Simple preparative gas chromatographic method for isolation of menthol and menthone from peppermint oil, with quantitative GC-MS and (1) H NMR assay

The quantitative performance of a simple home‐built preparative gas chromatography (prep‐GC) arrangement was tested, incorporating a micro‐fluidic Deans switch, with collection of the target compound in a deactivated uncoated capillary tube. Repeat injections of a standard solution and peppermint sample were made into the prep‐GC instrument. Individual compounds were eluted from the trapping capillary, and made up to constant volume. Chloronaphthalene internal standard was added in some cases. Recovered samples were quantitatively assayed by using GC‐MS. Calibration linearity of GC‐MS for menthol standard area response against number of injections (2–20 repeat injections) was excellent, giving R² of 0.996. For peppermint, menthol correlation over 2–20 repeated injections was 0.998 for menthol area ratio (versus IS) data. Menthone calibration for peppermint gave an R² of 0.972. ¹H NMR spectroscopy was conducted on both menthol and menthone. Good correspondence with reference spectra was obtained. About 80 μg of isolated menthol and menthone solute was collected over a sequence of 80 repeat injections from the peppermint sample, as assayed by 600 MHz ¹H NMR analysis (～100% recovery for menthol from peppermint). A procedure is proposed for prediction of number of injections required to acquire sufficient material for NMR detection.     

L-古洛糖酸γ-内酯对蔬菜中有机磷农药残留测定基质效应的补偿作用研究

建立了一种采用掩蔽试剂对有机磷农药残留测定时的基质效应进行补偿的方法.研究了其对仪器稳定性、耐受性的影响及对基质效应的补偿效果.结果显示,1.0 g/L的L-古洛糖酸γ-内酯对敏感农药甲胺磷、乙酰甲胺磷、氧乐果和久效磷的色谱行为改善显著,响应值分别提高了2.8、9.1、10.4和4.8倍,未对非敏感农药测定产生负面影响...     

Comparison of sample concentration methods and correlation chromatography for polymer dynamic head-space studies

Summary Gas chromatography has been used to study the kinetics of evolution of volatiles from polypropylene samples (at 70°C). Correlation chromatography (CC) and the trapping of volatiles on Tenax sorbents and activated charcoal were employed to improve the detector signal. As a reference, the kinetics of gas evolution was studied by making a series of direct single injections of polymer head-space gas on a GC column. The results of trapping differed from those obtained by single injection. However, the data from single injections and CC were in good agreement. The CC method was found to offer far more operator convenience for dynamic head-space analysis than sample trapping, being less subject to operator errors.     

Multiple component isolation in preparative multidimensional gas chromatography with characterisation by mass spectrometry and nuclear magnetic resonance spectroscopy

The preparative scale isolation of multiple components from an essential oil matrix is described using multidimensional gas chromatography (prep-MDGC) which allows their further characterisation by mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. Menthol, linalyl acetate, carvone and geraniol were isolated individually, and were also collected in various combinations. It was demonstrated to be possible to collect multiple selected components from numerous repeat injections of the sample, to permit increased mass recovery from an external cryotrap collection device. Peak retention times remained reproducible (<0.3 s) over the repeated injections and switching events. This methodology may be utilised to confirm peak identity or to produce unique mixed-component reference standards, for instance to allow their identification in other samples using GC/MS, or identify them in comprehensive two-dimensional gas chromatography (GC × GC) analysis.     

Headspace analysis with cryogenic focusing: A procedure for increasing the sensitivity of automated capillary headspace analysis

Summary A convenient procedure has been described for enhancing the sensitivity of equilibrium headspace gas chromatography. The technique involves the cryogenic focusing of headspace vapors at the head of a 0.32 mm fusedsilica capillary column which has been coupled to a packed column injection port. Cryofocusing is accomplished automatically by cooling the GC oven and results in enhanced sensitivity with improved resolution. With this simple focusing technique no sample splitting is required which gives at least a 10-fold increase in sensitivity. A Multiple Headspace Injection (MHI) technique has been described which allows several rapid headspace injections to be made at the start of a single chromatographic run. Cryofocusing causes the injections to be superimposed, thus increasing the sensitivity even further. These procedures have been demonstrated for flavor and aroma analyses of toothpaste and soft drink samples. Presented at the Symposium on Headspace GC, National American Chemical Society Meeting, Chicago, Ill., September 8–13, 1985     

