The analysis of essential oils and extracts (oleoresins) from seasonings ‐ A critical review

A critical review of the analytical methods employed for the determination of the relevant components of seasonings is presented. Where the available methods were inadequate, new ones have been devised. Particular emphasis has been placed on those methods of analysis that provide a rapid and sufficiently accurate appraisal of seasoning extracts and essential oils from seasonings under routine control laboratory conditions. At the same time, the margin of error of these methods has been determined. The individual seasoning extracts were assessed according to the following criteria: (1) essential oil — cardamom, laurel leaves, cloves, origanum (marjoram), sage, and thyme; (2) essential oil and nonvolatile lipids — dillseed, coriander, caraway, mace, nutmeg, pimento (allspice), and celery seed; (3) essential oil and/or pungent ingredients — capsicum, ginger, and pepper; (4) essential oil and/or coloring matter — turmeric (curcuma) and paprika; (5) essential oil and other components — garlic, onion, and cinnamon.     

The analysis of essential oils and extracts (oleoresins) from seasonings--a critical review.

A critical review of the analytical methods employed for the determination of the relevant components of seasonings is presented. Where the available methods were inadequate, new ones have been devised. Particular emphasis has been placed on those methods of analysis that provide a rapid and sufficiently accurate appraisal of seasoning extracts and essential oils from seasonings under routine control laboratory conditions. At the same time, the margin of error of these methods has been determined. The individual seasoning extracts were assessed according to the following criteria: (1) essential oil--cardamom, laurel leaves, cloves, origanum (marjoram), sage, and thyme; (2) essential oil and nonvolatile lipids--dillseed, coriander, caraway, mace, nutmeg, pimento (allspice), and celery seed; (3) essential oil and/or pungent ingredients--capsicum, ginger, and pepper; (4) essential oil and/or coloring matter--turmeric (curcuma) and paprika; (5) essential oil and other components--garlic, onion, and cinnamon.     

Extraction and separation of volatile and fixed oils from seeds of Myristica fragrans by supercritical CO₂: chemical composition and cytotoxic activity on Caco-2 cancer cells

Isolation of volatile and fixed oils from nutmeg have been obtained by supercritical fractioned extraction with carbon dioxide. Extraction experiments were carried out at pressures of 90 and 250 bar and temperature of 40 °C. The extraction step performed at 90 bar produced a volatile fraction mainly formed by myristicin (32.8%), sabinene (16.1%), α-pinene (9.8%), β-pinene (9.4%), β-phellandrene (4.9%), safrole (4.1%) and terpinen-4-ol (3.6%). The oil yield relative to this step of the process was 1.4% by weight of the charge. The last extraction step at 250 bar produced a butter-like material (nutmeg butter). The yield of this step was 14.4% by weight. The most represented fatty acids of fixed oil from nutmeg were 14:0 (79.2%), 18:1 n-9 (7.4%) and 16:0 (6.1%), and in particular the unsaturated fatty acids 18:1 n-9 averaged 32.96 μg/mg of oil. The level of myristicin in the nutmeg essential and fixed oils was also directly quantified by reversed HPLC-DAD. Moreover, the essential oil obtained from nutmeg, as well as myristicin, showed a significant in vitro inhibitory effect on the growth of a colon cancer cell line (undifferentiated Caco-2 cells). PRACTICAL APPLICATION: In this study, the chemical characterization and the anticancer activity of nutmeg oils obtained by supercritical extraction with carbon dioxide were investigated. This is important for their potential application in food and pharmaceutical industries.     

Chemical composition,antioxidant and cytotoxicity activities of the essential oils of Myristica fragrans and Morinda citrifolia

BACKGROUND: In this study the chemical composition, antioxidant activities and cytotoxic effect of the essential oils of Myristica fragrans (nutmeg) and Morinda citrifolia (mengkudu) were determined. RESULTS: Thirty‐eight compounds in nutmeg oil and six compounds in mengkudu oil were identified by gas chromatography–mass spectrometry. The free radical scavenging activity of nutmeg oil was superior of that mengkudu oil. The MTT assay of nutmeg oil on human colorectal carcinoma (HCT‐116) and human breast carcinoma (MCF‐7) cell lines showed IC₅₀ values of 78.61 and 66.45 µg mL^?1, respectively. The mengkudu oil exhibited IC₅₀ values of 91.46 and 78.15 µg mL^?1 for HCT‐116 and MCF‐7, respectively. CONCLUSION: The results showed that nutmeg oil can be developed as potent anti‐cancer and antioxidant drugs. Copyright © 2011 Society of Chemical Industry     

