Supplementary data
Enantioselective comprehensive two-dimensional gas chromatography.
A route to elucidate the authenticity and origin of Rosa damascena P. Miller essential oils
Ján Krupčík1*, Roman Gorovenko1, Ivan Špánik1, Pat Sandra2, Daniel W.Armstrong3
1
Institute of Analytical Chemistry, Faculty of Chemistry and Food Technology, STU, Bratislava, Slovak
Republic
2
Research Institute for Chromatography, Kennedypark 26, B-8500, Kortrijk, Belgium
3
Department of Chemistry and Biochemistry, University of Texas, Arlington, TX, USA
Introduction
The most comprehensive study on the composition of the essential oil of Rosa damascena P. Miller essential
oil was published by E.Kováts already in 1987 [2]. A “Bulgarian oil 1961“ sample from the harvest of 1960
was analysed by a complex analytical procedure. After classical group separation, the neutral part was
further subdivided by “group displacement chromatography” on deactivated silica gel into non-polar,
slightly polar and polar parts. Acids and phenols were analysed as methoxy and ethoxy derivatives. The
individual groups were first distilled. Pure components were isolated from the distillation fractions by
preparative gas chromatography. Fractions isolated on a hydrocarbon-type stationary phase (Apiezon L)
were further separated on a polyethylene glycol type sationary phase (Emulphor-O) to yield the pure
components. In a second analysis, the oil was separated in a continuous counter-current separator with 680
cells in order to isolate the fraction containing those compounds which are responsible for the “honey note”
of the oil. The enriched part (ca. 1% of the oil) was then separated as described above. As a result, 127
compounds were isolated and identified, representing 98.6% of the volatile part. Of these only 40 had been
previously reported. The compound mainly responsible for the sweet odor (“honey note”) was shown to be a
dehydroisoionone comprising 0.1% of the oil. Because of its organoleptic importance, damascenone was
proposed as common name for this substance. Table 2S shows the data obtained by analysis of Bulgarian
Rosa damascena P. Miller essential oil by Kováts [2]. For the quantitative analysis the oils resulting from
the group separation were chromatographed on a 100 m x 1 mm I.D. stainless-steel capillary caoted with
Apiezon L and operated at 90, 130 and 190°C with thermal conductivity detection.
Table 1S.
Data obtained by gas chromatographic analysis of volatile components in Rosa damascena P. Miller by
Kováts [2].
Compound
n-Alkanes (16)
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Eicosane
Heneicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Heptacosane
%
0.001
0.005
0.006
0.006
0.3
0.05
1.63
0.15
9.1
0.7
3.0
0.07
0.5
0.03
0.12
0.02
Monoterpenes (9)
Myrcene
cis-Ocimene
trans-Ocimene
-Terpinene
-Terpinene
Terpinolene
(+)-Dipentene
(-)--Pinene
(-)--Pinene
0.09
0.01
0.04
0.004
0.02
0.02
0.04
0.23
0.04
Sesquiterpenes (8)
trans-Sesquimyrcene
trans-trans-Sesquicitronellene
Humulene
(-)-Caryophyllene
(?)--Zingiberene
(+)-Ylangene
(-)-Guajene
(+)--Cadinene
0.02
0.01
0.24
4.49
0.008
0.01
0.16
0.1
Aromatic hydrocarbons (2)
o,p-Dimethylstyrene
p-Cymene
0.02
0.01
Alkenes (5)
cis-8-Heptadecene
7-Heptadecene
Octadecene
cis-9-Nonadecene
Eicosene
0.14
0.02
0.05
3.1
0.1
Alkanols (6)
Methanol
Ethanol
1-Pentanol
1-Hexanol
1-Heptanol
1-Octanol
0.08
1.61
0.02
0.19
0.02
0.01
Compound
Hemiterpenes (3)
(-)-2-Methyl-butan-1 -ol
3-Methyl-butan-1-ol
3-Methyl-2-buten- 1-ol
%
0.05
0.05
0.006
Monoterpene alcohols (7)
(-)-Linalool
Geraniol
Nerol
(-)-Citronellol
(-)-Terpinen-4-ol
(-)--Terpineol
(-)-Menthol
2.7
15.7
8.7
32.1
0.34
0.68
0.008
Sesquiterpene alcohols (3)
(+)-trans-Nerolidol
2-cis-6-trans-Farnesol
trans-trans-Farnesol
0.19
0.15
1.0
Aromatic alcohols (3)
Benzyl alcohol
2-Phenylethanol
2,4,6-Trimethylbenzyl alcohol
0.01
1.19
0.10
Miscellaneous (3)
trans-3-Hexen-1-ol
cis-3-Hexen-1-ol
(+)-Methyl heptenol
0.005
0.005
0.002
Alkanals (7)
Acetaldehyde
Pentanal
Hexanal
Heptanal
Nonanal
Decanal
Undecanal
0.04
0.02
0.006
0.03
0.03
0.005
0.01
Hemiterpene aldehydes (2)
2-Methylbutanal
3-Methylbutanal
0.004
0.004
Monoterpene aldehydes (3)
Neral
Geranial
(+)-1-p-Menthen-9-al
0.01
0.03
0.008
Aromatic aldehyde (1)
Benzaldahyde
0.02
Ketones (9)
Acetone
2-Undecanone
2-Tridecanone
2-Pentadecanone
Menthone
Isomenthone
0.003
0.03
0.02
0.03
0.009
0.004
Table 1S. Continuation.