离子色谱法测定气体中痕量二氧化硫

建立了测定气体中痕量二氧化硫的离子色谱法。采用氢氧化钠–过氧化氢溶液为吸收液,将气体样品中痕量二氧化硫转化为硫酸根离子,以离子色谱法测定硫酸根离子,从而得到气体中二氧化硫含量。二氧化硫气体含量在1~100μL/L范围内与色谱峰面积线性关系良好,相关系数为0.999 9。二氧化硫的检出限为0.1μg/L,测量结果的重复性小于2%(n=6),测定标准样品的回收率在98.1%~99.6%之间,准确度优于对照方法。     

Clean-up of plasma extracts by gel permeation chromatography during analysis of isosorbide nitrates by capillary gas chromatography.

This work describes how gel permeation chromatography (GPC) can be used for sample clean-up to reduce the fouling of the column in an automated on-column injector. The analytes were isolated from plasma together with the internal standard (isomannide dinitrate) by liquid-liquid extraction on Extrelut silica columns. The extracts were evaporated and reconstituted in tetrahydrofuran for separation of the analytes from non-volatile plasma components by GPC on a styrene-divinylbenzene column with 100 A pore size. A programmable autosampler with an additional three-way valve was used for injection and fraction collection. The molecular weight fraction between 100 and 700 a.m.u. was collected and transferred to the on-column autosampler for capillary gas chromatography on a 30-m column butt-connected to a 0.2-m pre-column. The pre-column was replaced after 50 sample injections. When the GPC purification was excluded from the work-up procedure a deposit of non-volatile components was formed at the injection zone of the pre-column which resulted in excessive peak-tailing after only five or six injections of plasma extract. The limit of determination was 0.2 ng/ml plasma for isosorbide dinitrate and 0.4 ng/ml for the mononitrates.     

Determination of polybrominated diphenyl ethers in river water by combination of liquid–liquid extraction and gas chromatography–mass spectrometry

In this work,a reliable and sensitive method for detecting polybrominated diphenyl ethers(PBDEs) has been developed by the combination of liquid–liquid extraction and gas chromatography–mass spectrometry.PBDEs were extracted from a large volume of water by liquid–liquid extraction and purified by silica gel chromatography.In order to reduce the deviation,dibromobiphenyl was exploited as the internal standard to minimize differences among the injections.The quantification was performed using an external standard.Good linear correlation coefficients(0.991) and a wide linearity range(1.0–500.0 ng/L) indicated the steadiness of the proposed method.Moreover,the satisfactory recovery(75%)suggested that successful determination of PBDEs in river water had been achieved.Furthermore,the deduction behavior of PBDEs in river water could be inferred according to the results.     

二甲醚气相色谱相对重量校正因子的测定

用冰冷却水吸收二甲醚配制样品,将ＴＣＤ和ＦＩＤ串联使用,测定出二甲醚在ＴＣＤ和ＦＩＤ上相对于甲醇的重量校正因子分别为０．８６和０．５５,并通过用甲醇催化脱水生成的二甲醚和水的化学计量关系,在线间接测定二甲醚在ＴＣＤ上相对于甲醇的重量校正因子,从而使上述测定结果得到佐证。     

顶空气相色谱法测定富氢水中的氢气

建立顶空气相色谱法测定富氢水中氢气的方法。采用顶空的方式将水中的微量氢气转移到气相中,通过分子筛色谱柱分离,用热导检测器测定。分析条件如下:分流比为5∶1,气液体积比为1.2∶1,平衡温度为40℃,平衡时间为15 min。水中氢气的质量浓度在0.080~1.603 mg/L范围内与色谱峰面积成良好线性关系,线性相关系数为0.999,方法检出限为0.005 mg/L。样品加标回收率为91.03%~94.25%,测定结果的相对标准偏差为0.61%~2.32%(n=6)。该法可用于富氢水中氢气的测定。     

