Application of hs-spme-gc-ms derived variables for monitoring ripening induced changes in cheese volatile compounds Fig. S1



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Application of HS-SPME-GC-MS derived variables for monitoring ripening induced changes in cheese volatile compounds



Fig. S1. Typical TIC chromatograms of the HS-SPME-GC-MS analyses of “Pirotski kačkavalj” cheese: sample EC1, extraction of flavor compounds carried out with PDMS (top) and PA fibers (bottom); 1-ethanol, 2- 3-methyl-1-butanol, 3- 2-heptanone, 4- 2-nonanone, 5- butanoic acid and 6- hexanoic acid



Fig. S2. a) Dendrogram (AHC analysis) representing chemical composition dissimilarity relationships (relative amounts of individual compounds were used as variables: PA and PDMS original variables) of 16 cheese samples (observations) obtained by Euclidian distance dissimilarity (dissimilarity within the interval [0, 3500], using aggregation criterion-Ward's method). Four statistically different groups of samples were found. b) PCA ordination (original variables) of 16 cheese samples (observations). Axes (F1 and F2 factors-the first and second principal component) refer to the ordination scores obtained for the samples. Axis F1 accounts for ca. 33% and axis F2 accounts for a further 16% of the total variance. c) Dendrogram (AHC analysis) representing chemical composition dissimilarity relationships (relative amounts of classes of compounds were used as variables: PA and PDMS transformed variables) of 16 cheese samples obtained by Euclidian distance dissimilarity (dissimilarity within the interval [0, 9200]). Three statistically different groups of samples were found. d) PCA ordination (transformed variables) of 16 cheese samples. Axis F1 accounts for ca. 38% and axis F2 accounts for a further 34% of the total variance


Table S1. The major compounds (relative abundance ? 2%) identified by HS-SPME-GC/MS analysis of the volatile fractions of two types of “Pirotski kačkavalj” cheese prepared from ewes’ (EC) and cows’ milk (CC) at four different ripening stagesa

RIc

Method of identificationd

RT (min)

Compound

Relative abundance (peak area, %)b

EC1

EC2

EC3

EC4

CC1

CC2

CC3

CC4

PDMSe

PAf

PDMS

PA

PDMS

PA

PDMS

PA

PDMS

PA

PDMS

PA

PDMS

PA

PDMS

PA










ACIDSg

















































600-700

MS, RI, CoI

1.73

Acetic acid

ndh

tri

2.5

4.0

1.6

7.1

5.1

16.2

nd

nd

nd

20.4

2.7

14.3

5.9

16.8

785

MS, RI, CoI

4.97

2-Methylpropanoic acid

nd

nd

tr

1.2

nd

tr

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

831

MS, RI, CoI

5.78

Butanoic acid

0.6

12.0

6.3

35.5

14.3

42.0

6.2

31.2

tr

1.5

tr

2.0

4.2

17.3

2.2

13.1

866

MS, RI, CoI

7.42

3-Methylbutanoic acid

nd

nd

tr

1.6

0.3

0.8

nd

0.8

nd

nd

nd

nd

nd

tr

nd

nd

875

MS, RI, CoI

7.66

2-Methylbutanoic acid

nd

nd

0.1

0.5

tr

0.3

nd

tr

nd

nd

nd

nd

nd

nd

nd

nd

908

MS, RI, CoI

8.60

Pentanoic acid

nd

nd

nd

0.2

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

1010

MS, RI, CoI

10.64

Hexanoic acid

tr

10.4

6.2

15.6

12.2

17.6

6.9

23.2

2.5

18.0

tr

tr

2.3

11.5

tr

6.9

1182

MS, RI, CoI

13.86

Octanoic acid

tr

tr

3.4

1.7

4.5

1.6

tr

3.5

tr

tr

1.7

nd

tr

tr

nd

nd

1377

MS, RI, CoI

16.61

Decanoic acid

nd

nd

0.6

0.9

tr

tr

nd

tr

nd

nd

nd

nd

nd

nd

nd

nd










Subtotal (%)

0.6

22.4

19.1

61.2

32.9

69.4

18.2

74.9

2.5

19.5

1.7

22.4

9.2

43.1

8.1

36.8










ESTERS

















































612

MS, RI, CoI

2.20

Ethyl acetate

3.0

nd

tr

tr

1.6

tr

7.2

nd

1.7

0.8

4.5

tr

4.9

tr

tr

3.5

779

MS, RI, CoI

5.01

2-Methylpropyl acetate

nd

nd

tr

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

801

MS, RI, CoI

5.88

Ethyl butanoate

tr

nd

tr

tr

0.5

2.2

tr

tr

nd

nd

nd

nd

tr

nd

nd

nd

873

MS, RI, CoI

7.11

Propyl butanoate

nd

nd

tr

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

879

MS, RI, CoI

7.33

1-Methylbutyl acetate

nd

nd

0.6

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

881

MS, RI, CoI

8.04

3-Methyl-1-butyl acetate

nd

nd

0.2

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

tr

nd

920

MS, RI, CoI

9.20

Methyl hexanoate

nd

nd

0.1

tr

tr

tr

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

966

MS, RI

9.73

Methyl 2-hydroxy-4-methylpentanoate

nd

nd

nd

nd

nd

nd

nd

nd

tr

1.1

nd

nd

nd

tr

nd

nd

950

MS, RI

9.80

Ethyl 3-oxobutanoate

nd

nd

nd

0.1

nd

nd

nd

0.3

7.0

5.7

0.6

nd

nd

0.7

nd

tr

958

MS, RI, CoI

9.86

2-Methylpropyl butanoate

nd

nd

0.5

0.1

tr

nd

nd

tr

nd

nd

nd

nd

nd

nd

tr

nd

1002

MS, RI, CoI

10.78

Ethyl hexanoate

1.2

nd

2.8

nd

5.7

2.4

1.8

tr

1.0

0.0

tr

nd

0.7

0.3

nd

nd

1030

MS, RI

11.26

1-Methylbutyl butanoate

nd

nd

0.2

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

1046

MS, RI, CoI

11.49

1-Methylethyl hexanoate

nd

nd

tr

nd

0.2

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

1047

MS, RI, CoI

11.83

Butyl 3-methylbutanoate

nd

nd

0.7

0.1

0.3

nd

tr

tr

nd

nd

nd

nd

nd

nd

2.1

nd

1068

MS, RI, CoI

11.88

3-Methylbutyl butanoate

tr

nd

tr

0.1

tr

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd
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