Phytochemicals, antioxidant, and antityrosinase activities of Achillea sivasica Çelik and Akpulat

Figures & data

Table 1. Essential oils and extract yields of Achillea sivasica.

	Plant part	Extracts
		MeOH	EtOAc	Aqueous	EO
Yield (%)	Herb	10.2	2.0	14.6	0.056
	Flower	9.3	2.9	10.5	0.048
	Leaf	9.6	2.5	14.0	0.036

EO: Essential oil.

Table 2. Chemical composition of Achillea sivasica essential oils obtained from the herb, flower, and leaves.

No	RRI^a	RRI^b	Compound	Herb	Flower	Leaf	ID method
				%^c
1.	1032	1034^[Citation77]	β-Pinene	11.5	9.3	6.7	^d
2.	1076	1052^[Citation78]	Camphene	1.2	0.5	1.2	^d
3.	1118	1118[^[Citation79]	β-Pinene	7.0	3.0	6.9	^d
4.	1132	1128^[Citation80]	Sabinene	1.7	1.7	1.0	^d
5.	1203	1206^[Citation80]	Limonene	1.0	-	1.4	^d
6.	1213	1216^[Citation81]	1,8-Cineole	18.0	22.1	6.7	^d
7.	1256	1257^[Citation81]	γ-Terpinene	1.0	1.1	0.7	^d
8.	1474	1484	trans-Sabinene hydrate	0.1	2.1	0.6	^d
9.	1497	1497^[Citation79]	β-Copaene	1.7	2.8	0.7	^d
10.	1532	1532^[Citation82]	Camphor	7.6	4.1	9.0	^d
11.	1586	1586^[Citation82]	Pinocarvone	2.0	2.5	1.3	^d
12.	1611	1611^[Citation82]	Terpinen-4-ol	2.2	3.2	1.4	^d
13.	1668	1636	(Z)-β-Farnesene	3.1	2.5	-	^d
14.	1670	1670^[Citation83]	trans-Pinocarveol	0.8	2.0	1.6	^d
15.	1719	1717^[Citation84]	Borneol	2.0	3.7	2.0	^d
16.	1722	1717^[Citation85]	Germacrene D	4.8	3.5	2.0	^d
17.	1804	1804^[Citation86]	Myrtenol	0.5	1.0	0.5	^d
18.	1868	1868^[Citation86]	(E)-Geranyl acetone	0.4	0.3	1.1	^d
19.	1957	1957^[Citation87]	Cubebol	0.6	1.1	0.3	^d
20.	2144	2150^[Citation82]	Spathulenol	0.6	1.1	0.5	^d
21.	2187	2185^[Citation82]	T-Cadinol	1.2	1.5	1.0	^d
22.	2232	2208^[Citation88]	β-Bisabolol	7.5	4.3	6.6	^d
23.	2256	2257^[Citation79]	β-Eudesmol	3.1	3.9	3.6	^d
24.	2265	2265^[Citation89]	Longiverbenone	2.9	1.0	4.9	^e
25.	2300	2300^[Citation86]	Tricosane	1.4	2.6	-	^d
26.	2622	2622^[Citation86]	Phytol	0.9	-	2.8	^e
27.	2900	2900^[Citation86]	Nonacosane	0.6	0.3	4.5	^d
28.	2931	2931^[Citation86]	Hexadecanoic acid	0.3	1.0	4.5	^d
Total				85.7	82.2	73.5

RRI: Relative retention indices calculated against n-alkanes; ^aRelative retention indices calculated against n-alkanes (C₉-C₄₀) on HP–Innowax column; ^bRelative retention indices on polar column reported in literature; ^cPercentage calculated from FID data, > % 0.3; ^dIdentification based on retention index and mass spectrum of genuine compounds on the HP–Innowax column; ^eIdentification on the basis of computer matching of the mass spectra from Adams, MassFinder, WileyNIST libraries; ID: Identification method. The bold values represents major components of the oils.

Figure 1. The distribution of major compound classes in Achillea sivasica herb, flower, and leaf essential oils. OM: oxygenated monoterpenes; MH: monoterpene hydrocarbons; OM: oxygenated sesquiterpenes; SH: sesquiterpene hydrocarbons.

Table 3. The total phenolic and flavonoid contents in the solvent extracts of Achillea sivasica (mean ± SD).

