Differentiation of essential oils in Atractylodes lancea and Atractylodes koreana by gas chromatography with mass spectrometry

Atractylodes rhizome is a valuable traditional Chinese medicinal herb that comprises complex several species whose essential oils are the primary pharmacologically active component. Essential oils of Atractylodes lancea and Atractylodes koreana were extracted by hydrodistillation, and the yield was determined. The average yield of essential oil obtained from A. lancea (2.91%) was higher than that from A. koreana (2.42%). The volatile components of the essential oils were then identified by a gas chromatography with mass spectrometry method that demonstrated good precision. The method showed clear differences in the numbers and contents of volatile components between the two species. 41 and 45 volatile components were identified in A. lancea and A. koreana, respectively. Atractylon (48.68%) was the primary volatile component in A. lancea, while eudesma‐4(14)‐en‐11‐ol (11.81%) was major in A. koreana. However, the most significant difference between A. lancea and A. koreana was the major component of atractylon and atractydin. Principal component analysis was utilized to reveal the correlation between volatile components and species, and the analysis was used to successfully discriminate between A. lancea and A. koreana samples. These results suggest that different species of Atractylodes rhizome may yield essential oils that differ significantly in content and composition.     

Comparative analysis in different organs and tissue-specific metabolite profiling of Atractylodes lancea from four regions by GC–MS and laser microdissection

Traditional Chinese medicine is made from the rhizome of Atractylodes lancea (Thunb.) DC. (Compositae), known as Cangzhu. In this study, gas chromatography-mass spectrometry was used to identify and quantify the volatile oils of different organs of A. lancea from four regions of China: Jiangsu, Anhui, Henan, and Hubei provinces. The volatile oils of A. lancea were qualitatively and quantitatively characterized using gas chromatography-mass spectrometry combined with laser microdissection. The results identified 21 components in A. lancea, the majority of the components were found in the rhizomes, followed by the fibrous roots, flowers, leaves, and stems. According to the contents of volatile oils in A. lancea, it was divided into Dabieshan (mainly includes hinesol and β-eudesmol) and Maoshan types (mainly includes atractylon and atractylodin), and the ratios of hinesol:β-eudesmol:atractylon:atractylodin were 17.06:4.55:0:1, 12.66:11.71:0.99:1, 7.43:6.23:0:1, and 0.13:0.16:1.52:1 in A. lancea from AH, HN, HB, and JS, respectively. Tissue-specific study indicated that Dabieshan type mainly includes elemol, hinesol, and β-eudesmol in the periderm and secretory cavities of A. lancea, whereas Maoshan type mainly includes atractylon, atractylodin, little hinesol, and β-eudesmol in the secretory cavities. Conversely, no volatile oils were detected in the cortex, phloem, xylem, vascular ray, or pith. This study provides a foundation for further evaluation and utilization of A. lancea.     

Development of direct microwave desorption/gas chromatography mass spectrometry system for rapid analysis of volatile components in medicinal plants

A new direct microwave desorption–gas chromatography‐mass spectrometry method was developed for the analysis of the essential oils of medicinal plants. A homemade direct microwave desorption system was fabricated and used for the desorption of volatile components of medicinal herbs. The desorbed volatiles are transferred directly into the gas chromatography injector for analysis in a one‐step process. Approximately 0.3 g of the herb was needed for the desorption of samples in 60 s. In this study, more than 53 volatile compounds were identified and quantified for Echinophora platyloba DC as model herb sample. The results were found to be in good agreement with the conventional hydrodistillation extraction data. The described results show that direct microwave desorption is fast, simple, and easy to automate and requires only a small amount of sample. The results indicate that essential oil components valuable for varietal identification and characteristic of each variety analyzed when direct microwave desorption–gas chromatography‐mass spectrometry was used for analysis.     