用于与全二维气相色谱联用的高通量飞行时间质谱仪的研制

研制了可与全二维气相色谱联用的高通量飞行时间质谱仪,并进行了性能水平测试。设计采用新型高灵敏度电子轰击源及具有垂直引入、双推斥脉冲、二级反射式结构的飞行时间质量分析器,结合高于20 kHz的推斥频率,可获得质量范围1~1000 amu,质量分辨>1000(m/z 219,ADC采集卡),检出限低于1 pg,线性动态范围超过4个数量级,同时最快可达400谱/s的高采集速度,完全满足全二维气相色谱与飞行时间质谱联用的检测要求。与一款完全国产化的全二维气相色谱仪联用,实现对石油、香精、环境等多个领域复杂样品的分析,获得令人满意的检测结果,显示了此质谱仪器与全二维气相色谱联用的适用性及其在复杂样品体系全组分分析中的应用潜力。     

催化裂化汽油中硫化物类型分布的气相色谱-硫化学发光检测的方法研究

采用气相色谱-硫化学发光检测器(GC-SCD),建立了催化裂化汽油(FCC汽油)中各种硫化物类型分布的分析方法。考察了色谱条件对催化裂化汽油中各种硫化物分离的影响,定性了某催化裂化汽油中的58个硫化物。采用该方法,硫化物中的硫在其质量浓度为0.5~800.0 mg/L时,其峰面积与质量浓度呈较好的线性关系,相关系数达0.999,其响应与硫化物的类型无关。FCC汽油中几种主要硫化物(噻吩、正丁硫醇、2-甲基噻吩、3-甲基噻吩、2,4-二甲基噻吩)的浓度测定值的相对标准偏差(RSD)均小于5.0%。当信噪     

Non‐polar lipids characterization of Quinoa (Chenopodium quinoa) seed by comprehensive two‐dimensional gas chromatography with flame ionization/mass spectrometry detection and non‐aqueous reversed‐phase liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection

A chemical characterization of major lipid components, namely, triacylglycerols, fatty acids and the unsaponifiable fraction, in a Quinoa seed lipids sample is reported. To tackle such a task, non‐aqueous reversed‐phase high‐performance liquid chromatography with mass spectrometry detection was employed. The latter was interfaced with atmospheric pressure chemical ionization for the analysis of triacylglycerols. The main triacylglycerols (>10%) were represented by OLP, OOL and OLL (P = palmitoyl, O = oleoyl, L = linoleoyl); the latter was present in the oil sample at the highest percentage (18.1%). Furthermore, fatty acid methyl esters were evaluated by gas chromatography with flame ionization detection. 89% of the total fatty acids was represented by unsaturated fatty acid methyl esters with the greatest percentage represented by linoleic and oleic acids accounting for approximately 48 and 28%, respectively. An extensive characterization of the unsaponifiable fraction of Quinoa seed lipids was performed for the first time, by using comprehensive two‐dimensional gas chromatography with dual mass spectrometry/flame ionization detection. Overall, 66 compounds of the unsaponifiable fraction were tentatively identified, many constituents of which (particularly sterols) were confirmed by using gas chromatography with high‐resolution time‐of‐flight mass spectrometry.     

顶空固相微萃取气相色谱法测定浓海水中的氯酚

建立浓海水中氯酚的顶空固相微萃取气相色谱法检测方法。采用顶空固相微萃取对海水淡化排放的浓海水样品中2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)进行分离富集,气相色谱-电子捕获检测器(μECD)测定浓海水样品中2,4,6-TCP和PCP的含量。讨论了萃取时间、萃取温度、水样盐度等实验条件对富集效率的影响,确定了萃取时间为40 min,萃取温度为60℃。2,4,6-TCP,PCP的质量浓度在0.500~20.0μg/L范围内与其色谱峰面积呈良好的线性关系,线性相关系数均大于0.999,2,4,6-TCP和PCP的检出限(2S/N)分别为0.055,0.128μg/L,测定结果的相对标准偏差为3.65%~11.4%(n=6),加标回收率为73.5%~119.0%。该方法快速,灵敏度高,适合于浓海水中氯酚的分析。     

Simultaneous determination of non-steroidal anti-inflammatory drugs in river water by gas chromatography-mass spectrometry

The gas chromatography/mass spectrometric assay method was developed for the determination of 13 non‐steroidal anti‐inflammatory drugs (NSAIDs) in river water. Extraction was achieved by a liquid‐phase extraction procedure using methylene chloride. The extract was reacted for 30 min at 80°C based on the formation of methyl ester with 1.0 M HCl in methanol and extraction of the derivative with ethyl acetate, which was then measured by gas chromatography‐mass spectrometry. The limit of quantification of NSAIDs was 1.0–60 ng/L and the calibration curve showed linearity being greater than r=0.997. The method was used to analyze ten river water samples from various regions in Korea. Diclofenac, indoprofen, ketoprofen and loxoprofen were detected at concentration of up to 1.29 μg/L in river water. The developed method may prove valuable for use in the national monitoring project of NSAIDs in surface water.     

