Next Article in Journal
Asymmetric Dearomative (3+2)-Cycloaddition Involving Nitro-Substituted Benzoheteroarenes under H-Bonding Catalysis
Next Article in Special Issue
A Practical Laboratory-Scale Synthesis of All Eight Stereoisomeric Forms of Terpene Linalool Oxide
Previous Article in Journal
Untargeted Metabolomics in Forensic Toxicology: A New Approach for the Detection of Fentanyl Intake in Urine Samples
Previous Article in Special Issue
Oxidation of Terpenoids to Achieve High-Value Flavor and Fragrances—Questioning Microalgae Oxidative Capabilities in the Biotransformation of the Sesquiterpene Valencene and of Selected Natural Apocarotenoids
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 26
Issue 16
10.3390/molecules26164991
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Subcritical Extracts from Major Species of Oil-Bearing Roses—A Comparative Chemical Profiling

by
Ana Dobreva
1,
Daniela Nedeltcheva-Antonova
2,*,
Nenko Nenov
3,
Kamelia Getchovska
2 and
Liudmil Antonov
4
1
Institute of Roses and Aromatic Plants, Agricultural Academy, 6100 Kazanlak, Bulgaria
2
Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
3
Department of Heat Engineering, Technical Faculty, University of Food Technologies, 4002 Plovdiv, Bulgaria
4
Institute of Electronics, Bulgarian Academy of Sciences, 1784 Sofia, Bulgaria
*
Author to whom correspondence should be addressed.
Molecules 2021, 26(16), 4991; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164991
Submission received: 16 July 2021 / Revised: 3 August 2021 / Accepted: 12 August 2021 / Published: 18 August 2021
(This article belongs to the Collection Recent Advances in Flavors and Fragrances)
Browse Figures
Versions Notes

Abstract

:
A comprehensive chemical profiling of 1,1,1,2-tetrafluoroethane (freon R134a) subcritical extracts from the main genotypes of oil-bearing roses, was performed by gas chromatography–mass spectrometry (GC/MS) and gas chromatography with flame ionization detection (GC-FID) in order to reveal the differences in their chemical composition. One hundred and three individual compounds were identified using GC/MS and their quantitative content was determined using GC-FID, representing 89.8, 92.5, 89.7 and 93.7% of the total content of Rosa gallica L., Rosa damascena Mill., Rosa alba L. and Rosa centifolia L. extracts, respectively. The compounds found in the extracts are representatives of the following main chemical classes: mono-, sesqui- and triterpenoids, phenylethanoids and phenylpropanoids and aliphatic hydrocarbons. Fatty acids, esters and waxes were found, as well. The study revealed that 2-phenylethanol is the most abundant component, ranging 9.0–60.9% followed by nonadecane and nonadecene with 5.1–18.0% geraniol (2.9–14.4%), heneicosane (3.1–11.8%), tricosane (0.1–8.6%), nerol (1.3–6.1%) and citronellol (1.7–5.3%). The extracts demonstrate a specific chemical profile, depending on the botanical species—phenylethanoids and phenyl propanoids are the main group for R. damascena, aliphatic hydrocarbons for R. alba and R. centifolia, while both are found in almost equal amounts in R. gallica. The terpenoid compounds show relatively broad variations: monoterpenes—11.9–25.5% with maximum in R. centifolia; sesquiterpenes—0.6–7.0% with maximum in R. gallica and triterpenes—0.4–3.7% with maximum in R. gallica extract.

Graphical Abstract

1. Introduction

The essential oils and extracts of oil-bearing roses are high-value natural products with a broad range of applications. They are indispensable in fine perfumery and cosmetics, as food additives and aromatherapy agents [1]. Nowadays, several species, namely, R. damascena Mill., R. gallica L., R. centifolia L. and R. alba L., are used for the commercial manufacturing of rose oil, rose water, absolute and concrete [2,3]. Rose aroma products are well known for their perfumery properties and rich pharmacological activity, showing antioxidant, antimicrobial, analgesic, antispasmodic, muscle relaxant, anti-inflammatory, anticonvulsant and antiviral effects, as described in the literature [2,3,4,5,6,7,8]. Bulgaria is the only country, where the industrial cultivation of R. alba and R. damascena takes place, along with small areas of R. gallica and R. centifolia [4,9]. The quality of the rose oil is standardized according to ISO9842 [10]. Turkey, Iran, India, Afghanistan, China and Saudi Arabia grow R. damascena, while Morocco cultivates mainly R. centifolia. In the northern countries, where the frost resistance plants are preferred (Russia, Ukraine, Moldova), R. gallica is mainly spread. Each of the rose genotypes has its own advantages, which are used in breeding and selection programs, resulting in crossbreeds (subsequently varieties) aimed to bring high economic value.
The aroma composition of rose oil has been investigated intensively [11,12,13,14,15,16,17,18,19,20,21,22], but alternatively, the rose scent could be extracted as a wax-like substance called rose concrete by non-polar solvent extraction (usually -n-hexane), which, followed by ethanol re-extraction, produces rose absolute [11,23]. Following the production process, it is considered that the rose absolute much better reflects the chemical composition of the rose flower [24,25]. There are, currently, few investigations of the rose absolute chemical composition, which are focused only on a few main constituents and predominantly on absolutes produced in Turkey [6,15,23,26,27,28,29].
The modern green-economy puts additional requirements for the solvents used in the extracts production, leading to a general trend to reduce or eliminate petrochemical solvents and to decrease energy consumption in addition. Therefore, an “eco-footprint” was determined for each solvent, based on the six principles of green extraction defined by Chemat and co-workers [30]. The application of liquefied gases brings additional advantages over traditional extraction techniques such as the flexibility of the processing and the lack of the residual solvent contamination of the final product, which eliminates the expensive post-processing treatment.
Since the last decade, 1,1,1,2-tetrafluoroethane has been widely used as a solvent for the extraction of valuable natural compounds from aromatic and medicinal plants [31,32,33,34,35]. The products of this type of extraction could be used as food grade aroma preparations according to existing regulations [36]. Except some environmental and cost consideration, 1,1,1,2-tetrafluoroethane is close to an ideal solvent for extraction due to the following:
-
High selectivity to smelling natural compounds (i.e., terpenes and their derivatives) [31,34,35];
-
Very high chemical resistance—no interaction with the processed plant, its compounds and equipment walls (high quality and purity of final product) [37];
-
Low viscosity and surface tension of liquid solvent [37]—intensive extraction process for short extraction times, even at low temperatures;
-
Low extraction temperatures [31,34,35]—close to ambient ones (no thermal degradation of heat sensitive compounds during extraction and separation and hence high aroma quality of final product);
-
Low boiling points [37]—easy and effective separation of final product from solvent;
-
Low values of vaporization heat [37]—high level of energy efficiency and low energy input for micellar separation;
-
Absence of own smells and taste [38]—high purity of final extracts;
-
Safe for the human health [38] and suitable for food-grade aroma preparations;
-
Fire and explosion safe properties [38];
-
Moderate extraction pressures [31,34,35]—relative light, low cost extraction equipment.
The hot compressed water is also used as an alternative for the extraction of valuable natural compounds. The use of hot compressed water can be advantageously exploited over a wide range of temperatures and appropriate pressures to cover extraction with targeted substrates. It is a new and powerful technique at temperatures between 100 and 374 °C and a pressure high enough to maintain the liquid state [39]. Its high boiling point for its mass and high dielectric constant make it most efficient to high polar target materials, whereas moderately polar and non-polar targets (as fragrances) require a less polar medium induced by an elevated temperature. The subcritical extraction of dried R. damascena flowers resulted in a high yield (38.14%), but the quality of the product is unsatisfactory [40]. Solvent-free microwave-assisted extraction and ohmic-assisted hydrodistillation are advanced and green distillation techniques, recently reported as promising alternatives in the extraction of rose aroma products [41].
Comparing the solvents for rose absolute production, the supercritical CO2 extraction of rose concrete was found to be perspective, giving a yield of 2-phenyl ethanol over 50% larger [42] in respect of traditionally used ethanol [43,44]. The extraction of R. damascena with CO2 (25.5 MPa) and co-solvent ethanol was used alternatively to produce quercetin [45]. Wilde and McClory [46] described the application of 1,1,1,2-tetrafluoroethane (known also as freon R134a) for the subcritical extraction of R. damascena, but details about the extract were not provided.
Baser et al. [47] reported extraction with a mixture of 90% tetrafluoroethane:10% diethyl ether, mentioning the importance of the extraction time. They found that 2-phenylethyl alcohol was the main component in almost all the extraction periods (45 min, 5, 8 and 24 h) with the best yield (69.6%) achieved at 45 min. The total terpenoids content decreases during prolonged extraction, while that of the paraffin’s increases, as expected. A comparative study of rose oil obtained through traditional technology and extracts obtained using supercritical CO2 and R134a shows that the chemical composition of the extracts was dominated by 2-phenylethyl alcohol (56.6% in the subcritical sample and 46.7% in the supercritical one), while the main aroma constituents were found substantially higher in the oil [48,49]. A comparison between 1,1,1,2-tetrafluoroethane and the more polar CO2 indicates that the former allows work at a lower pressure leading to much less degradation of the final products [50].
The chemical composition of the rose extracts, similarly to the rose essential oil, should be strongly affected by the botanical and geographical origin of the raw plant material, environmental conditions, the production method (the extraction selectivity of the liquefied gases, for example) and storage. However, up to now, these effects have not been systematically studied. Therefore, the aim of the current study is to investigate and compare the chemical profile of R134a extracts from the main commercially grown oil-bearing rose species, namely, R. damascena Mill., R. gallica L., R. centifolia L. and R. alba L., by means of gas chromatography. To the best of our knowledge, no such systematic comparative study has been performed up to now. The acquired quantitative data could have substantial, fundamental and practical value.

