Electronic supplementary material:
Journal: Food Analytical Methods
Title: Metabolic characterization of caviar specimens by 1H NMR Spectroscopy: Towards caviar authenticity and integrity
Authors: Clement Heude†*, Karim Elbayed*, Tangi Jezequel†, Mathieu Fanuel†,
Raphael Lugan#, Dimitri Heintz#, Philippe Benoit‡ and Martial Piotto†*
†Bruker BioSpin France, 34 rue de l’industrie, 67166 Wissembourg, France
*IMIS/ICube Laboratory, Strasbourg University, 67000 Strasbourg, France
#Institut de Biologie Moléculaire des Plantes- UPR 2357, 67084 Strasbourg, France
‡ SCEA Sturgeon, 102 route de Beauval, 33450 Saint Sulpice et Cameyrac, France
Corresponding Author
Martial Piotto E-mail:
Content:
A table presenting the chemical shifts of the metabolites detected in the 1H NMR spectrum of caviar samples (Table S-1). A table showing the predicted Y values obtained on the samples of the blind test (Table S-2). A figure showing the evolution of the different compounds in fermentation process on the NMR spectra for different time of storage during the study in Eppendorf tubes (Figure S-1). A figure showing the PCA scores plot of the evolution of caviar samples stored over a period of 6 months in a fridge for at 4°C (Figure S-2)
# / Metabolites / Group / 1H chemical shift (ppm) / 13C chemical shift (ppm) / TOCSY correlation (ppm)1 / Alanine / β-CH3 / 1.49 / 19.09
α-CH / 3.77 / 53.38
2 / Arginine / γ-CH2 / 1.70 / 1.92; 3.23; 3.73
β-CH2 / 1.92 / 30.52
δ-CH2 / 3.25 / 43.36
CH / 3.74 / 57.43
3 / Aspartate / CH2 / 2.67 / 39.31
CH2’ / 2.79 / 39.49
CH / 3.87 / 55.14
4 / Choline / CH3 / 3.21 / 56.72
β-CH2 / 3.52 / 70.44
α-CH2 / 4.06 / 58.48
5 / Creatine/Phosphocreatine / N-CH3 / 3.04 / 39.84
α-CH2 / 3.92 / 56.72
6 / Ethanolamine / α-CH2 / 3.13 / 44.24
β-CH2 / 3.82 / 60.59
7 / α-Galactose / CH2 / 3.73 / 63.76
CH-4 / 3.98 / 72.20
8 / β-Galactose / CH-2 / 3.48 / 74.84
CH-3 / 3.64 / 75.72
CH-5 / 3.69 / 78.00
CH2 / 3.73 / 63.76
CH-4 / 3.92 / 71.67
CH-1 / 4.58 / 99.46
9 / α-Glucose / CH-4 / 3.39 / 72.55
CH-2 / 3.53 / 74.48
CH-3 / 3.70 / 75.72
CH-6; CH’-6 / 3.82 / 63.58
CH-5 / 3.82 / 74.31
CH-1 / 5.22 / 95.06
10 / β-Glucose / CH-2 / 3.23 / 77.12
CH-4 / 3.39 / 72.55
CH-3; CH-5 / 3.46 / 78.88
CH-6 / 3.70 / 63.76
CH’-6 / 3.89 / 63.76
CH-1 / 4.63 / 98.93
11 / α-Glucuronate / CH-2 / 3.53 / 74.48
CH-3 / 3.70 / 75.72
CH-5 / 4.06 / 75.19
CH-1 / 5.22 / 95.06
12 / β-Glucuronate / CH-3 / 3.48 / 74.84
CH-1 / 4.63 / 98.93
13 / Glutamate / β-CH2 / 2.09 / 2.35; 3.73
γ-CH2 / 2.36 / 36.50
CH / 3.74 / 57.43
14 / Glycerol / CH2 / 3.55 / 65.34
CH2’ / 3.64 / 65.34
CH / 3.77 / 75.01
15 / Glycine / α-CH / 3.55 / 44.24
16 / Isoleucine / δ-CH3 / 0.95 / 13.99
γ-CH3 / 1.02 / 17.51
γ-CH / 1.26 / 0.94; 1.02;1.48;1.97
γ-CH’ / 1.48 / 0.94; 1.02; 1.26; 1.97
β-CH / 1.98 / 38.79
α-CH / 3.65 / 62.53
17 / Lactate / CH3 / 1.33 / 4.09
CH / 4.09 / 73.43
18 / Leucine / δ-CH3 / 0.96 / 23.84
δ-CH3’ / 0.98 / 24.89
γ-CH / 1.72 / 27.18
β-CH2 / 1.73 / 42.65
α-CH / 3.72 / 56.37
19 / Lysine / γ-CH2 / 1.45 / 1.73; 1.90; 1.90; 3.03; 3.74
δ-CH2 / 1.73 / 29.29
β-CH2 / 1.90 / 32.81
ε-CH2 / 3.03 / 41.95
α-CH / 3.74 / 57.43
20 / α-Maltose / CH-4 (2) / 3.39 / 72.55
CH-2 (2) / 3.53 / 74.48
CH-5 (2) / 3.70 / 75.72
CH2 (2) / 3.82 / 63.58
CH-3 (1) / 3.96 / 76.24
