GC/MS Analysis of Citrus aurantium L. Hydrolate and its Comparison with the Commercial Samples GC/MS Analysis of Citrus aurantium L. Hydrolate and its Comparison with the Commercial Samples

Authors

Abstract

The chemical composition of the Hydrolate of Citrus aurantium L. (Rutaceae) flowers (neroli) grown in Iran, and two commercial hydrolates were analyzed by GC/MS. Thirty compounds (90.3%) were identified in the Hydrolate by the use of laboratory apparatus, thirty-eight compounds (83.4%) in the Hydrolate from the traditional method and fifteen compounds (98.3%) in the industrially produced sample. The major compounds within the Hydrolate obtained in the laboratory were geraniol (26.6%), a-terpineol (20.7%), linalool (15.4%) and benzene acetaldehyde (5.5%). Linalool (44.1%), methyl anthranilate (11.8%) and cis-linalool oxide (6.1%) were found in high percentages in the Hydrolate from the obtained traditional sample. 1,8-Cineol (15.9%), linalool (13.8%) and a-terpineol (6.6%) were more than other constituents in the industrially obtained hydrolate.

Keywords


GC/MS Analysis of Citrus aurantium L. Hydrolate and its Comparison with the Commercial Samples

Iranian Journal of Pharmaceutical Research (2004) 3: 177-179
Received: February 2004
Accepted: March 2004

Copyright ? 2004 by School of Pharmacy
Shaheed Beheshti University of Medical Sciences and Health Services

Original Article

GC/MS Analysis of Citrus aurantium L. Hydrolate and its Comparison with the Commercial Samples

Hamid Reza Monsef-Esfahani*, Yaghoob Amanzade, Zahra Alhani, Homa Hajimehdipour, Mohammad Ali Faramarzi

Department of Pharmacognosy, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran

* Corresponding author: E-mail: monsefes@sina.tums.ac.ir

 

Abstract


The chemical composition of the Hydrolate of Citrus aurantium L. (Rutaceae) flowers (neroli) grown in Iran, and two commercial hydrolates were analyzed by GC/MS. Thirty compounds (90.3%) were identified in the Hydrolate by the use of laboratory apparatus, thirty-eight compounds (83.4%) in the Hydrolate from the traditional method and fifteen compounds (98.3%) in the industrially produced sample. The major compounds within the Hydrolate obtained in the laboratory were geraniol (26.6%), a-terpineol (20.7%), linalool (15.4%) and benzene acetaldehyde (5.5%). Linalool (44.1%), methyl anthranilate (11.8%) and cis-linalool oxide (6.1%) were found in high percentages in the Hydrolate from the obtained traditional sample. 1,8-Cineol (15.9%), linalool (13.8%) and a-terpineol (6.6%) were more than other constituents in the industrially obtained hydrolate.        
Keywords: Citrus aurantium L.; Neroli; Hydrolate; Commercial sample; GC/MS.

Introduction
 
The genus Citrus (Rutaseae) comprises various species, varieties and hybrids, most of them are found in the north, south and south-eastern parts of Iran (1). Among them, Citrus aurantium L. is the unique species, with pharmacological applications. The Hydrolate of its flowers has been used in traditional medicine as a remedy for the treatment of mild depression, sedation and as a heart tonic (2, 3).
A search through the literature revealed some reports on the chemical composition and pharmacological properties of C. aurantium. The physicochemical indices of neroli oils from different origins were firstly reported in 1949. GC analysis was then later made by Prager and Miskeiwicz (4). The quantitative composition of the flower water absolute was also studied and it was found that the major components were linalool (44.2%), a-terpineol (18.5%), and graniol (6.4%) (5).
Neroli is known to be an antidepressant, antibacterial and cytophylactic agent. Results showed that patients given Neroli experienced less anxiety compared to those not receiving it (6). Neroli is also reported to help promote skin renewal and in addition its smell is helpful in easing stress and also particularly useful for cases of mild depression (7).
Although several studies have been performed on the flower water absolute from other countries, no research has so far been conducted on the traditional used of its Hydrolate in Iran. In this work, GC/MS analysis was used for the Citrus aurantium Hydrolate and its comparison it with the commercial samples obtained traditionally and industrially.
 