2. Results and Discussion

As a result of the analysis, more than 150 compounds with concentrations higher than 0.01% were detected in the rose subcritical extracts and 103 of them, containing C7-C30 carbon atoms, were identified using GC/MS and simultaneously quantified using GC-FID. In Figure 1, the Total Ion Current (TIC) chromatograms of the R134a extracts are compared. The quantitative content, as determined using GC-FID, is shown in Table 1.
As seen from Table 1, the main constituents or rose extracts are representatives of the phenylethanoids and phenylpropanoids, aliphatic hydrocarbons and terpene compounds (mono-, sesqui- and triterpenoids). Fatty acids, higher alcohols and waxes were found as well.
It is worth mentioning that the studied extracts show a similar qualitative content with different quantitative characteristics. In general, according to our current and previous [24] results, the chemical profile of the subcritical extracts is closer to the rose absolute, than to the rose oil.

2.1. Phenylethanoids and Phenylpropanoids

2-Phenylethanol is one of the abundantly emitted scent compounds in rose flowers, responsible for the characteristic odour of rose. In the frame of the current study, 2-phenethyl alcohol is found to be the main component in the subcritical extracts, ranging from 9.0 (R. centifolia) to 59.6% (R. damascena). This content is comparable with the average concentration of 46.56 ± 0.18% in the R. damascena absolute, while it is only 0.66 ± 0.01% in the rose oil [24]. The results could be explained by the specificity of 2-phenethyl alcohol biosynthesis in each rose genotype [51,52], but also by environmental factors and storage conditions.
Phenylpropanoids (eugenol and methyl eugenol) are naturally occurring compounds in a number of oil-bearing species and essential oils, including roses and rose oil, with a definitely positive scent contribution.
Eugenol was found in R. damascena in the amount of 1.3% and as a trace component (<0.1%) in R. gallica and R. alba extracts.
In the last few decades, concerns were raised by the European Commission’s Scientific Committee on Consumer Products about the potentially allergic and carcinogenic effects of methyl eugenol [53]. Therefore, substantial efforts have been made to reduce its content in cosmetics and especially in food. In our study, methyl eugenol was detected only in the R. damascena extract, in the amount of 0.5%. By comparing this result with the existing data for CO2 extracts [43,44], it could be concluded that, in contrast with other extractants, R134a has no affinity for this compound [28] and could be used for the production of low methyl eugenol content products. The other studied rose species, except R. centifolia, are known to biosynthesize methyl eugenol in insignificant amounts [54], which was also reported for their essential oils [55,56] and has been confirmed for the subcritical extracts in the current study.

2.2. Terpenoids

Terpenes and terpenoids are the main biosynthetic building blocks and important mediators of ecological interactions in the plants. They are the primary constituents of the essential oils.

2.2.1. Monoterpenes and Their Oxygenated Derivatives

Monoterpene hydrocarbons, with main representatives α- and β-pinene, β-myrcene and limonene, are detected in low concentrations in all the samples from 0.2% in R. centifolia to 0.6% in R. damascena extract.
The acyclic alcohols geraniol, nerol and citronellol are the main monoterpene alcohols observed in the extracts. R. alba reached the maximum with amount of 14.4% for geraniol and 6.1% for nerol, while R. damascena shows the highest concentration of 5.3% for the citronellol. These results correspond to the literature data for rose concrete [28], CO2-extract and absolute [43,44]. It is worth noting that the main terpene alcohols, despite being observed in lower amounts, show the same citronellol:geraniol:nerol ratio as in the corresponding essential oils [2,55].
Another monoterpene alcohol found in the extract is linalool as a trace component (<0.1%) in all the extracts.
Monoterpene esters. Several geranyl and citronellyl esters (primarily as formates, acetates and propionates, but also as long chain organic acids esters) were found in a very broad range, from 0.3% in R. gallica to 17.7% in R. centifolia (Table 1).

