Journal of Analytical Methods in Chemistry

Research Article

Chemical Composition and Seasonality of Aromatic Mediterranean Plant Species by NMR-Based Metabolomics

Table 2

Main metabolites detected in plant extracts. ¹H-NMR data are measured in ppm and coupling constants () in Hertz. Relative amount is expressed as the mean value () ± SD. For some metabolites, the quantitative analysis was not possible due to strongly overlapping signals; hence the presence is indicated by “X.”


Plant species	Metabolites	NMR	Wi	Sp	Su	Au

Calamintha nepeta	Alanine	1.48 (H3, d = 7.2)	X	X	X	X
	Apigenin derivative 1	6.51 (H6 d = 2.1); 6.70 (H3 s); 6.78 (H8 d = 2.1); 7.10 (H3′/H5′ d = 8.7); 7.94 (H2′/H6′ d = 8.7)		8.52 ± 1.08		5.25 ± 3.73
	Apigenin derivative 2	6.54 (H6 d = 2.1); 6.67 (H3 s); 6.73 (H8 d = 2.1); 7.07 (H3′/H5′ d = 8.7); 7.90 (H2′/H6′ d = 8.7)		8.52 ± 1.08		5.25 ± 3.73
	Apigenin derivative 3	6.50 (H6 d = 2.1); 6.66 (H3 s); 6.78 (H8 d = 2.1); 7.02 (H3′/H5′ d = 8.7); 7.88 (H2′/H6′ d = 8.7)			7.81 ± 3.24
	Apigenin derivative 4	6.49 (H6 d = 2.1); 6.61 (H3 s); 6.69 (H8 d = 2.1); 7.06 (H3′/H5′ d = 8.7); 7.84 (H2′/H6′ d = 8.7)			7.81 ± 3.24
	Apigenin derivative 5	6.55 (H6 d = 2.1); 6.65 (H3 s); 6.69 (H8 d = 2.1); 7.12 (H3′/H5′ d = 8.7); 7.95 (H2′/H6′ d = 8.7)	5.16 ± 0.59
	Apigenin derivative 6	6.53 (H6 d = 2.1); 6.65 (H3 s); 6.66 (H8 d = 2.1); 7.09 (H3′/H5′ d = 8.7); 7.92 (H2′/H6′ d = 8.7)	5.16 ± 0.59
	Citric acid	2.59 (H2a, d, = 17.6); 2.72 (H2b, d, = 17.6)	8.38 ± 3.46	13.66 ± 3.31	8.04 ± 0.17	13.44 ± 0.02
	Glucose	4.59 (H1 β, d, = 7.8); 5.19 (H1 , d, = 3.8)	5.89 ± 2.33	6.87 ± 2.99	5.61 ± 0.28	5.64 ± 1.71
	Malic acid	2.39 (H3a, dd, = 15.6, 9.3); 2.78 (H3a, dd, = 15.6, 3.6); 4.31 (H2, dd, = 9.3, 3.6)	26.72 ± 10.80		37.57 ± 2.72	31.45 ± 7.13
	Phenylpropanoid 1	5.97 (H8 d = 15.9); 7.43 (H7 d = 15.9)	3.04 ± 3.01	5.94 ± 0.45	3.05 ± 0.62	2.57 ± 0.67
	Phenylpropanoid 2	6.17 (H8 d = 15.9); 7.30 (H7 d = 15.9)	X
	Phenylpropanoid 3	6.31 (H8 d = 15.9); 7.52 (H7 d = 15.9)	1.02 ± 0.99	4.62 ± 1.99	6.58 ± 1.51
	Phenylpropanoid 4	6.45 (H8 d = 15.9); 7.67 (H7 d = 15.9)	X	X	X	X
	Phenylpropanoid 5	6.16 (H8 d = 15.9); 7.25 (H7 d = 15.9)		X
	Phenylpropanoid 6	6.11 (H8 d = 15.9); 7.37 (H7 d = 15.9)			X
	Phenylpropanoid 7	6.14 (H8 d = 15.9); 7.39 (H7 d = 15.9)				X
	Quinic acid	1.87 (H2a, m); 1.96 (H6a, m); 2.01 (H2b, m); 2.02 (H6b, m), 3.40 (H4, ov); 4.00 (H3, ov); 4.11 (H5, ov);	45.28 ± 6.65	55.09 ± 4.83	64.02 ± 4.16	71.61 ± 8.84
	Sucrose	4.15 (H3′, d, = 8.4); 5.38 (H1, d, = 3.6)	8.24 ± 3.63	7.09 ± 3.01	15.51 ± 2.84	10.37 ± 0.54

