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Analysis of the chemical composition of dill essential oils (Anethum

graveolens L.) by the method of infra-red spectroscopy

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 НАУЧНИ ТРУДОВЕ НА SCIENTIFIC WORKS OF
УНИВЕРСИТЕТ ПО ХРАНИТЕЛНИ UNIVERSITY OF FOOD
ТЕХНОЛОГИИ - ПЛОВДИВ TECHNOLOGIES
2018 г. 2018
ТОМ 65, КНИЖКА 1 VOLUME 65 ISSUE 1

Analysis of the chemical composition of dill essential oils (Anethum

graveolens L.) by the method of infra-red spectroscopy
Milen Dimov1*, Krasimira Georgieva2, Yordan Denev2, Krasimira Dobreva1, Albena Stoyanova3
1
Trakia University, Faculty “Technics and technology”, Dept. “Food technology”, Yambol
2
University “Prof.Dr. Asen Zlatarov”, Faculty of technical sciences. Bourgas,
3
University of food technologies, Technologic Faculty, Dept.“Technology of tobacco, sugar, plant and essential oils”,

*Corresponding author: Assis. M. Dimov, Trakia University, Faculty “Technics and technology”, Dept. “Food
technology”, Graf Ignatiev str. № 38, Yambol, e - mail: [email protected], GSM 0876673550

Running title: Infra-red spectroscopy of dill essential oils

Abstract
The chemical composition of dill essential oils (Anethum graveolens L.) obtained from flowers, leaves and fruits
were studied by infra-red spectroscopy. The main component found in the oil from fruits was carvone. The main
component in the essential oils from flowers and leaves was carvacrol and its content in the oil from flowers was
higher.

Practical applications
Qualitative composition of dill essential oils by the method of infra-red spectroscopy.

Key words: infra-red spectroscopy, dill essential oils

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2018 г. 2018
ТОМ 65, КНИЖКА 1 VOLUME 65 ISSUE 1

Introduction Materials and Methods

Dill (Anethum graveolens L.) is a traditional and In the present work, dill essential oils (Anethum
widely spread flavoring in Bulgaria. The essential oil graveolens L.) obtained from flowers, leaves and
is secreted in canals in all parts of the plant: stem (0.1- fruits grown in Bulgaria on the land of the village of
0.2%), leaves (0.1-0.5%), umbels by buttoning and Tenevo, Yambol district in 2017 was studied. The oils
blossoming (1.2-2%), fruits (3-6%). The oil is used in were isolated by water distillation in a laboratory
cosmetics, food industry and medicine (Georgiev and apparatus of British Pharmacopeia, modified by
Stoyanova 2006; Stoyanova and Georgiev 2007). Balinova and Diakov, % (v/w). The yield of the
The essential oil is the main substance determining the essential oils were calculated against absolutely dry
smell and taste of dill. Two types of oils are obtained material (Stoyanova et al. 2007).
– from leaves and fruits. They differ both by The infra-red spectra were registered in the frequency
composition and their use. range from 4000 to 400 cm-1 at resolution of 4 cm-1.
The dill essential oil obtained from the leaves contains The IR spectra of the essential oils were obtained
-phellandrene (17.0-32.0%), limonene (20.0- Fourier transform IR spectrophotometer Bruker
32.0%), dihydrocarvone (4.0-9.0%) and carvone Tensor 27 connected to personal computer where
(25.0-45.0%) while the oil isolated from fruits Windows based software OPUS 6.5 was installed.
contains mainly: limonene (9.0-37.0 sometimes up to
68.0%), carvone (36.0-67.0%) and dihydrocarvone Results and Discussion
(0.9-7.8 and up to 18%) (Brunke et al. 1991; Georgiev
and Stoyanova 2006; Dimov et al. 2017; Jianu et al. The moisture of the flowers was 70.27%, of leaves
2012; Jirovetz et al. 2003; Nenov et al. 2013; Pedro et was 79.71%, and of fruits was 10.64%. The yields of
al. 2002). flower, leaves and fruit oils were 0.36% (v/w), 0.90%
No literary data were found about the contents of the (v/w) and 3.61% (v/w), respectively. All essential oils
main components in dill oil obtained from flowers. were light yellow liquids and had a specific odor.
Some authors used infra-red (IR) spectroscopy to The data of the IR spectra of essential oils obtained
characterize various products of biologic origin, e.g. from flowers, leaves and fruits of dill are presented in
chitin and chitosan (Tsaneva et al. 2018; Zvezdova Table 1 and Fig.1 shows the IR spectra of flowers,
and Stoeva 2010). Others sustain the opinion that IR leaves, and fruits of dill grown in Bulgaria.
is fast and convenient method to verify fake essential It can be seen from the spectra obtained that there was
oils from lavender, peppermint, pine, fir-tree and no significant difference in the characteristic
chicory (Samfira et al. 2015). absorption bands from flowers and leaves. The IR
IR spectroscopy is electromagnetic absorption spectra show absorption bands in the interval 3450
spectral method. It is based on the resonance between сm-1 (flower oil), 3431 сm-1 (leaves oil) and 3469 сm-
the energies of the vibrations of the inter-atom bonds
1
(fruits oil) which are characteristic for γOH – group
in the molecule and the energy of the IR radiation. (3550 – 3400 сm-1) and it was most pronounced in the
Traditionally and for convenience, IR spectroscopy is spectrum from flower oil (3469 сm-1). It suggests that
discussed in practice in terms of frequency actually the essential oil contained a component of the phenol
implying wave number and in plotted spectra the group. Additional confirmation for this is the band at
abscissa is dimensioned in сm-1. The convenience of 1301 сm-1 which was most intense for the flower oil.
this dimension is that it increases with the increase of It may be suggested that it is carvacrol (Tarasevich
the energy of the transition. The most widely used 2012; Dimov 1984; Andreev 1999) as this is in
range is 3800 до 600 сm-1 (Dimov 1984). accordance with our unpublished data.
In the present paper, an attempt is made to obtain In the spectrum of dill fruit oil, a clearly
preliminary information on the qualitative distinguishable band was observed at 1675 сm-1
composition of dill essential oils (obtained from which proves the presence of С=О adjacent to С=С in
flowers, leaves and fruits) by the method of IR α,β position with respect to the keto-group, once again
spectroscopy. confirmed by the band at 1436 сm-1 indicating
vibration of ketone, δ СН2. This band lead us to the
assumption that the predominating component in the