2.2.2. Sesquiterpenes

Sesquiterpene hydrocarbons are found in a relatively low concentration, with the following main representatives: β-caryophyllene, germacrene D, β-cubebene, β-elemene, β-cadinene, etc. In respect of the total sesquiterpene content, the extracts could be divided in the following two groups: the first one with a higher concentration of 7.0% for R. gallica and 5.2% for R. centifolia, and the second, with a substantially lower amount of 2.1% for R. alba and 0.6% for R. damascena.

2.2.3. Triterpenoids

Triterpenes are one of the most numerous and diverse groups of plant natural products. Simple triterpenes are components of surface waxes and membranes and may potentially act as signalling molecules. Triterpenes have a broad spectrum of biological activity: antioxidant, anticancer, antibacterial, antivirus, gastroprotective, hepatoprotective, antipancreatitic, anticholytic, antihyperglycemic and hypolipidemic effects [57] and have a wide range of applications in the food, health and industrial biotechnology sectors.
The most frequently found triterpenoids in the rose species are lupeol, α-amyrin, β-amyrin, oleanolic acid, ursolic acid, carotenoids and tocopherols [58]. In our study, we identified eight triterpene compounds; among them most abundant are lupeol (1.2% in R. damascena and 0.7% in R. gallica) and β-amyrin (0.9% in R. gallica and 0.5% in R. damascena). The total amount ranges from 2.7 to 3.6%. The maximum is in R. gallica, in R. damascena and R. centifolia the level is equal, while in R. alba they are found in the amount of only 0.4%. Up to date, there were no data in the literature for identified triterpenes in CO2 extracts [42,43,44,59], while for the rose absolute, the values are comparable [24].

2.3. Aliphatic Hydrocarbons (Stearopten)

Aliphatic hydrocarbons (saturated and unsaturated) are the main building blocks on the surface of rose flowers. Aliphatic hydrocarbons, despite being odourless, play an important role in the rose extracts’ chemical composition as compounds, responsible for the odor stability, i.e., they serve as odor fixators. The content of heptadecane and nonadecene/nonadecane is considered to be of particular importance. The total content of alkanes and alkenes found in the rose extracts is in the range from 12.8% in R. damascena to 41.7%. in R. centifolia. The most abundant are nonadecane and nonadecene with 5.1 ÷ 17.9%, followed by heneicosane (3.1 ÷ 11.8%), tricosane (0.1 ÷ 8.6%), pentacosane (0.5 ÷ 2.6%) and heptadecane—0.5 ÷ 1.5%. The distribution of aliphatic hydrocarbons in the extracts of the different roses show the same pattern as in the essential oils, but in lower values [2,55].

2.4. Others

Fatty acids, alcohols and aldehydes. These compounds, naturally presenting in the rose flowers, are normally not observed in the essential oil samples due to their low volatility, but they were found in relatively high amounts in the subcritical extracts (from 0.4% in R. centifolia to 5.0% in R. alba), which could be explained with the extraction selectivity of the R134a used as an extractant.
The components’ distribution in different chemical classes in the subcritical rose extracts is presented in Figure 2.
As seen from Figure 2, R. alba and R. centifolia extracts have very similar chemical profiles dominated by the saturated and unsaturated aliphatic hydrocarbons (41.9 and 41.7%, respectively), followed by monoterpenes (25.4 and 25.5%, respectively), phenylethanoids (14.4 and 9.0%, respectively) and sesquiterpenes (2.1 and 5.2%, respectively). R. damascena extract is the richest in phenylethanoids with 60.9%, followed by aliphatic hydrocarbons (12.8%) and monoterpenes (11.9%), with a minimum of sesquiterpenes content of 0.6%. The extract of R. gallica has almost an equal quantity of aliphatic hydrocarbons and phenylethanoids (33.9 and 27.3%, respectively), the next are monoterpenes (13.4%) and the last are sesquiterpenes (7.0%).

3. Materials and Methods

3.1. Raw Plant Material

The experiment was conducted in 2019. The plants of R. damascena Mill., R. gallica var. officinalis Thory., R. centifolia L. and R. alba L. (Figure S1) are part of a roses collection in the experimental field of Institute for Roses and Aromatic Plants, Kazanlak, Bulgaria. The fresh blossoms were picked up in the morning (6–10 a.m.) in the most appropriate development phase, according to Staikov et al. [60]. Due to the different flowering periods of the species, the raw material was kept by freezing at −20 °C until processing, which, according to Seify et al. [61], is the most appropriate storage method, best preserving the raw material quality. Pictures of the raw material of R. damascena Mill. before and after extraction as well as of the obtained products are shown in Figure S2.
The moisture content of the material was 80–82%, measured by drying to constant weight.

3.2. Extraction

Extraction of the raw material using 1,1,1,2-tetrafluoroethane was performed on a pilot apparatus. The unit consists of a 1-liter extraction vessel, a 5.5-liter collector vessel, equipped with a 200 W electric heater, compressor and heat exchanger unit, and a filtration set. The system is equipped with temperature and pressure sensors. It is controlled by a fully automatic Programmable Logic Controller (PLC) screen interface with first level safety functionality and user programmable parameters (extraction pressure, number of extractions, separation end pressure and extraction time). The heating mantle was constructed around a collector vessel to maximize the freon transfer rate from liquid to gas state.
The used extraction equipment, model TFE-EXV-1L (www.e-xtracts.com, accessed on 14 August 2021) is produced by InnoSolv ltd., Plovdiv, Bulgaria. Most of the details for the working principles and main part of the equipment are confidential according to signed third party agreements. From a scientific point of view, the equipment features are static raw material and the percolation of solvent by gravity with continuous removing of miscella and adding of fresh solvent, initial vacuuming of extractor and raw material, solvent recovery of residue, isobaric process (equal solvent pressure in system extractor/evaporator/condenser), etc.
Periodic stationary extractions were carried out using 300 g of plant material for a single charge. The raw material was sputtered with solvent and after double extraction at 0.5–0.6 MPa and temperature 20–25 °C, the supernatant was drained into a separator, where the solvent was evaporated at a lower pressure, and in the last few minutes, low heat was used to completely eliminate the vapor.
Extraction conditions were as follows: liquid/solid ratio of 4.0 BV/h, solvent conditions in the extraction chamber being thermodynamically close to saturated, boiling liquid at pressure 0.73–0.77 MPa and corresponding saturation temperature in range 28–30 °C, single extraction step, extraction time was 40 min. As the process is an isobaric one, the separation pressure is equal to the extraction pressure.
The extraction parameters were chosen according to our previous experience and different plants trials for the extraction of targeted smelling compounds [31,34,35] (for heat resistant, low molecular weight compounds usually pressure in range 0.6–1.0 MPa and extraction time between 30 to 60 min).
A food grade 1,1,1,2-tetrafluoroethane (CAS number 811-97-2), purchased from the Frigo Chem Ltd. (Bulgaria), was used as an extractant. It is non-polar, pressurized gas solvent featuring colourless and practically odourless liquid with the following parameters: dipole moment of 2.058 Debay [38]; dielectric constant of 3.54 [62]; boiling temperature of −26 °C at 0.101 MPa; saturation pressure at 20 °C of 0.57 MPa [37]; dynamic viscosity at 20 °C of 0.2 mPa; surface tension at same temperature 8.5 mN/m [37].