	Extracts
	Plant part	MeOH	EtOAc	Aqueous
Total phenolic content (mg GAEs/g extract)	Herb	34.5 ± 1.7^§	32.4 ± 2.1	17.4 ± 0.2
	Flower	51.1 ± 0.8	28.5 ± 1.0	17.9 ± 0.2
	Leaf	54.7 ± 2.2	38.6 ± 0.5	22.7 ± 0.6
Total flavonoid content (mg QEs/g extract)	Herb	31.7 ± 1.0	12.5 ± 2.8	3.9 ± 1.2
	Flower	27.1 ± 2.0	14.5 ± 4.3	3.7 ± 0.2
	Leaf	31.4 ± 3.9	15.3 ± 1.6	4.4 ± 0.5

GAE: mg gallic acid equivalents/g extract; QE: mg quercetin equivalents/g extract; ^§data obtained from experiments were expressed as mean standard error (±SEM).

Table 4. Mass spectral data and putative identification of Achillea sivasica herb extracts components.

tR (min)	[M-H]^−(m/z)	MS/MS (m/z)	Identification	Extracts			Ref.
				MeOH extract	EtOAc extract	Aqueous extract
6.9	353	191, 173	5-Caffeoylquinic acid	+	+	+	^[Citation15]
7.0	401	269, 161	Apigenin pentoside			+	^[Citation90]
7.8	563	503, 473, 425, 383, 353	Apigenin C-hexoside-C-pentoside	+		+	^[Citation16]
7.9	593	353, 383, 473, 443	Apigenin C-hexoside-C-hexoside	+		+	^[Citation16]
8.1	447	357, 327, 429, 285	Luteolin 6-C-glucoside	+	+	+	^[Citation16]
8.3	461	341, 313, 298, 285	Chrysoeriol C-hexoside	+	+	+	^[Citation63]
9.9	431	341, 311, 283	Apigenin −8-C glucoside	+			^[Citation64]
9.9	461	429, 371, 341, 313, 298	300 amu flavonoid + C glucoside like Swertiajaponin	+	+	+	^[Citation91]
10.3	447	285	Luteolin glucoside	+	+		^[Citation92]
10.3	493	331, 315,287	Patuletin-7-glucoside	+			^[Citation93]
10.5	477	315, 299	Isorhamnetin O-hexoside or Eupafolin-7-glucoside	+			^[Citation16]
11.8	353	191, 179, 173, 135	3-Caffeoylquinic acid	+			^[Citation15]
14.3	423 /421	163 /161	Coumaric acid hexoside derivative		+		^[Citation94]
12.5	515	353, 191, 179, 173	4,5-Dicaffeoylquinic acid	+			^[Citation95]
12.6	461	446, 313, 298, 283, 255	Hispidulin-7-glucoside		+		^[Citation65,Citation96]
25.1	313	297, 283, 255, 163, 117	Cirsimaritin		+		^[Citation18]
25.3	343	328, 313, 298, 285	Santin	+	+		^[Citation97]

Table 5. Biological activities of the essential oils and extracts of Achillea sivasica (mean ± SD).

		Antioxidant activity
	Extract type	β-Carotene^a	CUPRAC^b	DPPH^c	Antityrosinase activity^d
Herb	MeOH	49.9 ± 3.5	0.6 ± 0.02	0.22 ± 0.025	4.9 ± 0.4
	EtOAc	40.2 ± 4.6	0.5 ± 0.02	NE	NE
	Aqueous	29.7 ± 4.2	0.31 ± 0.04	0.53 ± 0.37	NE
	EO	22.1 ± 4.3	0.81 ± 0.03	NE	NE
Flower	MeOH	41.5 ± 2.9	0.6 ± 0.03	0.38 ± 0.055	3.05 ± 0.4
	EtOAc	30.2 ± 3.4	0.5 ± 0.03	NE	2.9 ± 0.2
	Aqueous	35.5 ± 2.2	0.25 ± 0.008	4.88 ± 3.13	NE
	EO	17.0 ± 3.3	0.57 ± 0.1	NE	NE
Leaf	MeOH	53.9 ± 3.1	0.94 ± 0.02	0.12 ± 0.003	5.5 ± 0.8
	EtOAc	55.8 ± 2.8	0.46 ± 0.01	NE	6.2 ± 0.5
	Aqueous	30.1 ± 3.6	0.22 ± 0.02	0.90 ± 0.33	NE
	EO	10.8 ± 3.0	0.74 ± 0.008	NE	NE
GA^e				0.001 ± 0.0001
BHT^f		85.45 ± 6.26

^a% Inhibition;^bTrolox equivalent, mM; ^cIC₅₀, mg/mL; ^dKojic acid equivalent, mg/g; NE: Not effective; ^eGA: gallic acid; ^fBHT: butylated hydroxytoluene.