Helichrysum Italicum	Alanine	See C. nepeta	1.24 ± 0.19	0.87 ± 0.60	0.91 ± 0.15	1.51 ± 0.44
	Chlorogenic acid	1.84–2.20 (H2 and H6 quinic acid, m); 5.45 (H5, m); 6.37 (H8′, d, = 15.9); 6.90 (H5′, d, = 8.1); 7.07 (H6′, dd, = 8.4, 2.1); 7.15 (H2′, d, = 2.1); 7.62 (H7′, d, = 15.9)	8.31 ± 1.55	9.03 ± 1.24	3.63 ± 2.59	3.26 ± 0.77
	Dicaffeoylquinic acid	6.30 (H8′, d, = 16.2); 6.48 (H8′′, d, = 15.6); 7.65 (H7′, d, = 16.2); 7.66 (H7′′, d, = 15.6)	10.86 ± 1.38	10.88 ± 5.16	11.53 ± 2.38	7.83 ± 2.07
	Glucose	See C. nepeta	3.77 ± 1.74	3.56 ± 0.04	2.73 ± 0.59	3.78 ± 2.01
	3-OH benzofuran	5.18 (H2 d = 6.3); 5.22 (H3 d = 6.3); 6.90 (H7 ov); 8.04 (H6 dd = 8.4, 1.8)	4.06 ± 0.27	3.13 ± 1.39	5.37 ± 1.89	4.06 ± 1.47
	Isobenzofuranone	5.33 (H3 s); 6.73 (H4 d = 1.8); 6.84 (H6 d = 1.8)	6.03 ± 2.70
	Malic acid	See C. nepeta	X	X	X	X
	Neochlorogenic acid	6.39 (H8′, d, = 15.9); 7.52 (H7′, d, = 15.9)	X	X	X	X
	Sucrose	See C. nepeta	16.93 ± 8.55	9.15 ± 4.57	10.24 ± 4.45	10.14 ± 3.75

Foeniculum vulgare	Alanine	See C. nepeta	1.17 ± 0.05	0.90 ± 0.49	1.24 ± 0.25	1.09 ± 0.09
	Caffeic acid	6.29 (H8′, d, = 15.9); 6.88 (H5′, d, = 8.1); 7.03 (H6′, dd, = 8.4, 2.1); 7.12 (H2′, d, = 2.1); 7.52 (H7′, d, = 15.9)	X	X	X	X
	Chlorogenic acid	See H. italicum	X	X	X	X
	Dicaffeoylquinic acid	See H. italicum		X	X	X
	Glucose	See C. nepeta	1.17 ± 0.02	5.55 ± 2.89	5.77 ± 1.64	6.29 ± 1.38
	GABA (-aminobutyric acid)	1.92 (H3, m); 2.36 (H2, t, = 7.5); 3.01 (H4, t, = 7.5)	X	X		X
	Kaempferol	6.35 (H6, d, = 2.1); 6.52 (H8, d, = 2.1); 7.00 (H2′/H6′, d, = 8.4); 8.09 (H3′/H5′, d, = 8.4)	1.28 ± 0.17	1.78 ± 1.56	1.46 ± 0.44	1.18 ± 0.82
	Malic acid	See C. nepeta	44.68 ± 7.11	47.40 ± 10.23	168.52 ± 11.15	86.62 ± 3.49
	Quercetin	6.27 (H6, d, = 2.1); 6.48 (H8, d, = 2.1); 6.99 (H5′, d = 8.5); 7.59 (H6′, d = 8.5, 2.1); 7.75 (H2′, d = 2.1)	1.93 ± 0.36	5.55 ± 3.61	6.23 ± 1.25	2.94 ± 2.09
	Quinic acid	See C. nepeta	25.09 ± 2.62	31.61 ± 17.48	33.49 ± 6.73	27.30 ± 2.25
	Sucrose	See C. nepeta	44.94 ± 2.28	36.80 ± 13.85	54.36 ± 11.86	30.62 ± 9.03
	Threonine	1.32 (H4, d, = 6.6)	X	X	X	X