3.3. Analysis

3.3.1. Gas Chromatography-Mass Spectrometry (GC/MS)

The GC/MS analysis was performed on an Agilent 7820A GC System Plus gas chromatograph coupled with 5977B Mass Selective detector and flame-ionization detector (Agilent Technologies, Palo Alto, CA, USA). A fused silica capillary column, a mid-polar DB-17HT (J&W Scientific, Folsom, CA, USA) with 60 m column length, 0.25 mm i.d., 0.25 μm film thickness, was used. The oven temperature was programmed from 60 °C (2.5 min held) to 100 °C at a rate of 5 °C/min, from 100 to 225 °C at a rate of 2.5 °C/min and from 225 to 275 °C at a rate of 5 °C, 10 min held at the final temperature was applied. Helium (99.999%) was used as a carrier gas at a constant flow rate of 0.8 mL/min. The split ratio was 1:125, the inlet temperature was set to 260 °C and the transfer line temperature was 280 °C. Mass selective detector operated in electron impact ionization (EI) mode at 70 eV electron energy, the ion source temperature was set to 230 °C and the quadrupole temperature was 150 °C. The mass scan range was 45–1050 m/z.

3.3.2. Gas Chromatography with Flame-Ionization Detector (GC-FID)

The GC-FID analysis was performed on the same instrument under the same temperature gradient as described above. The system is equipped with a post-column split of the flow, allowing simultaneous analysis on both detectors. Instrument control and data collection were carried out using Mass Hunter Workstation Software (Revision B.06.07, Agilent Technologies).

3.3.3. Identification, Quantitative Analysis and Chemometrics

The identification of the compounds was performed using commercial mass spectral libraries (NIST 14, Wiley 7th Mass spectra register) and retention times (Linear retention indices, LRI). In the cases of a lack of the corresponding reference data, the structures were proposed based on their general fragmentation pattern and/or using the reference literature mass spectra. The quantification of the main compounds was carried out using an internal normalisation method with response factor set equal to unity for all of the sample constituents. Although not being considered as a true quantification, a simple GC-FID percentage allows for a comparison between the studied rose extract samples.

4. Conclusions

The liquefied gases extraction of rose flowers yields aroma products, which could be considered as a promising alternative to the traditional rose oil and absolute. The chemical composition of subcritical (1,1,1,2-tetrafluoroethane) extracts from the major oil-bearing rose species, namely, R. damascena Mill., R. gallica L., R. centifolia L. and R. alba L., investigated by means of gas chromatography (CG/FID and GC/MS), has revealed that the studied extracts show a similar qualitative content with different quantitative characteristics. The representatives of the phenylethanoids and phenylpropanoids, aliphatic hydrocarbons and terpene compounds (mono-, sesqui- and triterpenoids) are the main constituents. The chemical composition is dominated by 2-phenylethyl alcohol in the range of 9.0–59.3%. R. alba and R. centifolia extracts have very similar chemical profiles dominated by the saturated and unsaturated aliphatic hydrocarbons, followed by monoterpenes, phenylethanoids and sesquiterpenes. The R. damascena extract is the richest in phenylethanoids with 60.9%, followed by aliphatic hydrocarbons and monoterpenes. The extract of R. gallica has an almost equal quantity of aliphatic hydrocarbons and phenylethanoids, the next are mono- and sesquiterpenes. The chemical profile of the subcritical extracts brings them closer to the rose absolute and could be successfully used as its green alternative in cosmetics and aromatherapy.

Supplementary Materials

The following are available online, Figure S1: Rose species blossom, Figure S2: R. damascena raw material, Figure S3: R. damascena aroma products.

Author Contributions

Conceptualization, A.D., N.N. and D.N.-A.; methodology, N.N. and D.N.-A.; formal analysis, D.N.-A. and L.A.; investigation, K.G. and D.N.-A.; resources, L.A.; writing—original draft preparation, D.N.-A. and A.D.; writing—review and editing, D.N.-A.; visualization, L.A.; supervision, L.A.; project administration, D.N.-A. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by The Bulgarian National Science Fund, project KP-06-OPR-01/5 “BG ROSEnsing: Traditional and e-sensing of Bulgarian Rose aromatic products: towards fast authenticity and quality control”. The APC was funded by project KP-06-OPR-01/5.

Data Availability Statement

The data presented in this study are available in this article.

Acknowledgments

The financial support of the project KP-06-OPR-01/5 “BG ROSEnsing: Traditional and e-sensing of Bulgarian Rose aromatic products: towards fast authenticity and quality control”, funded by the Bulgarian National Science Fund, is gratefully acknowledged.

Conflicts of Interest

No available.

Sample Availability

Samples of the compounds are not available from the authors.