Application of Comprehensive Two‐Dimensional Gas Chromatography (GC×GC) to the Qualitative Analysis of Essential Oils

This paper investigates the separation of moderately complex samples by comprehensive two‐dimensional gas chromatography (GC×GC). The analysis of peppermint (Mentha piperita) and spearmint (Mentha spicata) essential oil components, including acetates, alcohols, furans, ketones, sesquiterpenes, and terpenes, was achieved by one‐dimensional gas chromatography with quadrupole mass spectrometry detection (GC/MSD) and GC×GC with flame ionization detection. Peppermint essential oil was found to contain 89 identifiable peaks by GC×GC compared to 30 peaks in the GC/MSD chromatogram. Likewise, 68 peaks were found in the GC×GC chromatogram of spearmint (compared to 28 in GC/MSD). Plots of the first dimension versus second dimension retention times provided a fingerprint of the two essential oils, which revealed 52 similar compounds between the two essential oils as opposed to 18 matches by 1D GC.     

A study of the compositional variation of the essential oil of ylang-ylang (Cananga odorata Hook Fil. et Thomson,formagenuina) during flower development

Volatile secondary metabolites from Colombian ylang-ylang flowers were obtained by combined steam distillation - solvent extraction. The samples were analyzed by high resolution gas chromatography with flame ionization, nitrogen/phosphorus, or mass spectrometric detection. The chemical composition of the oils extracted from flowers at different stages of development differed both qualitatively and quantitatively. The generation of total volatile metabolites, light oxygenated compounds in particular, increased markedly during flower maturation. In this work the quality of the ylang-ylang essential oils was studied as a function of flower maturity.     

Chemical Composition and Antimicrobial Activity of the Essential Oils Extracted by Microwave-Assisted Hydrodistillation from the Flowers of Two Plumeria Species

Microwave-assisted hydrodistillation (MAHD) was applied to obtain essential oils from the fresh flowers of Plumeria rubra Linn (PRL) and Plumeria rubra Linn var. acutifolia (PRLA) cultivated in China, which were subsequently analyzed via gas chromatography with flame ionization detection and gas chromatography with mass spectrometry. The essential oils were assessed for their antimicrobial activity. A variation of the chemical composition attributed to varieties was revealed. The essential oil of PRLA was found to have a high content of carboxylic acids (59.7%) with n-hexadecanoic acid (35.8%) and n-tetradecanoic acid (11.2%) as main components. Whereas, the PRL oil was characterized by high hydrocarbon content (38.6%), in which 9-hexacosene (14.6%) was found to be the major constituent. All essential oils possessed antimicrobial activity especially against five bacteria with diameter of inhibition zone (DD) and minimum inhibitory concentrations (MIC) values in the range of 6.8 to 21.3 mm and 2.8 to 46.5 mg/mL, respectively.     

Comparison of MAHD with UAE and Hydrodistillation for the Analysis of Volatile Oil From Four Parts of Perilla frutescens Cultivated in Southern China

Three different isolation techniques, specifically microwave-assisted hydrodistillation (MAHD), ultrasound-assisted extraction (UAE), and conventional hydrodistillation (HD) were employed to obtain essential oils from whole plants, leaves, roots, and stems of Perilla frutescens. The essential oils were analyzed using gas chromatography with flame ionization detection and gas chromatography with mass spectrometry. Variations in chemical composition were observed; these were attributed to differences in plant organs. Variations in the percentages of the main constituents of the oils extracted based on plant organ were irregular and affected the quantity and composition of the oils. Oil yields were affected by the method of extraction and extraction organ variation. The maximum volume of oil was extracted from leaves via MAHD and the minimum was extracted from roots via UAE. Oil yields ranged from 0.05% to 0.53%. The contents of essential oil varied significantly with the plant organ. In the essential oils of the plant parts studied were showed a predominance of oxygenated monoterpenes. Variation of extraction methods and organs may influence the oil components either qualitatively or quantitatively.     

Enantioselective comprehensive two‐dimensional gas chromatography. A route to elucidate the authenticity and origin of Rosa damascena Miller essential oils

The analysis of Bulgarian and Turkish Rosa damascena Miller essential oils was performed by flow‐modulated comprehensive two‐dimensional gas chromatography using simultaneous detection of the second column effluent by flame ionization and quadrupole mass spectrometric detection. Enantioselective separations were obtained by running the samples on 2,3‐di‐O‐ethyl‐6‐O‐tert‐butyldimethylsilyl‐β‐cyclodextrin column as the first column and on polyethylene glycol as the second column. The determination of enantiomeric or diastereomeric excess of some terpenoic solutes is a possible route for quality or authenticity control as well as for the elucidation of the country of origin.     