Kaul, P.N.; Rajeswara Rao, B.R.; Singh, K.; Bhattacharya, A.K.; Mallavarapu, G.R.; Ramesh, S. Volatile Constituents of Essential Oils Isolated from Different Parts of Alpinia calcarata Rosc. Journal of Essential Oil Research 2005, 17(1), 7–9.

 Web of Science ®Google Scholar

Keefover-Ring, K.;. Making Scents of Defense: Do Fecal Shields and Herbivore-Caused Volatiles Match Host Plant Chemical Profiles? Chemoecology 2013, 23(1), 1–11.

 Web of Science ®Google Scholar

Noorizadeh, H.; Farmany, A.; Noorizadeh, M. Application of GA-PLS and GA-KPLS Calculations for the Prediction of the Retention Indices of Essential Oils. Química Nova 2011, 34(8), 1398–1404.

 Web of Science ®Google Scholar

Cavaleiro, C.; Pinto, E.; Goncalves, M.; Salgueiro, L. Antifungal Activity of Juniperus Essential Oils against Dermatophyte, Aspergillus and Candida Strains. Journal of Applied Microbiology 2006, 100(6), 1333–1338.

 PubMed Web of Science ®Google Scholar

Asikin, Y.; Fukunaga, H.; Yamano, Y.; Hou, D.X.; Maeda, G.; Wada, K. Effect of Cultivation Line and Peeling on Food Composition, Taste Characteristic, Aroma Profile, and Antioxidant Activity of Shiikuwasha (Citrus depressa Hayata) Juice. Journal of the Science of Food and Agriculture 2014, 94(12), 2384–2392.

 PubMed Web of Science ®Google Scholar

Maggio, A.; Rosselli, S.; Bruno, M.; Spadaro, V.; Raimondo, F.M.; Senatore, F. Chemical Composition of Essential Oil from Italian Populations of Artemisia alba Turra (Asteraceae). Molecules 2012, 17(9), 10232–10241.

 PubMed Web of Science ®Google Scholar

Saraccedil, H.T.; Akın, M.; Huuml, K.; Başer, C. Chemical Composition and Antibacterial Activity of Essential Oils from Different Parts of Some Bupleurum L. Species. African Journal of Microbiology Research 2012, 6(12), 2899–2908.

 Google Scholar

Bignell, C.; Dunlop, P.; Brophy, J. Volatile Leaf Oils of Some South‐Western and Southern Australian Species of the Genus Eucalyptus (Series 1). Part XIX. Flavour and Fragrance Journal 1998, 13(2), 131–139.

 Web of Science ®Google Scholar

Brophy, J.J.; Goldsack, R.J.; Punruckvong, A.; Bean, A.R.; Forster, P.I.; Lepschi, B.J.; Doran, J.C.; Rozefelds, A.C. Leaf Essential Oils of the Genus Leptospermum (Myrtaceae) in Eastern Australia. Part 7. Leptospermum petersonii, L. Liversidgei and Allies. Flavour and Fragrance Journal 2000, 15(5), 342–351.

 Web of Science ®Google Scholar

Noorizadeh, H.; Farmany, A. Exploration of Linear and Nonlinear Modeling Techniques to Predict of Retention Index of Essential Oils. Journal of the Chinese Chemical Society 2010, 57(6), 1268–1277.

 Web of Science ®Google Scholar

Demirci, B.; Hüsnü Can Başer, K.; Yıldız, B.; Bahçecioǧlu, Z. Composition of the Essential Oils of Six Endemic Salvia Spp. from Turkey. Flavour and Fragrance Journal 2003, 18(2), 116–121.

 Web of Science ®Google Scholar

Lopes-Lutz, D.; Alviano, D.S.; Alviano, C.S.; Kolodziejczyk, P.P. Screening of Chemical Composition, Antimicrobial and Antioxidant Activities of Artemisia Essential Oils. Phytochemistry 2008, 69(8), 1732–1738.

 PubMed Web of Science ®Google Scholar

Viljoen, A.; Van Vuuren, S.; Ernst, E.; Klepser, M.; Demirci, B.; Başer, H.; Van Wyk, B.-E. Osmitopsis asteriscoides (Asteraceae)-The Antimicrobial Activity and Essential Oil Composition of a Cape-Dutch Remedy. Journal of Ethnopharmacology 2003, 88(2), 137–143.