References

  1. Panda, H. Cultivation and Utilization of Aromatic Plants; Asia Pacific Business Press: Delhi, India, 2006; ISBN 978-81-7833-027-3. [Google Scholar]
  2. Kovacheva, N.; Zheljazkov, V.D.; Astatkie, T. Productivity, Oil Content, Composition, and Bioactivity of Oil-Bearing Rose Accessions. HortScience 2011, 46, 710–714. [Google Scholar] [CrossRef] [Green Version]
  3. Pal, P.K. Evaluation, Genetic Diversity, Recent Development of Distillation Method, Challenges and Opportunities of Rosa damascena: A Review. J. Essent. Oil Bear. Plants 2013, 16, 1–10. [Google Scholar] [CrossRef] [Green Version]
  4. Mileva, M.; Ilieva, Y.; Jovtchev, G.; Gateva, S.; Zaharieva, M.M.; Georgieva, A.; Dimitrova, L.; Dobreva, A.; Angelova, T.; Vilhelmova-Ilieva, N.; et al. Rose Flowers—A Delicate Perfume or a Natural Healer? Biomolecules 2021, 11, 127. [Google Scholar] [CrossRef]
  5. Mahboubi, M. Rosa damascena as Holy Ancient Herb with Novel Applications. J. Tradit. Complement. Med. 2016, 6, 10–16. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  6. Ulusoy, S.; Boşgelmez-Tınaz, G.; Seçilmiş-Canbay, H. Tocopherol, Carotene, Phenolic Contents and Antibacterial Properties of Rose Essential Oil, Hydrosol and Absolute. Curr. Microbiol. 2009, 59, 554–558. [Google Scholar] [CrossRef] [PubMed]
  7. Aromatherapie: Grundlagen-Wirkprinzipien-Praxis; Wabner, D.; Beier, C. (Eds.) 2. Aufl.; Elsevier, Urban & Fischer: München, Germany, 2012; ISBN 978-3-437-56991-3. [Google Scholar]
  8. Ayati, Z.; Ramezani, M.; Amiri, M.S.; Sahebkar, A.; Emami, S.A. Genus Rosa: A Review of Ethnobotany, Phytochemistry and Traditional Aspects According to Islamic Traditional Medicine (ITM). In Pharmacological Properties of Plant-Derived Natural Products and Implications for Human Health; Barreto, G.E., Sahebkar, A., Eds.; Springer International Publishing: Cham, Switzerland, 2021; Volume 1308, pp. 353–401. ISBN 978-3-030-64871-8. [Google Scholar]
  9. Kovacheva, N.; Rusanov, K.; Atanassov, I. Industrial Cultivation of Oil Bearing Rose and Rose Oil Production in Bulgaria During 21st Century, Directions and Challenges. Biotechnol. Biotechnol. Equip. 2010, 24, 1793–1798. [Google Scholar] [CrossRef] [Green Version]
  10. International Organization for Standardization. ISO Standard 9842:2003 Oil of Rose (Rosa x damascena Miller); International Organization for Standardization: London, UK, 2003. [Google Scholar]
  11. Babu, K.G.D.; Singh, B.; Joshi, V.P.; Singh, V. Essential Oil Composition of Damask Rose (Rosa damascena Mill.) Distilled under Different Pressures and Temperatures. Flavour Fragr. J. 2002, 17, 136–140. [Google Scholar] [CrossRef]
  12. Buccellato, F. An Anatomy of Rose. Perfum. Flavorist 1980, 5, 29–32. [Google Scholar]
  13. Dobreva, A.; Getchovska, K.; Nedeltcheva-Antonova, D. A Comparative Study of Saudi Arabia and Bulgarian Rose Oil Chemical Profile: The Effect of the Technology and Geographic Origin. Flavour Fragr. J. 2020, 35, 584–596. [Google Scholar] [CrossRef]
  14. Dobreva, A.; Kovacheva, N. Daily Dynamics of Essential Oils of Rosa damascena Mill. and Rosa alba L. Agric. Sci. Technol. 2010, 2, 71–74. [Google Scholar]
  15. Garnero, J.; Guichard, G.; Buil, P. L’huile Essentielle et La Concrete de Rose de Turquie. Riv. Ital. Essenze Profumi Piante Off. Aromi Saponi Cosmet. Aerosol 1976, 58, 160–179. [Google Scholar]
  16. Koksall, N.; Aslancan, H.; Sadighazadi, S.; Kafkas, E. Chemical Investigation on Rosa damascena Mill. Volatiles: Effects of Storage and Drying Conditions. Acta Sci. Pol. Hortorum Cultus 2015, 14, 105–114. [Google Scholar]
  17. Kováts, E. Composition of Essential Oils. J. Chromatogr. A 1987, 406, 185–222. [Google Scholar] [CrossRef]
  18. Nedkov, N.; Dobreva, A.; Kovacheva, N.; Bardarov, V.; Velcheva, A. Bulgarian Rose Oil of White Oil-Bearing Rose. Bulg. J. Agric. Sci. 2009, 15, 318–322. [Google Scholar]
  19. Ohloff, G.; Demole, E. Importance of the Odoriferous Principle of Bulgarian Rose Oil in Flavour and Fragrance Chemistry. J. Chromatogr. A 1987, 406, 181–183. [Google Scholar] [CrossRef]
  20. Pellati, F.; Orlandini, G.; van Leeuwen, K.A.; Anesin, G.; Bertelli, D.; Paolini, M.; Benvenuti, S.; Camin, F. Gas Chromatography Combined with Mass Spectrometry, Flame Ionization Detection and Elemental Analyzer/Isotope Ratio Mass Spectrometry for Characterizing and Detecting the Authenticity of Commercial Essential Oils of Rosa damascena Mill.: GC/MS, GC/FID and GC/C/IRMS Analysis of Rosa damascena Essential Oil. Rapid Commun. Mass Spectrom. 2013, 27, 591–602. [Google Scholar] [CrossRef] [PubMed]
  21. Xiao, Z.; Luo, J.; Niu, Y.; Wu, M. Characterization of Key Aroma Compounds from Different Rose Essential Oils Using Gas Chromatography-Mass Spectrometry, Gas Chromatography–Olfactometry and Partial Least Squares Regression. Nat. Prod. Res. 2018, 32, 1567–1572. [Google Scholar] [CrossRef] [PubMed]
  22. Cebi, N.; Arici, M.; Sagdic, O. The Famous Turkish Rose Essential Oil: Characterization and Authenticity Monitoring by FTIR, Raman and GC–MS Techniques Combined with Chemometrics. Food Chem. 2021, 354, 129495. [Google Scholar] [CrossRef]