Volatile Constituents of Achillea ligustica All. by HS-SPME/GC/GC-MS. Comparison with Essential Oils Obtained by Hydrodistillation from Corsica and Sardinia

The volatile components extracted from the headspace (HS) of Achillea ligustica All. samples and their separated organs using solid phase microextraction (SPME) were investigated by gas chromatography and gas chromatography-mass spectrometry. Fiftyseven compounds were identified, the main components were camphor (14.2–29.8%), artemisia ketone (0.3–26.7%), santolina alcohol (0.5–9.4%), camphene (3.0–9.0%) and trans-sabinyl acetate (1.6–5.5%). Moreover, the chemical composition of Corsican and Sardinian A. ligustica oils obtained from flowers and leafy stems harvested in four regions of both islands, were investigated. Two collective oils of A. ligustica were also investigated, comparison between both oils as well as from data literature were reported. A comparison of hydrodistillation and HS-SPME extraction of volatile components in term of isolation time, plant-consuming and chemical composition was discussed. HS-SPME technique was clearly fast in contrast to hydrodistillation (90 min/300 min). HS extraction was performed with a much smaller amount of plant than hydrodistillation. Although the aromatic profiles of HS-fractions and oils showed several quantitative differences HS-SPME can be applied to routine control analysis of aromatic and medicinal plants.

     

Separation of aromatic solvents from oil refinery reformates by a newly designed ionic liquid using gas chromatography with flame ionization detection

The aim of this study was to determine whether the new ionic liquid, N,N‐dimethyl‐2‐oxopyrrolidonium iodide, synthesized in our laboratory is a suitable solvent for the separation of aromatic components benzene, toluene, ethylbenzene, and xylenes from petroleum mixtures (reformates) in liquid–liquid extraction. In pursuance of the above aim, a method to extract all components of a mixture, containing four aromatic components simultaneously, was developed. A new ionic liquid and a previously used liquid were compared for their extraction abilities. These ionic liquids were, respectively, N,N‐dimethyl‐2‐oxopyrrolidinium iodide and 1‐ethyl‐3‐methyl imidazolium ethyl sulfate. The concentrations of each benzene, toluene, ethylbenzene, and xylenes component in the extract and raffinate phases were measured by gas chromatography with flame ionization detection as volume percent to determine the extraction ability of the ionic liquids. The results obtained for both the reformate samples and model mixtures indicated that the new ionic liquid was effective as an extracting solvent for the recovery of aromatic components from reformates. Also the analysis results, using gas chromatography with flame ionization detection, for the reformate samples were as good as the results obtained by a local oil refinery. The extraction results also show that the developed method is very suitable for the separation and analysis of aromatic components in reformates.     

Chemical composition and variability of the volatile components from inflorescences of Cirsium species

The present study aimed to investigate the chemical composition of the essential oils of inflorescences Cirsium spp. (Asteraceae) by GC/MS method. Essential oils were extracted from the inflorescences of Cirsium pannonicum (Link), Cirsium ligulare Boiss., Cirsium heterophyllum (L.) Hill., Cirsium acaule (L.) Scop., Cirsium oleraceum (L.) Scop., Cirsium dissectum (L.) Hill., Cirsium decussatum (Janka) and Cirsium eriophorum (L.) Scop., using the steam distillation method. A gas chromatography–mass spectrometry method was employed for the analysis of essential oils. Our study shows the differences in chemical composition of volatile oils in the inflorescences of Cirsium spp. The main components of the essential oil were ketones and aldehydes with a long carbon side-chain. Volatile oils also contained small amounts of terpenes: thymol, β-linalool, eugenol, carvacrol and fatty acids with odd number of carbon atoms–waxes. The compounds in the essential oils obtained from inflorescences Cirsium L. species have been identified for the first time.     