Compound
Methylheptenone
trans-Geranylacetone*
trans-Damascenone*
%
0.003
0.1
0.1
Methoxy derivatives (3)
Benzyl methyl ether
Methyleugenol
trans-Anethol
0.01
2.3
0.008
Ethoxy derivatives (1)
Acetaldehyde diethyl acetal
0.005
Monoterpene oxides (5)
(-)-cis-Rose oxide
(-)-trans-Rose oxide
(±)-Nerol oxide
1,8-Cineol
2-(3'-Methyl-2'-butenyl)-3-methylfuran
0.38
0.17
0.09
0.003
0.01
Esters (18)
Neryl acetate
Geranyl acetate
(-)-Citronellyl acetate
2-Phenylethyl acetate
Menthyl acetate
(?)-Citronellyl caprinate
2-Phenylethyl caprinate
Ethyl laurate
0.07
0.68
0.53
0.05
0.01
0.005
0.003
0.03
Compound
(+)-2-Phenylethyl-2-methylbutyrate
Benzyl tiglate
2-Phenylethyl trans-geraniate
Methyl trans-geraniate
Methyl cis-geraniate
Ethyl benzoate
Benzyl benzoate
2-Phenylethyl benzoate
Dibutyl phthalate
2-Phenylethyl isobutyrate
%
0.04
0.2
0.01
0.08
0.001
0.02
0.05
0.07
0.2
0.1
Miscellanous (1)
( ±)- trans-Linalool oxide
0.04
Acids (9)
Valeric acid
Capronic acid
Enanthic acid
Caprylic acid
Pelargonic acid
Capric acid
(-)-Citronellic acid
cis-Geranic acid
trans-Geranic acid
0.001
0.001
0.002
0.004
0.006
0.002
0.01
0.004
0.18
Phenols (2)
Eugenol
Methyl salicylate
0.55
0.01
Table 2S.
ISO 9842:2003. Oil of rose (Rosa×damascena Miller).
Compound
Ethanol
Citronellol
Nerol
Geraniol
-Phenyl ethanol
Heptadecane
Nonadecane
Heneicosane
Bulgaria
Min.
Max
2.0
20.0
34.0
5.0
12.0
15.0
22.0
3.5
1.0
2.5
8.0
15.0
3.0
5.5
Turkey
Min.
Max
7
34.0
49.0
3.0
11.0
8.0
20.0
3.0
0.8
3.0
6.0
13.0
2.0
4.0
Table 3S.
Variability of major components in Turkish Rosa damascena P. Miller essential oil produced during years
1986 to 2001 [28].
Name
Citronellol
Geraniol
Nonadecane
Nerol
1-Nonadecene
Methyl eugenol
Heneicosane
Geranyl acetate
Linalool
2-Phenylethyl alcohol
-Caryophyllene
Citronellyl acetate
Germacrene D
(2E,6E)-Farnesol
Min %
30.9
9.3
8.3
5.2
2.6
2.7
2.5
1.0
0.6
1.2
0.7
0.7
0.7
0.6
Max %
43.9
14.1
14.7
7.6
4.9
4.0
4.2
2.2
2.1
1.9
1.6
1.4
1.4
1.4
Table 4S.
Elution order of stereoisomers and enantiomers present in Rosa damascena P. Miller essential oil on a
heptakis(2,3-O-diethyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin capillary column.
Name
Camphor
Camphene
Carvone
Citronellal
β-Citronellol
Limonene
cis and trans Linalool oxide
Elution order
(R)-(+)-, (S)-(-)(-)-, (+)(-)-, (+)(-)-, (+)-
Linalool
(R)-(−)-, (S)-(+)-
Linalyl acetate
Limonene
cis, trans Nerolidol
(R)-(-)-, (S)-(+)(-)-, (+)two peaks (+/-)-cis-, two peaks (+/-)-trans-
α-Pinene
β-Pinene
(R)-(+)-, (S)-(-)
(R)-(+)-, (S)-(-)
α-Phellandrene
β-Phellandrene
Terpinen-4-ol
α-Terpineol
(-)-, (+)(-)-, (+)(+)-, (-)(-)-, (+)-
Sabinene
(R)-(+)-, (S)-(-)-
(S)-(-)-, (R)-(+)(S)-(-)-, (R)-(+)(+)-trans-, (-)-cis-, (-)trans-, (+)-cis-
Ref.
C, D
C
B
B
B
B, E
B
E
B, C
C
A
E
E
C
C
C
C
E
(A) GC-Columns-Brochure. Red Analytical. 2009-2013. www.dot-red.com
(B) A Guide to the Analysis of Chiral Compounds by GC, Lit. Cat.# 59889, 1997 Restek Corporation.
www.restek.com/pdfs/59889.pdf
(C) Bonaccorsi I., Sciarrone, D., Cotroneo, A., Mondello, L., Dugo, P., Dugo. G., Rev. Bras. Farmacogn.
Braz. J. Pharmacogn. 2011, 21, 841-849.
(D) Tateo, F., Bononi, M. , De Dominicis, E., Fumagalli, V., Anal. Commun. 1999, 36, 149-151.
(E) Schipilliti, L., Bonaccorsi, I., Cotroneo, A., Dugo, P., Mondello, L., J. Agric. Food Chem. 2013, 61,
1661-1670.