  23. Aydinli, M.; Tutaș, M. Production of Rose Absolute from Rose Concrete. Flavour Fragr. J. 2003, 18, 26–31. [Google Scholar] [CrossRef]
  24. Nedeltcheva-Antonova, D.; Stoicheva, P.; Antonov, L. Chemical Profiling of Bulgarian Rose Absolute (Rosa damascenaMill.) Using Gas Chromatography–Mass Spectrometry and Trimethylsilyl Derivatives. Ind. Crops Prod. 2017, 108, 36–43. [Google Scholar] [CrossRef]
  25. Ohashi, T.; Miyazawa, Y.; Ishizaki, S.; Kurobayashi, Y.; Saito, T. Identification of Odor-Active Trace Compounds in Blooming Flower of Damask Rose (Rosa damascena). J. Agric. Food Chem. 2019, 67, 7410–7415. [Google Scholar] [CrossRef]
  26. Aycı, F.; Aydınlı, M.; Bozdemir, Ö.A.; Tutaş, M. Gas Chromatographic Investigation of Rose Concrete, Absolute and Solid Residue. Flavour Fragr. J. 2005, 20, 481–486. [Google Scholar] [CrossRef]
  27. Krupčík, J.; Gorovenko, R.; Špánik, I.; Sandra, P.; Armstrong, D.W. Enantioselective Comprehensive Two-Dimensional Gas Chromatography. A Route to Elucidate the Authenticity and Origin of Rosa damascena Miller Essential Oils: Gas Chromatography. J. Sep. Sci. 2015, 38, 3397–3403. [Google Scholar] [CrossRef] [PubMed]
  28. Kurkcuoglu, M.; Baser, K.H.C. Studies on Turkish Rose Concrete, Absolute, and Hydrosol. Chem. Nat. Compd. 2003, 39, 457–464. [Google Scholar] [CrossRef]
  29. Özkan, G.; Sagdiç, O.; Baydar, N.G.; Baydar, H. Antioxidant and Antibacterial Activities of Rosa damascena Flower Extracts. Food Sci. Technol. Int. 2004, 10, 277–281. [Google Scholar] [CrossRef]
  30. Chemat, F.; Rombaut, N.; Fabiano-Tixier, A.-S.; Pierson, J.T.; Bily, A. Green Extraction: From Concepts to Research, Education, and Economical Opportunities. In Green Extraction of Natural Products; Chemat, F., Strube, J., Eds.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2015; pp. 1–36. ISBN 978-3-527-67682-8. [Google Scholar]
  31. Gochev, V.; Girova, T.; Stoilova, I.; Atanasova, T.; Nenov, N.; Stanchev, V.; Stoyanova, A. Low Temperature Extraction of Essential Oil Bearing Plants by Liquefied Gases. 7. Seeds from Cardamom (Elettaria Cardamomum (L.) Maton). J. Biosci. Biotechnol. 2012, 1, 135–139. [Google Scholar]
  32. Khambay, B.P.S. Extraction and Isolation of Artemisin with HFC-134a. In Proceedings of the Artemisinin Forum 2008, Guilin, China, 26 November 2008. [Google Scholar]
  33. Mihov, R.; Nikovska, K.; Nenov, N.; Slavchev, A. Evaluation of Mayonnaise-like Food Emulsions with Extracts of Herbs and Spices. Emir. J. Food Agric. 2012, 24, 191–199. [Google Scholar]
  34. Nenov, N.; Gochev, V.; Girova, T.; Stoilova, I.; Atanasova, T.; Stanchev, V.; Stoyanova, A. Low Temperature Extraction of Essential Oil Bearing Plants by Liquefied Gases. 6. Barks from Cinnamon (Cinnamomum Zeylanicum Nees). J. Essent. Oil Bear. Plants 2011, 14, 67–75. [Google Scholar] [CrossRef]
  35. Stoyanova, A.; Nenov, N.; Slavchev, A.; Jirovetz, L.; Buchbauer, G.; Lien, H.; Schmidt, E.; Geissler, M. C2H2F4-Oleoresins of Black Pepper(Piper NigrumL.)and Ginger (Zingiber Officinale(L.)Rosc.) from Vietnam: Antimicrobial Testings, Gas Chromatographic Analysis and Olfactoric Evaluation. Electron. J. Environ. Agric. Food Chem. 2006, 5, 1615–1623. [Google Scholar]
  36. Directive 2009/32/EC of the European Parliament and of the Council of 23 April 2009 on the Approximation of the Laws of the Member States on Extraction Solvents Used in the Production of Foodstuffs and Food Ingredients. Off. J. Eur. Union 2009, 52.
  37. Solkane®134a Thermodynamics; SOLVAY FLUOR GMBH: Hannover, Germany, 2018; Release 1.05.
  38. SOLKANE® 227 Pharma SOLKANE® 134a Pharma; SOLVAY FLUOR: Hannover, Germany, 2018.
  39. Haghighi, A.; Khajenoori, M. Subcritical Water Extraction. In Mass Transfer-Advances in Sustainable Energy and Environment Oriented Numerical Modeling; Nakajima, H., Ed.; InTech: London, UK, 2013; ISBN 978-953-51-1170-2. [Google Scholar]
  40. Özel, M.Z.; Göğüş, F.; Lewis, A.C. Comparison of Direct Thermal Desorption with Water Distillation and Superheated Water Extraction for the Analysis of Volatile Components of Rosa damascena Mill. Using GCxGC-TOF/MS. Anal. Chim. Acta 2006, 566, 172–177. [Google Scholar] [CrossRef]
  41. Manouchehri, R.; Saharkhiz, M.J.; Karami, A.; Niakousari, M. Extraction of Essential Oils from Damask Rose Using Green and Conventional Techniques: Microwave and Ohmic Assisted Hydrodistillation versus Hydrodistillation. Sustain. Chem. Pharm. 2018, 8, 76–81. [Google Scholar] [CrossRef]
  42. Reverchon, E.; Delta Porta, G. Rose Concrete Fractionation by Supercritical CO2. J. Supercrit. Fluids 1996, 9, 199–204. [Google Scholar] [CrossRef]
  43. Boelens, M.H.; Boelens, H. Differences in Chemical and Sensory Properties of Orange Flower and Rose Oils Obtained from Hydrodistillation and from Supercritical C02 Extraction. Perfum. Flavorist 1997, 22, 31–35. [Google Scholar]
  44. Reverchon, E.; Della Porta, G.; Gorgoglione, D. Supercritical CO2 Extraction of Volatile Oil from Rose Concrete. Flavour Fragr. J. 1997, 12, 37–41. [Google Scholar] [CrossRef]
  45. Ghoreishi, S.M.; Hedayati, A.; Mousavi, S.O. Quercetin Extraction from Rosa damascena Mill via Supercritical CO2: Neural Network and Adaptive Neuro Fuzzy Interface System Modeling and Response Surface Optimization. J. Supercrit. Fluids 2016, 112, 57–66. [Google Scholar] [CrossRef]