Antimicrobial and antioxidant activity of spice essential oils

Essential oils of anise, bastard cardamom, cinnamon, dill, mace, zedoary, prikhom, and bitter ginger were determined for their antimicrobial and antioxidant activities. Of all, cinnamon oil had the highest antibacterial activity. The most sensitive bacteria was Bacillus cereus (0.5mg/mL minimum inhibitory concentration, MIC). Anise, cinnamon, dill, and prikhom exhibited strong antifungal activity against Rhodotorula glutinis, Aspergillus ochraceus, and Fusarium moniliforme. Two oil combinations: i) cinnamon and mace oils and ii) cinnamon and prikhom oils showed a synergistic effect against Staphylococcus aureus, Pseudomonas fluorescens, and Salmonella Rissen (0.32–0.38 mg/mL fractional inhibitory concentration index, FICI). Cinnamon, mace, and prikhom oils had strong antioxidant activity with 0.29–5.66 mg/mL IC₅₀, 61.46–68.52% antioxidant activity, 0.22–2.19 mM/mg reducing capacity, and 78.28–84.30% inhibition by 2,2-diphenyl-1-picrylhydrazyl (DPPH), β-carotene bleaching, ferric reducing (FRAP), and superoxide anion scavenging activity assays, respectively. These oils contained high amount of total phenolics (51.54–140.9 μg gallic acid equivalents/mg oil).     

Quorum Sensing Inhibitory and Anti-Biofilm Activity of Essential Oils and Their in vivo Efficacy in Food Systems

The present study investigated the effect of the essential oils of Cuminium cymium, Murraya koenigii, Curcuma longa, Zingiber officinale, Myristica fragrans (mace and nutmeg), Trigonella foenum graceum, and Elettaria cardamomum on AHL-mediated quorum sensing and biofilm formation. Inhibition of quorum sensing (QS) regulated phenotypes by the essential oils at subinhibitory concentrations was investigated using the biosensor bacteria Chromobacterium violaceum (C. violaceum 12472 and C. violaceum CV026) and Pseudomonas aeruginosa PA01. Sub-MIC of essential oils was screened for inhibition of quorum-sensing regulated pigment production, motility and biofilm formation in the biosensors. The essential oil of M. koenigii showed the most promising QS inhibitory and anti-biofilm activity at a concentration of 0.02% v/v and hence was used for further studies. Anti-biofilm activity against food spoilage Pseudomonas species was studied by crystal-violet MTP method and fluorescence microscopy. The essential oil of M. koenigii at sub-MICs inhibited biofilm formation in the pseudomonads by inhibiting cell attachment, reducing metabolic activity and EPS production, and preventing biofilm maturation. Further, it was capable of delaying spoilage by psychrotrophic P. psychrophila PSPF19 in refrigerated milk. The major components present in M. koenigii essential oil were caryophyllene, caryophyllene oxide, cinnamaldehyde, α-, and β-phellandrene and eugenol. Application of M. koenigii essential oil and its constituents based on the quorum-sensing inhibitory and anti-biofilm activity would be a novel intervention strategy to enhance shelf life and food safety.     

Development of Advance Extraction Methods for the Extraction of Myristicin from <Emphasis Type="Italic">Myristica fragrans</Emphasis>

Myristicin in a psychoactive, hallucinogenic substance and as a constituent of nutmeg and mace (Myristica fragrans nut and its aril, respectively) is widely available for people seeking so-called legal highs of natural origin. In this work, we present three methods for determination of myristicin from plant material. The methods consist of optimized extraction procedures: microwave-assisted extraction, ultrasound-assisted extraction utilizing ultrasound bath or sonotrode and gas chromatography-mass spectrometry (GC-MS) analysis method. The methods were validated: repeatability and intermediate were below 10 % and recovery ranged from 97 to 109 %. The developed methods were then used for determination of myristicin in commercially available nutmeg and mace samples. The concentration ranged from 0.58 to 12.94 μg mg^?1, and the highest concentration of myristicin was observed in samples of those producers, which are often recommended by individuals experimenting with nutmeg. The microwave-assisted extraction (MAE) method has been proven to be the most effective one for the extraction of myristicin from plant material, as it also generates deeper changes in sample structure than UAE techniques. The MAE/GC-MS method was successfully used for nutmeg residue analysis, allowing identification of five characteristic violate constituents of nutmeg.     

