI St. 3, 71-459 Szczecin, Poland
Phone: (091) 449 65 26
email: Grazyna.Bortnowska@zut.edu.pl

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