Micromeria graeca	Alanine	See C. nepeta	0.93 ± 0.55	1.40 ± 0.88	2.09 ± 0.89	5.75 ± 4.04
	Citric acid	See C. nepeta	19.89 ± 9.44	18.65 ± 1.56	17.13 ± 6.84	15.43 ± 5.10
	Glucose	See C. nepeta	4.81 ± 2.49	6.87 ± 2.99	5.61 ± 0.28	5.64 ± 1.71
	Malic acid	See C. nepeta	X	X	X	X
	Quinic acid	See C. nepeta	39.75 ± 10.68	55.09 ± 4.83	64.02 ± 4.16	57.41 ± 11.24
	Rosmarinic acid	3.00 (H7′a, dd, = 14.1, 9.6); 3.15 (H7′b, dd, = 14.1, 3.6); 5.02 (H8′, dd, = 10.0, 3.3); 6.30 (H8, d, =15.9); 6.71 (H6′, dd, = 7.8, 2.1); 6.81 (H5′, d, = 7.8); 6.82 (H5, d, = 8.1); 6.89 (H2′, d, = 2.1); 7.00 (H6, dd, = 8.1, 1.8); 7.11 (H2, d, = 1.8); 7.50 (H7, d, = 15.9)	1.02 ± 0.99	4.62 ± 1.98	6.58 ± 1.51	1.54 ± 0.79
	Sucrose	See C. nepeta	7.99 ± 2.60	7.09 ± 3.02	15.51 ± 2.84	8.22 ± 3.73
	Threonine	See F. vulgare		X

Origanum vulgare	Apigenin derivative 2	See C. nepeta	4.32 ± 0.24	2.95 ± 0.91		—
	Alanine	See C. nepeta	0.58 ± 0.12	0.90 ± 0.17	1.07 ± 0.14	—
	Choline	3.20 (s)	X	X		—
	Citric acid	See C. nepeta	14.74 ± 1.02	22.92 ± 4.13	15.54 ± 1.91	—
	Glucose	See C. nepeta	16.59 ± 2.64	3.62 ± 2.88	4.39 ± 3.82	—
	Lithospermic acid	3.00 (H7′a and b, ov) 6.30 (H8, d, = 15.9); 7.82 (H7, d, = 15.9)	X	X	X	—
	Malic acid	See C. nepeta	27.59 ± 1.69	32.40 ± 8.10	14.74 ± 8.51	—
	Quinic acid	See C. nepeta	30.94 ± 2.86	45.91 ± 1.83	43.12 ± 9.81	—
	Rosmarinic acid	See M. graeca	11.47 ± 6.11	15.73 ± 4.82	35.50 ± 5.91	—
	Sucrose	See C. nepeta	10.05 ± 1.58	4.98 ± 0.45	14.92 ± 4.36	—

Satureja montana	Apigenin derivative 5	See C. nepeta	X
	Apigenin derivative 6	See C. nepeta	X
	Alanine	See C. nepeta	X	X	X	X
	Choline	See O. vulgare	X	X		X
	Chlorogenic acid	See H. italicum	9.47 ± 1.20	15.01 ± 0.51	12.50 ± 5.54	3.66 ± 1.84
	Glucose	See C. nepeta	1.01 ± 0.67	3.96 ± 1.55	2.87 ± 1.47	4.27 ± 1.54
	Malic acid	See C. nepeta	39.32 ± 2.60	32.40 ± 0.99	8.55 ± 3.31	48.76 ± 6.78
	Rosmarinic acid	See M. graeca	7.15 ± 1.26	10.90 ± 1.64	8.84 ± 4.32
	Sucrose	See C. nepeta	10.09 ± 0.93	8.56 ± 4.42	10.07 ± 1.25	9.37 ± 3.91

Thymus longicaulis	Alanine	See C. nepeta	0.34 ± 0.24	1.05 ± 0.11	1.08 ± 0.22	1.28 ± 0.07
	Citric acid	See C. nepeta	X	X	X	X
	Malic acid	See C. nepeta	26.92 ± 15.44	60.05 ± 3.28	35.56 ± 6.80	54.64 ± 14.72
	Quinic acid	See C. nepeta	19.85 ± 8.63	41.16 ± 7.50	40.71 ± 8.30	31.96 ± 3.17
	Glucose	See C. nepeta	3.06 ± 0.33	3.20 ± 0.83	2.65 ± 1.76	3.36 ± 1.41
	Phenylpropanoid 8	6.13 (H8 d = 15.9); 7.46 (H7 d = 15.9)	3.67 ± 1.13	5.65 ± 0.61	4.77 ± 1.24	1.90 ± 1.24
	Rosmarinic acid	See M. graeca	7.10 ± 3.70	7.78 ± 1.98	10.12 ± 1.76	4.87 ± 2.14
	Sucrose	See C. nepeta	7.10 ± 3.70	7.78 ± 1.98	10.12 ± 1.76	4.87 ± 2.14

Signal multiplicity indicated as follows: d = doublet, dd = doublet of doublets, m = multiplet, ov = overlapped, q = quartet, s = singlet, and t = triplet.
Apigenin derivatives 1 and 2; 3 and 4; 5 and 6 were quantified together due to overlapping signals.