Chemical fingerprinting and quantitative analysis of volatiles in <Emphasis Type="Italic">Shexiang Baoxin Pill</Emphasis> by gas chromatography with flame ionization and mass spectrometric detection

An approach to fingerprinting and the quantitative analysis of volatiles in Shexiang Baoxin Pill (SBP) was proposed by using gas chromatography (GC) with a flame ionization detector and a mass spectrometric detector (MS). Using the proposed method, the chemical fingerprint of SBP extract was established, in which the separation of more than 30 volatiles was realized in about 30 min, and 26 peaks were identified by GC/MS analysis. Seven major volatiles, including borneol, isoborneol, isopropyl methylphenol, mascone, cinnamaldehyde, cinnamic acid, and benzyl benzoate, were further quantified. The linearity, precision, stability, repeatability, and accuracy were acceptable. The proposed method was successfully applied to the determination of volatiles in 11 batches of SBP samples. To evaluate their quality, principal components analysis (PCA) was performed on the basis of the data of chemical fingerprints, and the score plot clearly revealed the variations of samples produced in different years. Moreover, the results of the quantitative analysis of various samples were also comparatively studied. The results indicated that, to ensure the quality of SBP, more efficient storage and package techniques are needed. The proposed method enables chemical fingerprinting and the simultaneous determination of multicomponents to be performed in one run, and can be applied as a comprehensive quality control technique for traditional Chinese medicine containing volatile constituents. The text was submitted by the authors in English.     

Comparison of the volatile constituents of different parts of Cortex magnolia officinalis by GC‐MS combined with chemometric resolution method

Volatile compositions of different parts (stem, branch and root barks) of Cortex magnolia officinalis, cultivated in China, were investigated for the first time by GC‐MS with the help of heuristic evolving latent projection (HELP). Identification of components was conducted by similarity matching to NIST mass library but also assisted by comparison of temperature‐programmed retention indices (PTRIs) with the data web available. A total of 90, 82 and 76 volatile compounds in the essential oils of the three samples taken from the same batch aforementioned were qualitatively and quantitatively determined, representing 84.03, 83.68 and 83.10% of the total content, respectively. Among the constituents determined, there were 50 components coexisting. Eudesmol and its isomers were shown to be the principal compounds in the studied samples, accounting for 47.66, 36.74 and 36.31%, respectively. The three kinds of isomers (α‐, β‐ and γ‐eudesmol) in houpo volatile oils have been tentatively qualified and quantified simultaneously for the first time. By comparative analysis, significant qualitative and semi‐quantitative differences and similarities were observed among the three samples. The results achieved provide a scientific evidence for further exploitation of Magnolia bark and clinical medication.     

Effects of gamma irradiation on the yields of volatile extracts of Angelica gigas Nakai

The study was carried out to determine the effects of gamma irradiation on the volatile flavor components including essential oils, of Angelica gigas Nakai. The volatile organic compounds from non- and irradiated A. gigas Nakai at doses of 1, 3, 5, 10 and 20 kGy were extracted by a simultaneous steam distillation and extraction (SDE) method and identified by GC/MS analysis. A total of 116 compounds were identified and quantified from non- and irradiated A. gigas Nakai. The major volatile compounds were identified 2,4,6-trimethyl heptane, α-pinene, camphene, α-limonene, β-eudesmol, α-murrolene and sphatulenol. Among these compounds, the amount of essential oils in non-irradiated sample were 77.13%, and the irradiated samples at doses of 1, 3, 5, 10 and 20 kGy were 84.98%, 83.70%, 83.94%, 82.84% and 82.58%, respectively. Oxygenated terpenes such as β-eudesmol, α-eudesmol, and verbenone were increased after irradiation but did not correlate with the irradiation dose. The yields of active substances such as essential oil were increased after irradiation; however, the yields of essential oils and the irradiation dose were not correlated. Thus, the profile of composition volatiles of A. gigas Nakai did not change with irradiation.     

Composition and antioxidant activity of the essential oil of Artemisia annua L

Abstract

Artemisia annua L. is an annual Eurasian desert-steppe plant. The composition of essential oils found in Artemisia annua from Russian (Buryatian) flora was analyzed in this work using gas chromatography mass-spectrometry method. Artemisia ketone, β-selinene, caryophyllene, caryophyllene oxide, germacrene D were the main components of the analyzed essential oils. The comparison of own and literature data showed that the essential oils of A. annua conditionally could be divided into “Asian” and “European” groups. Our samples, referring to “Asian” profile, exhibited higher antiradical activity in comparison with data from previously published studies.     