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ТОМ 65, КНИЖКА 1 VOLUME 65 ISSUE 1

fruit oil is carvone which is of the ketone group https://www.btu.bg/images/annual/2017/annual_vhti

(Tarasevich 2012; Dimov 1984; Andreev 1999). _book_1_2017.pdf
In the spectra of the oils from leaves and flowers, an Dimov, N. Organic Analysis. Technika, Sofia, 1984.
absorption band can be observed at 1639 сm-1 which [In Bulgarian].
indicates for non-conjugated C=C bond, low intensity Dimov, N., Boneva S. Practice book on structural
НRС=СН2 end vinyl. Additional confirmation for the studies and analysis of organic compounds.
presence of C=C bond provide the bands at 914 сm-1 University “Prof. Dr. A. Zlatarov”, Bourgas, 1987.
(flowers) and 913 сm-1 (leaves) which correspond to [In Bulgarian].
absorption from C–H bond in alkenes of the type Georgiev, E., Stoyanova A. A Guide for the Specialist
НRС=СН2. Furthermore, this is in accordance with in Aromatic Industry, Plovdiv, 2006. [In Bulgarian].
the band at 816 сm-1 observed for the two oils (flowers Jianu, C., Misca C., Pop G., Rusu L.-C., Ardeleanu
and leaves) which proves the substitution at double L., Gruia A. Chemical composition and antimicro-
bonds of type RR`С=СR``Н in both samples. It bial activity of essential oils obtained from dill
suggests that the predominant substance in both (Anethum graviolens L.) grown in western
samples was limonenewhich is in the group of non- Romania. Revista de Chimie, 2012, 63(6): 641-645.
conjugated alkenes (Tarasevich 2012; Dimov and Available at:
Boneva 1987; Andreev 1999). http://www.revistadechimie.ro/pdf/RUSU%20L.C..
pdf%206%2012.pdf
Conclusion Jirovetz, L., Buchbauer G., Stoyanova A., Georgiev
IR spectroscopy is a method which can preliminarily E., Damianova S. Composition, quality control, and
provide idea about the qualitative composition of the antimicrobial activity of the essential oil of long-
essential oil. time stored dill (Anethum graveolens L.) seeds from
The interpretation of the IR spectra of essential oil Bulgaria. Food Chemistry, 2003, 51(13): 3854-
obtained from flowers, leaves and fruits of dill lead us 3857.
to the following conclusions: https://pubs.acs.org/doi/abs/10.1021/jf030004y
- The main components in the essential oils obtained Nenov, N., Atanasova T., Stoilova I., Gochev V.,
from flowers, leaves and fruits of dill (Anethum Girova T., Stoyanova A. Low temperature
graveolens L.) grown in Bulgaria are carvone, extraction of essential oils by liquefied gases. Dill
liminene and carvacrol. leaves (Anethum graveolens L.), Scientific Works of
- The predominant substance in dill fruit oil is University of Food Technologies, 2013, 60(1): 561-
carvone. 565. Available at: http://uft-
- The main component in the essential oils obtained plovdiv.bg/site_files/file/scienwork/scienworks_20
from flower and leaves of dill is carvacrol and its 13/docs/01-tech/04-tech-tut-kozm/24-
content was higher in the flower oil. Teodora_Atanasova_-_UFT_Plovdiv.pdf
Pedro, A., Santos G., Figueiredo C., Lourenço P.,
References Barroso J., Pedro L., Oliviera M., Schripsema J.,
Andreev, G. Molecular Spectroscopy. P. Hilendarski Deans S., Scheffer J. Hairy root cultures of Anethum
Plovdiv University Publishing House, Plovdiv, graveolens (dill): establishment, growth, time-
1999. course study of their essential oil and its comparison
Brunke, E.-J., Hammerschmidt F.-J., Koester F.-H., with parent plants oils. Biotechnology Letters, 2002,
Mair P. Constituents of dill (Anethum graviolens L.) 24: 1031-1036.
with sensory importance. Journal of Essential Oil https://link.springer.com/article/10.1023/A:101565
Research, 1991, 3(4): 257-267. 3701265
https://doi.org/10.1080/10412905.1991.9697936 Samfira, I., Rodino S., Petrache P., Cristina R., Butu
Dimov, M., Dobreva K., Damianova S., Stoyanova A. M., Butnariu M. Characterization and identity
Chemical composition, antioxidant and conformation of essential oils by mid infrared
antimicrobial activities of dill essential oils absorption spectrophotometry. Digest Journal of
(Anethum graveolens L.). Annual Assen Zlatarov Nanomaterials and Biostructures, 2015, 10 (2):557-
University, Burgas, Bulgaria, 2017, 66(1): 37-42. 566. Available at: http://www. chalcogen.ro/557_
Samfira.pdf