Effect of gamma-irradiation on the phenolic acids of some Indian spices

Five commercially important spices, namely cinnamon, clove, cardamom, nutmeg and mace, were subjected to gamma-irradiation using a dose of 10 kGy, which is recommended for microbial decontamination. Various phenolic acids present in these spices were analysed by high-performance liquid chromatography (HPLC). In clove and nutmeg, quantitatively significant changes were noted in some of the phenolic acids upon irradiation. The content of gallic and syringic acids in irradiated clove increased by 2.2- and 4.4-fold respectively, whereas in irradiated nutmeg many of the phenolic acids showed wide increases and decreases in the range of two- to sixfold compared with the control samples. No qualitative and major quantitative changes were, however, observed in the phenolic acids of cinnamon, cardamom and mace upon irradiation. The possibility that gamma-radiation induced breakdown of tannins could be responsible for the changes in phenolic acids content of clove and nutmeg is discussed.     

基于主成分和聚类分析评价国产不同批次肉豆蔻挥发油的质量

本文对16批次肉豆蔻样品的挥发油进行化学成分分析鉴定，对其共有化学成分采用主成分分析和聚类分析，从而对肉豆蔻挥发油进行综合质量评价。通过对其形状、气味、色泽等性状进行记录，采用水蒸气蒸馏法提取肉豆蔻挥发油，通过气相色谱-质谱联用色谱仪（GC-MS）所得挥发性成分，结合NIST08系列标准谱库、人工检索等方式对其进行鉴定分析，利用主成分分析和聚类分析对16批次肉豆蔻样品进行综合评价。16批次肉豆蔻多为卵圆形或椭圆形、香气浓烈、灰棕色；从肉豆蔻挥发油化学成分中共筛选出17个共有成分，经主成分分析概括为4个主成分，包含源信息量的86.26%；聚类分析结果显示，16批次肉豆蔻样品可聚为两大类，S15批次聚为一类，S1-S14，S16批次聚为一类；两种分析结果达成一致。通过主成分分析和聚类分析，同时结合性状品质与安全性分析，可以建立肉豆蔻挥发油的质量评价体系，为肉豆蔻挥发油的药食两用以及其他方面的进一步开发研究提供参考依据，该评价方法综合性强、全面性高。     

Synergetic Use of Principal Component Analysis Applied to Normed Physicochemical Measurements and GC × GC‐MS to Reveal the Stabilization Effect of Selected Essential Oils on Heated Rapeseed Oil

Lipid oxidation leads to the formation of volatile compounds and very often to off‐flavors. In the case of the heating of rapeseed oil, unpleasant odors, characterized as a fishy odor, are emitted. In this study, 2 different essential oils (coriander and nutmeg essential oils) were added to refined rapeseed oil as odor masking agents. The aim of this work was to determine a potential antioxidant effect of these essential oils on the thermal stability of rapeseed oil subject to heating cycles between room temperature and 180 °C. For this purpose, normed determinations of different parameters (peroxide value, anisidine value, and the content of total polar compounds, free fatty acids and tocopherols) were carried out to examine the differences between pure and degraded oil. No significant difference was observed between pure rapeseed oil and rapeseed oil with essential oils for each parameter separately. However, a stabilizing effect of the essential oils, with a higher effect for the nutmeg essential oil was highlighted by principal component analysis applied on physicochemical dataset. Moreover, the analysis of the volatile compounds performed by GC × GC showed a substantial loss of the volatile compounds of the essential oils from the first heating cycle.     