CH-1 (1) / 5.23 / 94.36
CH-1 (2) / 5.39 / 102.62
21 / β-Maltose / CH-2 (2) / 3.53 / 74.48
CH-5 (2) / 3.70 / 75.72
CH-3 (1) / 3.73 / 78.88
CH2 (1) / 3.77 / 63.58
CH2 (2) / 3.85 / 63.58
CH-1 (1) / 4.63 / 98.93
CH-1 (2) / 5.39 / 102.62
22 / α-Melibiose / CH-2 (1) / 3.53 / 74.48
CH-3 (1) / 3.70 / 75.72
CH2 (2) / 3.73 / 63.76
CH-2 (2) / 3.81 / 71.32
CH-4 (2) / 3.98 / 72.20
CH-1 (2) / 4.95 / 100.86
CH-1 (1) / 5.23 / 95.59
23 / β-Melibiose / CH-5(1) / 3.23 / 77.12
CH2 (2) / 3.73 / 63.76
CH-2 (2) / 3.81 / 71.32
CH-4 (2) / 3.98 / 72.20
CH-1 (2) / 4.95 / 100.86
24 / Phenylalanine / β-CH / 3.12 / 3.97
β-CH’ / 3.29 / 3.97
α-CH / 3.98 / 59.01
δ-CH / 7.33 / 132.34
ζ-CH / 7.37 / 130.58
ε-CH / 7.42 / 131.99
25 / Serine / α-CH / 3.82 / 59.36
β-CH2 / 3.98 / 63.23
26 / Threonine / γ-CH3 / 1.33 / 22.43
α-CH / 3.56 / 63.41
β-CH / 4.24 / 68.86
27 / Tyrosine / β-CH / 3.04 / 3.92
β-CH’ / 3.21 / 3.92
α-CH / 3.92 / 59.01
ε-CH / 6.90 / 118.80
δ-CH / 7.20 / 133.75
28 / Valine / γ-CH3 / 0.99 / 19.44
γ'-CH3 / 1.04 / 20.85
β-CH / 2.27 / 32.10
α-CH / 3.6 / 63.23
Table S-1: Assignment of the metabolites detected by NMR in the aqueous extract of caviar. A blank in the 13C chemical shift indicates a signal not observed in the 1H-13C HSQC spectrum for sensitivity reasons or peak overlap.
ID / Predicted values (IGP) / Predicted values (Foreign)Sturgeon 1 / 0,7756 / 0,2244
Sturgeon 2 / 0,6386 / 0,3614
Sturgeon 3 / 1,0097 / -0,0097
Sturgeon 4 / 0,9610 / 0,0390
Sturgeon 5 / 1,3272 / -0,3272
Sturgeon 6 / 1,3222 / -0,3222
Sturgeon 7 / 0,8836 / 0,1164
Sturgeon 8 / 0,9729 / 0,0271
Sturgeon 9 / 1,0909 / -0,0909
Sturgeon 10 / 1,1610 / -0,1610
Sturgeon 11 / 0,8909 / 0,1091
Sturgeon 12 / 0,9543 / 0,0457
Sturgeon 13 / 0,8408 / 0,1592
Sturgeon 14 / 0,9999 / 0,0001
Sturgeon 15 / 1,0905 / -0,09905
Sturgeon 16 / 1,1816 / -0,1816
China 1 / 0,1970 / 0,8030
China 2 / 0,1170 / 0,8830
China 3 / 0,2999 / 0,7001
China 4 / 0,2188 / 0,7812
Italy 5 / -0,1248 / 1,1248
Italy 6 / -0,1453 / 1,1453
Uruguay 7 / 0,2858 / 0,7142
Uruguay 8 / 0,4717 / 0,5283
Italy 9 / -0,6223 / 1,6223
Italy 10 / -0,9451 / 1,9451
China 11 / -0,0464 / 1,0464
China 12 / -0,1534 / 1,1534
China 13 / -0,1056 / 1,1056
Aquadem 1 / 0,9056 / 0,0944
Aquadem 2 / 1,0403 / -0,0403
Aquadem 3 / 1,0515 / -0,0515
Aquadem 4 / 1,1092 / -0,1092
Truite Argentière 1 / 1,0427 / -0,0427
Truite Argentière 2 / 0,9765 / 0,0235
Truite Argentière 3 / 0,7649 / 0,2351
Truite Argentière 4 / 0,7404 / 0,2596
Table S-2: Predicted Y values obtained on the different samples of the blind test. Samples attributed unambiguously are shown with a Y value colored in green. Ambiguous samples are shown in orange. All the samples but one are correctly classified. Only sample Uruguay 8 is borderline.
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Figure S-1: Evolution of the different compounds involved in the fermentation processes on 1D 1H NOESY NMR spectra of caviar samples stored in Eppendorf tubes in a fridge for different times of storage up to 18 weeks: a) ethanol, b) α-glucose, c) β-glucose, d) maltose and sucrose, e) acetate and f) lactate.
Figure S-2: PCA scores plot showing the evolution of caviar samples stored over a period of 6 months in a fridge for at 4°C
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