Determination of volatile residual solvents in traditional Chinese medicines by headspace solid-phase microextraction and cryogenic gas chromatography with flame ionization detection

A method based on headspace solid-phase microextraction and cryogenic gas chromatography with flame ionization detection was developed for the determination of volatile residual solvents in traditional Chinese medicines. A laboratory-made cryogenic chromatographic system was used for the separation of 15 kinds of residual solvents. During the analysis, a 65 microm PDMS/DVB fiber was used to extract the residual solvents, the extraction time was controlled at 0 degrees C for 15 min, and the NaCl content of the sample was maintained at 30%. The limits of detection ranged from 0.08 (for octane) to 5000 microg/L (for ethanol), and the relative standard deviations were < 8%. The recoveries from spiked samples ranged from 88 to 112%. Trace levels of residual solvents in several traditional Chinese medicines were effectively identified and quantified.     

Chemical composition and anti-inflammatory activities of the essential oils from Acacia mearnsii de Wild

The volatile oils of the leaves and the stem bark of Acacia mearnsii de Wild obtained by hydro-distillation were analysed by gas chromatography–mass spectrometry. A total of 20, 38, 29 and 38 components accounted for 93.8%, 92.1%, 78.5% and 90.9% of the total oils of the fresh, dry leaves and fresh, dry stem bark, respectively. The major components of the oil were octadecyl alcohol (25.5%) and phytol (10.5%); cis-verbenol (29.5%); phytol (10.1%) and phytol (23.4%) for the fresh leaves, dried leaves, fresh stem, dry stem bark, respectively. Oral administration of essential oils at a dose of 2% showed significant (p < 0.05) anti-inflammatory properties in the albumin-induced test model in rats. Oils from the fresh leaves and dry stems inhibited inflammation beyond 4 h post treatment. The potent anti-inflammatory activity of essential oils of A. mearnsii hereby confirmed its traditional use in treating various inflammatory diseases.     

莪术药材的闪蒸气相色谱测定及其模式识别分析研究

建立了莪术药材的闪蒸-气相色谱法(FE-GC),采用FE-GC测定了3个产地的9个莪术样品.0.4mg的粉末样品, 在200℃下闪蒸,经色谱分离,基于闪蒸色谱图上分离鉴定到的35个共有峰的相对强度,结合化学模式识别即主成分分析和系统聚类分析法对莪术样品进行了鉴别分析.3个产地的莪术样品可以很好地得到区别.本法快速、简便、准确, 不失为药材质量控制的良好方法.     

Volatile constituents of Amomum maximum Roxb and Amomum microcarpum C. F. Liang & D. Fang: two Zingiberaceae grown in Vietnam

The chemical composition of essential oils obtained from the hydrodistillation of different parts of Amomum maximum Roxb and Amomum muricarpum C. F. Liang & D. Fang (Zingiberaceae) grown in Vietnam are reported. The analysis was performed by means of gas chromatography–flame ionisation detectoorand gas chromatography coupled with mass spectrometry. The major compounds identified in the oils of A. maximum were β-pinene (20.4–40.8%), α-pinene (6.8–15.0%), β-elemene (2.5–12.8%) and β-caryophyllene (2.3–10.3%). Moreover, β-phellandrene (11.6%) was present in the root oil. The main compound identified in all the oil samples of A. muricarpum was α-pinene (24.1–54.7%) and β-pinene (9.2–25.9%). In addition, limonene (7.4%) and δ-3-carene (9.4%) were present in the leaves and stem oils, respectively. However, while β-phellandrene (8.3%) could be seen prominent in the root oil, the fruits contained significant amount of zingiberene (6.3%). The largest amount of τ-muurolol (13.0%) was found in the flower oil.     

Correlation of TLC/densitometry-data with capillary GC-data of some main volatile components of essential oils

The results of the densitometric and the capillary gas chromatographic investigations of numerous lavender oils of different origin and of essential oils of the woody group were correlated. Especially the main components, the monoterpenes linalool (¯1) and linalyl acetate (¯2), were quantified by densitometry with an average standard deviation of 6–7% in the examined oils. The use of TLC in combination with densitometry in the quantification of the main components to essential oils is thus a valuable addition to capillary gas chromatographic investigation. In addition to this, a useful and efficient alternative is given to groups specialized in TLC/densitometry to obtain data on such volatile compounds of essential oils during quantification. The use of TLC/densitometry thus combines the advantage of LC-with detection of also less volatile compounds—and the possibility of the parallel investigation of more samples in one step in a very efficient way.