 PubMed Web of Science ®Google Scholar

Clifford, M.N.; Johnston, K.L.; Knight, S.; Kuhnert, N. Hierarchical Scheme for LC-MS Identification of Chlorogenic Acids. Journal of Agricultural and Food Chemistry 2003, 51, 2900–2911.

 PubMed Web of Science ®Google Scholar

Guimarães, R.; Barros, L.; Dueñas, M.; Carvalho, A.M.; Queiroz, M.J.R.; Santos-Buelga, C.; Ferreira, I.C. Characterisation of Phenolic Compounds in Wild Fruits from Northeastern Portugal. Food Chemistry 2013, 141(4), 3721–3730.

 PubMed Web of Science ®Google Scholar

Dias, M.I.; Barros, L.; Duenas, M.; Pereira, E.; Carvalho, A.M.; Alves, R.C.; Oliveira, M.; Santos-Buelga, C.; Ferreira, I. Chemical Composition of Wild and Commercial Achillea millefolium L. and Bioactivity of the Methanolic Extract, Infusion and Decoction. Food Chem 2013, 141(4), 4152–4160.

 PubMed Web of Science ®Google Scholar

Saeidnia, S.; Yassa, N.; Gohari, A.R.; Shafiee, A. Isolation and Identification of Flavonoid Constituents from of Achillea conferta DC. Journal of Medicinal Plants 2005, 2(14), 12–20.

 Google Scholar

Krenn, L.; Miron, A.; Pemp, E.; Petr, U.; Kopp, B. Flavonoids from Achillea nobilis L. Zeitschrift Fur Naturforschung. C, Journal of Biosciences 2003, 58(1–2), 11–16.

 PubMed Web of Science ®Google Scholar

Valant, K.; Besson, E.; Chopin, J. C-Glycosylflavones from the Genus Achillea. Phytochemistry 1978, 17(12), 2136–2137.

 Web of Science ®Google Scholar

Dall’Acqua, S.; Bolego, C.; Cignarella, A.; Gaion, R.M.; Innocenti, G. Vasoprotective Activity of Standardized Achillea millefolium Extract. Phytomedicine 2011, 18(12), 1031–1036.

 PubMed Web of Science ®Google Scholar

Abhilasha, D.; Quintana, N.; Vivanco, J.; Joshi, J. Do Allelopathic Compounds in Invasive Solidago canadensis Sl Restrain the Native European Flora? Journal of Ecology 2008, 96(5), 993–1001.

 Web of Science ®Google Scholar

Gavrilova, V.; Kajdzanoska, M.; Gjamovski, V.; Stefova, M. Separation, Characterization and Quantification of Phenolic Compounds in Blueberries and Red and Black Currants by HPLC− DAD− ESI-MS N. Journal of Agricultural and Food Chemistry 2011, 59(8), 4009–4018.

 PubMed Web of Science ®Google Scholar

Clifford, M.N.; Kirkpatrick, J.; Kuhnert, N.; Roozendaal, H.; Salgado, P.R. LC–Msn Analysis of the Cis Isomers of Chlorogenic Acids. Food Chemistry 2008, 106(1), 379–385.

 Web of Science ®Google Scholar

Vieira, L.M.; Kijjoa, A.; Pereira, J.; Gedris, T.E.; Herz, W. Germacranes and Flavonoids from Achillea ageratum. Phytochemistry 1997, 45(1), 111–115.

 Web of Science ®Google Scholar

Borrás-Linares, I.; Stojanović, Z.; Quirantes-Piné, R.; Arráez-Román, D.; Švarc-Gajić, J.; Fernández-Gutiérrez, A.; Segura-Carretero, A. Rosmarinus officinalis Leaves as a Natural Source of Bioactive Compounds. International Journal of Molecular Sciences 2014, 15(11), 20585–20606.

 PubMed Web of Science ®Google Scholar

Awad, B.; Ibrahim, A.K.; Sand, E.; Wanas, A.S.; Radwan, M.M.; Elsohaly, M.; Ahmed, S.A. Anticancer Metabolites from Achillea fragrantissima. Planta Medica 2015, 81(05), PC13.

 Google Scholar

Tuberoso, C.I.G.; Montoro, P.; Piacente, S.; Corona, G.; Deiana, M.; Dessi, M.A.; Pizza, C.; Cabras, P. Flavonoid Characterization and Antioxidant Activity of Hydroalcoholic Extracts from Achillea ligustica All. Journal of Pharmaceutical and Biomedical Analysis 2009, 50(3), 440–448.

 PubMed Web of Science ®Google Scholar