Chemical composition of the essential oil of three Iranian Satureja species (S. mutica,S. macrantha and S. intermedia)

Essential oils from aerial parts of Satureja mutica Fisch. & C. A. Mey., Satureja macrantha C. A. Mey. and Satureja intermedia C. A. Mey. were obtained by hydro-distillation. The oils were analyzed by capillary gas chromatography, using flame ionization and mass spectrometric detection. Forty five components were identified in the oil of S. mutica with carvacrol (30.9%), thymol (26.5%), γ-terpinene (14.9%) and p-cymene (10.3%) as main constituents. Sixty five compounds were identified in the oil of S. macrantha, with p-cymene (25.8%), limonene (16.3%) and thymol (8.1%) as main components. Thirty eight compounds were characterized in the oil of S. intermedia with thymol (32.3%), γ-terpinene (29.3%) and p-cymene (14.7%) as main constituents. The results showed different compositions of the essential oils of these Satureja species. There are some minor components in each oil that are not present in the others.     

不同产地南瓜籽油组成及氧化稳定性的差异

以我国8 个不同产地南瓜籽为原料,压榨制备南瓜籽油,对比分析不同南瓜籽油的组成和氧化稳定性。结果表明,南瓜籽油主要含有棕榈酸、硬脂酸、油酸、亚油酸4 种脂肪酸,不饱和脂肪酸含量占80.565%～84.964%,总酚含量为167.21～204.50 mg/kg,总甾醇含量为1 204.38～1 604.51 mg/kg,α-生育酚含量为25.7～58.7 mg/kg,γ-生育酚含量为1 839.8～2 728.3 mg/kg,δ-生育酚含量为248.8～518.7 mg/kg。Pearson双变量相关性分析表明,总酚与极性组分自由基清除能力有显著相关性（P＜0.05）,α-生育酚等油脂伴随物也发挥了一定的抗氧化作用。主成分分析和聚类分析的结果显示：不同产地的南瓜籽油功能性成分相似,由于含量差别显示出具有显著差异的2 个集群,甘肃省白银市产的南瓜籽油综合评分最高。本研究对南瓜籽资源的开发利用具有一定的指导意义。     

新疆不同品种薰衣草精油特征香气成分及感官属性分析

通过水蒸汽蒸馏法对新疆五种薰衣草花中精油进行提取,采用气相色谱-质谱联用(GC-MS)技术对薰衣草精油中挥发性成分及特征香气成分进行了分析,并对其香气轮廓进行了感官评定。结果显示,五个品种的薰衣草精油(70-1、74262、杂花、法国兰、白花)中,70-1精油含量最高,为6.88%。经鉴定薰衣草精油中挥发性成分主要为萜烯类、酯类、醛类、酮类和醇类,其中白花精油中挥发性化合物种类最多,含量也最高,五种精油中挥发性物质含量差异最大的为萜烯类,分别为17.15%、12.36%、16.33%、16.16%、20.48%;五种精油中特征香气成分如芳樟醇及乙酸芳樟酯等含量具有较大差异。通过感官分析发现74262精油中花香、酯香气最浓郁,五种精油中花香,酯香、凉气、油蜡气和萜气均有较大差异,其原因主要是由于品种以及所含有的挥发性物质存在差异。     

Antibacterial properties of plant essential oils

Fifty plant essential oils were examined for their antibacterial properties against 25 genera of bacteria. Four concentrations of each oil were tested using an agar diffusion technique. The ten most inhibitory oils were thyme, cinnamon, bay, clove, almond (bitter), lovage, pimento, marjoram, angelica and nutmeg. The most comprehensively inhibitory extracts were angelica (against 25 genera), bay (24), cinnamon (23), clove (23), thyme (23), almond (bitter) (22), marjoram (22), pimento (22), geranium (21) and lovage (20).     