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Stoyanova, A., Georgiev E. Technology of essential black sea. Annual Assen Zlatarov University,
oils, University of Food Technologies, Plovdiv, Burgas, Bulgaria, 2010, 39: 37-41. Available at:
2007. https://www.btu.bg/images/annual/2010/t1-7.pdf
Stoyanova, A., Georgiev E., Atanasova T. Practice
book on technology of essential oils. Acad. Publ.
house, University of Food Technologies, Plovdiv,
2007.
Tarasevich, B. IR spectra of basic classes of organic
compounds, Lomonosov Moscow State University,
Moscow, 2012. Available at: http://chem.
msu.su/rus/teaching/tarasevich/Tarasevich_IR_tabl
es_29-02-2012.pdf
Tsaneva, D., Petkova Z., Petkova N., Stoyanova M.,
Stoyanova A., Denev P. Isolation and
characterization of chitin and biologically active
substances from honeybee (Apis mellifera). Journal
of Pharmaceutical Sciences & Research, 2018,
10(4): 884-888. Available at: https://www.jpsr.
pharmainfo.in/Documents/Volumes/vol10Issue04/j
psr10041844.pdf
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characterization of chitin from marine sources in

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Table 1. IR spectra of essential oil from dill (flowers, leaves, fruits).

Characteristic bands (cm-1) Group type

Flowers Leaves Fruits Reference data
3450 3431 3469 3550 – 3400 γОН intramolecular H Н – bond
3002 - - 3000 – 2975 γСН2 cyclic derivative
- - 3083 3095 -3075 Isolated C=C bonds (CH2=CH), γ =C–H
2958 2958 2966 2970 – 2950 linear γas CH3
2929 2927 2925 2940 – 2915 γas –CH2–
- 2872 - 2885 – 2860 Presence of CH3 group
- 2855 - 2870 – 2845 γs –CH2–
2835 - - 2830 – 2815 Alk–O–CH3, γs CH3
- 1737 1714 1775 – 1700 Cyclic aromatic ketones
1677 - 1675 1695 – 1660 C=O adjacent to C=C in α,β – position vs.
keto-group
1639 1639 - 1648 – 1640 Non-conjugated C=C, low intensity.
HRC=CH2 end vinyl
1511 1511 - 1510 – 1480 Carcass vibrations of aromatic ring, γ С=С
1464 1464 - 1465 – 1440 Aromatic ring
- - 1436 1435 – 1405 Vibrations of ketones, δ СН2
1439 - - 1465 – 1440 Aromatic ring
- 1369 1372 1375 – 1360 Branched bonds, δs CH3 – doublet
1301 1301 - 1350 – 1260 О–Н group
1247 1247 1247 1260 – 1240 γas С–О–С
- - 1143 1160 – 1140 Branched carcass vibrations
1177 1177 - 1175 – 1165 CH3–CH–CH3
1111 1111 1111 1150 – 1050 γ С–О–С, ether bond
as

1038 1038 1058 1070 – 1020 =С–О–С, γs С–О–С, aromatic and vinyl
994 993 - 995 – 985 С–Н bond in alkenes of type НRС=СН2
- - 960 990 – 960 Trans double bond, γ =С–Н
914 913 - 995 – 985 С–Н bond in alkenes of type НRС=СН2
- - 893 900 – 865 Trisubstituted aromatic ring in positions 1,2,4
816 816 - 850 – 790 Substitution at the double bond of type
RR'C=C R''H
- - 801 855 – 800 Trisubstituted aromatic ring γ Ar – H in
positions 1,2,4

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Figure 1. IR spectra of flowers (curve 3), leaves (curve 2) and fruits (curve 1).

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