Experimental
 
Plant Material 
The flowers of C. aurantium were collected from Darab on the south of Fars province in Iran at an altitude of 1107 m, during April 2003. Voucher specimens have been deposited in the herbarium of Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran. The traditional Hydrolate sample was obtained from the local producer and the industrial Hydrolate sample was purchased from the market (Camo Trade Mark).
Isolation procedures
The oil isolation procedure was performed via a Clevenger-type apparatus using air-dried flowers (100 g) by the hydrodistillation method for 3.5 h. Liquid-liquid extraction for obtaining the aromatic fraction was carried out on 200 ml of Hydrolate with normal pentane (99+%, Merck). The organic layer was separated, dried over anhydrous sodium sulphate and the solvent was evaporated at room temperature.
 
Identification of oil components
GC/MS was performed on a Thermoquest 2000 with a quadropole detector, on a DB-5 capillary column (30 m x 0.25 mm; 0.25 mm film thickness). The carrier gas was helium with a flow of 1.5 ml/min, split ratio of 1/25 and a flame ionisation detector. The column temperature was programmed at 50°C for 1 min and then heated to 260°C with a 2.5°C/min rate and then kept constant at 260°C for 20 min. The MS operated at 70eV ionisation energy. Mass range was from m/z 50-300 amu. Retention indices were calculated by using retention times of n-alkanes, which were injected at the same chromatographic conditions. The compounds were identified by comparison of the relative retention indices (RRI, DB-5) with those in the literature (8) and by computer searching followed by matching the mass spectra data with those stored in the computer library.
 
Results and Discussion
 
Three kinds of hydrolates (laboratory obtained, traditional and industrial samples) were extracted using pentane by a liquid-liquid extractor. The yield of oils obtained was 0.015, 0.003 and 0.002 percents, respectively. The chemical and class composition of the oils are presented in Tables 1 and 2.

The laboratory obtained Hydrolate was mainly consisted of alcohol monoterpenes (66.1%) and the major compounds were geraniol (26.6%), a-terpineol (20.7%) and linalool (15.4%). In the traditional hydrolate, although the main constituent was alcohol monoterpenes (50.5%), but the chief components were linalool (44.1%), methyl anthranilate (11.8%) and linalool oxide (6.1%), which were different from the laboratory obtained Hydrolate to some extent. Despite of the other results, hydrocarbon monoterpenes (49.2%) were the predominant constituents within the industrial sample, followed by alcohol monoterpenes (22.3%), ether and oxide monoterpens (16.9%).
The major components in the industrial Hydrolate were limonene (46.6%) and 1,8-cineol (15.9%). Limonene, however, was not found in the laboratory obtained and also traditional hydrolate, as already reported that it was present in lower than twenty four percent in Neroli oil and five percent in Hydrolate (9). However, 1,8-cineol was observed only in this hydrolate.
According to the literature (10), the percentage of limonene observed in this sample could be a case of adulteration. It seems that it is contaminated with the flowers and other parts of the plant. Citrus species peels normally contain more than 70% limonene (9). The differences observed in the traditional and laboratory obtained Hydrolate have presumably risen from the applied fresh flowers in the traditional procedure.
References

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Dictionary of Iranian Plant Names. Farhang Mo'aser Publishers, Tehran (1996) 131  
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Medicinal Plants. Vol. 1, 4th ed. Tehran University Press, Tehran (1986), 478-485
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(4) Prager M and Miskiewicz M. Gas chromatographic-mass spectrometric analysis, identification and detection of adulteration of perfumery products from bitter orange trees. Assos. Off. Anal. Chem. (1981) 64: 131-138
(5) Peyron L and Bonaccorsi I. Extracts from the bitter orange flowers (Citrus aurantium L.): composition and adulteration. In: Dugo G. (ed.) Citrus. Taylor & Francis Inc., London (2002) 413-424
(6) Schiffman. S. New frontiers in fragrance use. Cosmetics and toiletries (1991) 106: 44-45
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(10) Juchelka D, Steil A, Witt K and Mosandl A. Chiral compound of essential oil. XX. Chirality evaluation and authenticity profiles of neroli and Petitgrain oil. J.  Essent. Oil Res. (1996) 8: 487-497