ANTIOXIDATIVE AND ANTIBACTERIAL POTENTIALS OF ESSENTIAL OILS AND EXTRACTS ISOLATED FROM VARIOUS SPICE MATERIALS†

The antioxidant and antibacterial potentials of essential oils and acetone extracts of black pepper, cumin, black cumin and mace were carried out by different techniques. The antioxidative capacity of the essential oils and acetone extracts were evaluated against mustard oil by measuring peroxide and thibarbituric acid values at fixed intervals. In addition, their antioxidant potential was evaluated by 2, 2′‐diphenyl‐1‐picrylhydracyl radical and conjugated diene assays. Their reducing power was determined with standards, which proved the strong antioxidant capacity of essential oils and extracts. The antioxidant activity of essential oils and extracts exerted by all the antioxidant assays can be compared with synthetic antioxidants such as butylated hydroxyanisole and butylated hydroxytoluene. The antibacterial activity was studied by disk diffusion and poison food methods. Black cumin essential oil showed complete zone of inhibition (P < 0.05) against tested bacterial strains of Staphylococcus aureus, Bacillus cereus and Bacillus subtilis at 2 and 6 µL level by disk diffusion method. Black cumin and black pepper extracts showed complete reduction of colonies against tested bacterial strains of S. aureus, B. cereus and B. subtilisat 5 and 10 µL level by poison food method. Poison food method exhibited good results for the tested essential oils and extracts. Essential oils of black pepper, cumin, black cumin and mace may be used to stabilize mustard oil after screening.     

GC-MS和GC-IMS分析食用油对熟炕马铃薯挥发性成分的影响

以恩施马尔科品种的马铃薯为原料,利用菜籽油、花生油、大豆油、玉米油和漆油5种食用油对马铃薯进行炕制加工,借助气相色谱-质谱联用(GC-MS)和气相离子迁移谱(GC-IMS)对其挥发性成分进行测定。结果发现,GC-MS共鉴定出24种挥发性成分,主要为醛类、吡嗪类、酯类和酮类等,漆油炕制马铃薯的挥发性成分与其他4种食用油的有显著差异,未检测到吡嗪类化合物,而其他4种食用油炕制的马铃薯均是醛类、吡嗪类占主导地位,在鉴定出的挥发性成分中醛类、吡嗪类约占80%～88%,花生油炕制马铃薯风味物质含量最高,热图聚类和PLS-DA分析结果较为一致,均表明大豆油和玉米油炕制马铃薯挥发性成分较为相似,VIP分析结果显示2-乙基-(5或6)-甲基吡嗪、反,反-2,4-庚二烯醛等8种成分对炕制马铃薯的风味影响最大。GC-IMS鉴定出了46种挥发性成分,对GC-IMS测定数据进行主成分和指纹图谱分析,结果显示大豆油和玉米油炕制马铃薯中挥发性化合物较为相似,这与GC-MS聚类结果相呼应,由此可见GC-MS和GC-IMS均可很好区分不同食用油熟炕的马铃薯。     

Spice oils for the control of co-occurring mycotoxin-producing fungi

The effect of nine different oils was evaluated on the growth of Aspergillus parasiticus and Fusarium moniliforme. The experimental design to examine the inhibition of mycotoxins involved the incorporation of each of seven oils into broth and patty cultures. The fungal mycotoxin was identified by high-pressure liquid chromatography. Clove oil (eugenol) was the most inhibitory to the growth of A. parasiticus and F. moniliforme, followed by cinnamon (cinnamic aldehyde), oregano (thymol and carvacol) and mace oils (myristin). Neem and eucalyptus oil (cineole) did not affect fungal growth. The feasibility of implementing the results of this study to control mycotoxin toxicity was examined by costoring whole and ground cloves with mycotoxin-infected grain. Addition of both whole and ground cloves markedly reduced the aflatoxin contamination of the grain. These results clearly suggest that commonly occurring mycotoxigenic fungi can be controlled with clove oil (eugenol), thus spice oil successfully inhibited the growth of A. parasiticus and F. moniliforme, regulated the production of fumonisins. and prevented the formation of aflatoxins. The social implication of this finding is that rural communities can prevent the formation of fungal toxins in contaminated grain by simple measures.     