  46. Wilde, P.F.; McClory, P.J. New Solvents for Extraction. Perfum. Flavorist 1994, 19, 25–28. [Google Scholar]
  47. Baser, K.H.C.; Kurkcuoglu, M.; Özek, T. Turkish Rose Oil Research: Recent Results. Perfum. Flavorist 2003, 28, 34–42. [Google Scholar]
  48. Antonova, D.V.; Medarska, Y.N.; Stoyanova, A.S.; Nenov, N.S.; Slavov, A.M.; Antonov, L.M. Chemical Profile and Sensory Evaluation of Bulgarian Rose (Rosa damascena Mill.) Aroma Products, Isolated by Different Techniques. J. Essent. Oil Res. 2020, 1–11. [Google Scholar] [CrossRef]
  49. Nenov, N.; Atanasova, T.; Gochev, V.; Merdzhanov, P.; Girova, T.; Djurkov, T.; Stoyanova, A. New Product from Bulgarian Rose. Int. Sci. Pract. Conf. World Sci. 2016, 1, 17–22. [Google Scholar]
  50. Roth, M. Thermodynamic Prospects of Alternative Refrigerants as Solvents for Supercritical Fluid Extraction. Anal. Chem. 1996, 68, 4474–4480. [Google Scholar] [CrossRef]
  51. Joichi, A.; Yomogida, K.; Awano, K.; Ueda, Y. Volatile Components of Tea-Scented Modern Roses and Ancient Chinese Roses. Flavour Fragr. J. 2005, 20, 152–157. [Google Scholar] [CrossRef]
  52. Hirata, H.; Ohnishi, T.; Watanabe, N. Biosynthesis of Floral Scent 2-Phenylethanol in Rose Flowers. Biosci. Biotechnol. Biochem. 2016, 80, 1865–1873. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  53. Rusanov, K.; Kovacheva, N.; Rusanova, M.; Atanassov, I. Reducing Methyl Eugenol Content in Rosa damascena Mill Rose Oil by Changing the Traditional Rose Flower Harvesting Practices. Eur. Food Res. Technol. 2012, 234, 921–926. [Google Scholar] [CrossRef]
  54. Tan, K.H.; Nishida, R. Methyl Eugenol: Its Occurrence, Distribution, and Role in Nature, Especially in Relation to Insect Behavior and Pollination. J. Insect Sci. 2012, 12, 1–60. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  55. Dobreva, A.; Velcheva, A.; Bardarov, V.; Bardarov, K. Chemical Composition of Different Genotypes Oil - Bearing Roses. Bulg. J. Agric. Sci. 2013, 19, 1213–1218. [Google Scholar]
  56. Rusanov, K.; Kovacheva, N.; Atanassov, I. Comparative GC/MS Analysis of Rose Flower and Distilled Oil Volatiles of The Oil Bearing Rose Rosa damascena. Biotechnol. Biotechnol. Equip. 2011, 25, 2210–2216. [Google Scholar] [CrossRef] [Green Version]
  57. Ghosh, S. Triterpenoids: Structural diversity, biosynthetic pathway, and bioactivity. In Studies in Natural Products Chemistry; Elsevier: Amsterdam, The Netherlands, 2020; Volume 67, pp. 411–461. ISBN 978-0-12-819483-6. [Google Scholar]
  58. Riffault-Valois, L.; Destandau, E.; Pasquier, L.; André, P.; Elfakir, C. Complementary Analytical Methods for the Phytochemical Investigation of ‘Jardin de Granville’, a Rose Dedicated to Cosmetics. Comptes Rendus Chim. 2016, 19, 1101–1112. [Google Scholar] [CrossRef] [Green Version]
  59. Da Porto, C.; Decorti, D.; Natolino, A. Application of a Supercritical CO 2 Extraction Procedure to Recover Volatile Compounds and Polyphenols from Rosa damascena. Sep. Sci. Technol. 2015, 50, 1175–1180. [Google Scholar] [CrossRef]
  60. Staikov, V.; Decheva, R.; Balinova-Tsvetkova, A. Studies on the Composition of Rose Oil Obtained from the Flowers in Different Stages of Their Development. Riv. Ital. 1975, 57, 192–195. [Google Scholar]
  61. Seify, Z.; Yadegari, M.; Pirbalouti, A. Essential Oil Composition of Rosa damascena Mill. Produced With Different Storage Temperatures and Durations. Korean J. Hortic. Sci. Technol. 2018, 36. [Google Scholar] [CrossRef]
  62. Barao, T.; de Castro, C.A.N.; Mardolcar, U.V.; Okambawa, R.; St-Arnaud, J.M. Dielectric Constant, Dielectric Virial Coefficients, and Dipole Moments of 1,1,1,2-Tetrafluoroethane. J. Chem. Eng. Data 1995, 40, 1242–1248. [Google Scholar] [CrossRef]
Molecules 26 04991 g001 550
Figure 1. GC/MS profile of subcritical (1,1,1,2-tetrafluorethane) extracts on a DB-17HT column: (a) R. gallica; (b) R. damascena; (c) R. alba; (d) R. centifolia.
Figure 1. GC/MS profile of subcritical (1,1,1,2-tetrafluorethane) extracts on a DB-17HT column: (a) R. gallica; (b) R. damascena; (c) R. alba; (d) R. centifolia.
Molecules 26 04991 g001
Molecules 26 04991 g002 550
Figure 2. Main chemical classes distribution, according to the data from Table 1: (a) R. gallica, (b) R. damascena, (c) R. alba and (d) R. centifolia.
Figure 2. Main chemical classes distribution, according to the data from Table 1: (a) R. gallica, (b) R. damascena, (c) R. alba and (d) R. centifolia.
Molecules 26 04991 g002
Table
Table 1. Chemical composition of R134a rose extracts, as determined using GC/MS/FID on a DB-17HT column.
Table 1. Chemical composition of R134a rose extracts, as determined using GC/MS/FID on a DB-17HT column.
NoCompoundLRIexp
DB-17HT		Rel.%, as Determined Using GC-FID
R. galicaR. damascenaR. albaR. centifolia
1.α-Pinene8450.240.420.120.16
2.β-Pinene944n.d.0.080.010.02
3.β-Myrcene9680.170.090.030.02
4.Limonene1003n.d.n.d.0.080.01
5.p-Cymene1026n.d.n.d.0.01n.d.
6.Benzaldehyde1051n.d.n.d.n.d.n.d.
7.Linalool12010.070.070.10n.d.
8.Rose oxide1205n.d.0.01n.d.n.d.
9.Benzyl alcohol12230.841.484.430.27