Microwave assisted fluidized bed drying of nutmeg mace for essential oil enriched extracts: An assessment of drying kinetics,process optimization and quality

The drying mechanism of the myristicin enriched nutmeg mace has been optimized in a microwave assisted fluidization bed dryer (MWFBD) through multiple linear regression (MLR) and artificial neural network (ANN) modeling. The developed drying technique overcomes the non-uniformity heating problems in microwave heating and prolonged drying in fluidized bed drying. During the novel method of drying selected input variables were drying air temperature (DT) (40–50 °C) and microwave power (MP) (480–800 W) and output variables involving colour, oil yield, and myristicin quantity have been investigated by a continuous air velocity of 5.1 m/s. Six mathematical models about one to four conditions have fitted with an experimental design. Suitable enforcement of such models was evaluated through statistical measures. The coefficient of determination (R²) of MLR varied from 0.89 to 0.98, and the sum of squared error (SSE) varied within 6 × 10⁻³ to 158.18, while R² of ANN fluctuated from 0.82 to 0.95, and the mean squared error (MSE) varied between 0.006 and 0.1450, which shows MLR design performance superior than ANN design. The processing conditions of 48.24 °C DT and 637.431 W MP with a drying time of 1.3 h were identified as optimum conditions with a desirability value of 0.98 to obtain maximum oil yield (13.38%) and good colour (L* (20.83), a* (17.34), b* (8.62)) of nutmug mace. Moreover, no myristicin (5.92%) degradation was observed compared with the sun and convective drying. Among the tested models, page and logarithmic models gave a better prediction of moisture ratio.     

不同压榨工艺下花生油风味成分的变化

该研究采用顶空固相微萃取-气相色谱-质谱联用仪（HS-SPME-GC-MS）及电子鼻对不同压榨工艺下花生油挥发性风味成分和脂肪酸组成进行分析。6种不同压榨工艺花生油中共检测到10类38种挥发性成分,其中包含19种风味成分。在热榨花生油中以呋喃类（63.43%~66.68%）、醛类（10.04%~5.47%）、酚类（8.83%~7.18%）为主要的挥发性成分,在冷榨花生油中以酯类（26.43%）、醛类（23.47%）、酸类（22.10%）为主要的挥发性成分。此外,热榨花生油检测出少部分吡嗪、吡啶、酮类关键风味成分,其在冷榨花生油中并没有检出。电子鼻结果基本与GC-MS一致,硫化物、芳香化合物、氮氧化合物和甲基类化合物对花生油整体风味贡献率较大,通过主成分分析和K-mean聚类分析结果显示6种花生油挥发性成分变化差异显著。6种花生油脂肪酸组成都以油酸、亚油酸、棕榈酸为主,含量可达到90%以上。然而通过对比不同温度下花生油脂肪酸组成发现随着压榨温度的升高,不饱和脂肪酸的氧化加速。综上,对比不同压榨工艺下花生油风味和营养成分的变化发现高温条件压榨下花生油的风味成分显著增加,花生油品质略有下降,利用电子鼻可快速区分不同压榨工艺花生油。     

3种淡水鱼内脏粗鱼油品质及挥发性风味成分分析比较

为提高淡水鱼类加工副产物的高值化利用,本文以3种常见的淡水鱼(草鱼、青鱼和鲢鱼)内脏为原料提取粗鱼油,进行理化指标评价、脂肪酸组成及挥发性风味成分分析。结果表明,青鱼油的理化指标最佳,其过氧化值、酸价、水分及挥发物、茴香胺值、不皂化物等较低;鲢鱼油次之,草鱼油最差。青鱼油、鲢鱼油和草鱼油中分别检测出16、22、27种脂肪酸,均以棕榈酸(C_16:0)、油酸(C_18:1n-9c)、亚油酸(C_18:2n-6c)为主,鲢鱼油的相对营养价值最高。3种粗鱼油共检测出66种挥发性物质,包括烃类17种,醇类7种,醛类15种,酮类3种,酯类8种,酸类10种,酚类3种,其他类3种。草鱼油中含量最高的是酚类物质(59.86%);青鱼油中挥发性物质以醇类为主,含量为53.23%;鲢鱼油中含量最高的是酸类物质(27.64%)。3种粗鱼油共得到10种关键风味成分,主要以醛类、醇类和酚类物质为主。反式-2,4-癸二烯醛、壬醛、反式-2,4-庚二烯醛、苯乙醛、1-辛烯-3-醇等是粗鱼油中主要的鱼腥味、油脂味风味物质。