10.Octanoic acid12980.14n.d.0.02n.d.
11.2-Phenyl ethyl alcohol131727.2259.1514.078.99
12.β-Citronellol13661.725.272.842.85
13.Nerol13742.241.496.131.26
14.Phenyl ethyl formate13810.120.120.08n.d.
15.Geraniol14148.463.0114.412.87
16.Neral1392n.d.0.210.070.10
17.Geranial14400.340.240.950.09
18.Phenyl ethyl acetate1469n.d.0.150.040.11
19.β-Elemene1472n.d.0.120.01n.d.
20.Cytronellyl acetate1475n.d.n.d.0.08n.d.
21.Anethole (Benzene,1-methoxy-4(1-propenyl))1482n.d.n.d.0.25n.d.
22.Pentadecane(C15)15000.070.060.09n.d.
23.β-Caryophyllene15060.250.170.980.16
24.Geranic acid15220.110.480.260.37
25.β-Copaene1520n.d.n.d.n.d.0.26
26.α-Guaiene1518n.d.0.06n.d.n.d.
27.Geranyl acetate15400.170.160.03n.d.
28.α-Caryophyllene1552n.d.n.d.n.d.n.d.
29.Hydroxy linalool1568n.d.n.d.0.03n.d.
30.Eugenol15740.071.260.08n.d.
31.Germacrene D15930.090.11n.d.0.74
32.β-Cubebene1598n.d.n.d.n.d.n.d.
33.α-Muurolene1607n.d.n.d.n.d.n.d.
34.β-Guaiene1611n.d.0.06n.d.n.d.
35.β-Copaene1616n.d.n.d.n.d.n.d.
36β-Cadinene1646n.d.n.d.n.d.0.12
37.Methyl eugenol1654n.d.0.49n.d.n.d.
38.Heptadecane (C17)17001.480.461.650.88
39.Bulnesol17030.810.090.251.10
40.Tetradecanal(Myristyl aldehyde)17060.10n.d.n.d.n.d.
41.Heptadecene (C17:1)1710n.d.n.d.0.01n.d.
42.Benzyl tiglate + Heptadecadiene (C17:2)17140.14n.d.0.070.27
43.Octadecane(C18)17440.140.06n.d.0.07
44.γ-Eudesmol1796n.d.n.d.0.020.05
45.τ-Cadinol1805n.d.n.d.n.d.n.d.
46.α-Eudesmol18190.24n.d.0.020.49
47.β-Eudesmol18260.36n.d.0.140.81
48.α-Cadinol1833n.d.n.d.0.09n.d.
49.Nonadecane + Nonadecene (C19 + C19:1)190017.975.0915.6612.75
50.Hexadecanal19360.07n.d0.04n.d
51.Eicosane(C20)20000.980.461.500.65
52.Selina-4.7-diol20460.08n.dn.d0.43
53.Unknown sesquiterpene20540.31n.dn.d0.92
54.Heneicosane(C21)21009.673.0911.838.34
55.Heneicosene(C21:1)21050.240.171.310.34
56.Heneicosene(C21:1), isomer2121n.d0.030.250.07
57.Docosane(C22)22000.470.12n.d0.44
58.Docosene(C22:1)2211n.dn.dn.d0.06
59.Eudesm-4-en-3-one,11-hydroxy22434.67n.dn.d0.11
60.Tricosane(C23)23000.071.272.468.63
61.Tricosene(C23:1)23180.300.181.861.65
62.Tricosene(C23:1), isomer23340.100.210.330.35
63.1,1,9-Eicosadiene23480.090.040.120.08
64.Tetracosane (C24)24000.250.09n.d0.44
65.Farnesol acetate24230.14n.dn.dn.d
66.Hexanoic acid,2-ethyl,tetradecyl ester24490.330.09n.dn.d
67.Pentacosene(C25:1)25110.220.070.210.17
68.Pentacosene(C25:1)25240.070.050.970.88
69.Pentacosene(C25:1)2532n.dn.d0.320.30
70.Octanoic acid, tetradecyl ester25480.100.070.04n.d
71.Hexacosane(C26)26000.100.060.050.11
72.Hexacosene(C26:1)2612n.d0.050.200.13
73.Octanoic acid, hexadecyl ester2668n.dn.dn.d0.22
74.Heptacosane +Heptacosene (C27 + C27:1)27000.100.080.210.80
75.Heptacosene(C27:1), isomer27080.420.320.270.33
76.Heptacosene(C27:1), isomer2721n.dn.d1.191.93
77.Heptacosanol2789n.dn.dn.d0.10
78.Citronellyl ester (stearate)28430.080.18n.d0.25
79.Geranyl ester2876n.dn.dn.d0.10
80.Nonacosene(C29:1)29111.030.810.492.13
81.Phenyl ethyl ester29250.330.520.520.71
82.Squalene29310.620.08n.d0.55
83.Dodecanoic acid, phenyl methyl ester2939n.dn.dn.d0.16
84.Citronellyl ester (phenyl acetate)2942n.dn.dn.d1.28
85.Neryl ester (phenyl acetate)2956n.d0.06n.d1.15
86.Neryl ester2961n.dn.dn.d7.35
87.Phenyl ethyl ester2964n.dn.dn.d1.95
88.Phenyl ethyl ester (linoleate)29840.080.29n.d0.10
89.Citronellyl ester3016n.dn.dn.d0.55
90.Geranyl ester (stearate)3058n.dn.dn.d0.87
91.Neryl ester (stearate)30760.070.06n.d4.82
92.Phenyl ethyl ester (stearate)3112n.dn.dn.d1.83
93.Citronellyl ester3224n.dn.dn.d0.54
94.Phenyl ethyl ester34210.13n.dn.d0.45
95.Neryl ester3432n.d0.060.290.86
96.β-Amyrin34420.930.45n.d0.14
97.Phenyl ethyl ester34560.310.12n.d0.35
98.9,19-Cyclolanost-24-en-3-ol acetate3462n.dn.dn.d0.27
99.Olean-12-en-3-one (Amirenone)34680.270.280.150.65
100.α-Amyrin + Unindentified triterpene34760.140.170.090.78
101.Unindentified triterpene35190.790.23n.d0.25
102.Lup20(29)-en-3-one35460.200.35n.dn.d
103.Lupeol36160.741.170.150.19
Phenylethanoids and phenylpropanoids27.2960.9014.408.99
Monoterpenes13.6711.8925.4425.52
-Monoterpene hydrocarbons0.410.590.250.21
-Oxygeneted monoterpenes13.2611.3025.1925.31
Aliphatic hydrocarbons33.9212.7740.9841.70
Sesquiterpenes6.950.612.055.19
Triterpenes3.692.730.382.83
Others1.151.484.960.38
TOTAL identified89.8192.5489.7393.68
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Dobreva, A.; Nedeltcheva-Antonova, D.; Nenov, N.; Getchovska, K.; Antonov, L. Subcritical Extracts from Major Species of Oil-Bearing Roses—A Comparative Chemical Profiling. Molecules 2021, 26, 4991. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164991

AMA Style

Dobreva A, Nedeltcheva-Antonova D, Nenov N, Getchovska K, Antonov L. Subcritical Extracts from Major Species of Oil-Bearing Roses—A Comparative Chemical Profiling. Molecules. 2021; 26(16):4991. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164991

Chicago/Turabian Style

Dobreva, Ana, Daniela Nedeltcheva-Antonova, Nenko Nenov, Kamelia Getchovska, and Liudmil Antonov. 2021. "Subcritical Extracts from Major Species of Oil-Bearing Roses—A Comparative Chemical Profiling" Molecules 26, no. 16: 4991. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164991

Article Metrics

Back to TopTop