Comparative study of ink photoinitiators in food packages using gas chromatography with vacuum ultraviolet detection and gas chromatography with mass spectrometry

This work focused on the development and validation of the analytical procedure using gas chromatography equipped with vacuum‐ultraviolet detection for the specific and sensitive determination of nine photoinitiators in food packages. Subsequently, a comparison of the combination of vacuum ultraviolet spectroscopy with gas chromatography and a developed gas chromatography with mass spectrometry method was performed. The vacuum‐ultraviolet spectra of all tested photoinitiators were collected and found to be highly distinct, even for isomers. Under the optimal conditions, the limits of detection for nine photoinitiators ranged from 1 to 5 mg/L using vacuum ultraviolet detection and from 0.15 to 0.5 mg/L using mass spectrometric detection. Both techniques were successfully applied for screening of photoinitiators in seven kinds of food packages and the obtained data showed good agreement (the relative difference was between 3 and 18%). The variability in concentrations found in triplicate samples was assessed to be below 18%. Predominantly benzophenone was found in all analysed samples in the range of 0.31–4.23 mg/kg. It appears to be preferably selected by food packaging manufacturers. This study proposes a new simple and sensitive technique used for analysis of photoinitiators that could be a good alternative to gas chromatography with mass spectrometry.     

Chemical composition and in vitro antimicrobial activity of the essential oil of the flowers of Tridax procumbens

The essential oil of the flowers of Tridax procumbens L. was obtained by hydro-distillation and analyzed by gas chromatography equipped with a flame ionization detector (GC-FID) and gas chromatography coupled with mass spectrometry (GC/MS). Twenty-six compounds were identified, which comprised 90.6% of the total constituents. The most abundant compound was (Z)-falcarinol (25.9%), followed by alpha-selinene (15.3%), limonene (8.3%) and zerumbone (4.3%). Antimicrobial activity was tested against six Gram-positive and eight Gram-negative bacteria, and three fungi. The oil was active against the tested Gram-positive bacteria at a concentration range of 0.14 +/- 0.03 - 0.57 +/- 0.05 mg/mL, while 0.67 +/- 0.12 - 4.58 +/- 0.41 mg/mL was effective against the studied Gram-negative bacteria. Remarkable antifungal activity was found against the tested fungi at a concentration range of 0.06 +/- 0.008 - 0.10 +/- 0.01 mg/mL.     

Low‐temperature headspace‐trap gas chromatography with mass spectrometry for the determination of trace volatile compounds from the fruit of Lycium barbarum L.

The total saccharides content of Lycium barbarum L. is very high, and a high temperature would result in saccharide decomposition and the emergence of a large amount of water. Moreover, the volatile compounds from the fruit of L. barbarum L. are rather low in concentration. Hence, it is difficult for a conventional headspace method to study the volatile compounds from the fruit of L. barbarum L. Since headspace‐trap gas chromatography with mass spectrometry is an excellent method for trace analysis, a headspace‐trap gas chromatography with mass spectrometry method based on low‐temperature (30°C) enrichment and multiple headspace extraction was developed to explore the volatile compounds from the fruit of L. barbarum L. The headspace of the sample was extracted in 17 cycles at 30°C. Each time, the compounds extracted were concentrated in the trap (Tenax TA and Tenax GR, 1:1). Finally, all the volatile compounds were delivered into the gas chromatograph after thermal desorption. With the method described above, a total of 57 compounds were identified. The identification was completed by mass spectral search, retention index, and accurate mass measurement.     

Evaluation of gas chromatographic columns for the determination of methylmercury in aqueous head space extracts from biological samples.

Several gas chromatographic columns were evaluated for the determination of methylmercury in aqueous solution. The goal of the study was to further decrease the detection limit of the recently developed method of head space gas chromatography with microwave-induced plasma detection (HS-GC-MIP) for the determination of methylmercury in biological samples. The columns were first evaluated using gas chromatography with electron-capture detection (ECD). At the same time, the column efficiencies for the determination of ethyl- and phenylmercury were also studied. Of the packed columns the stationary phase used previously in HS-GC-MIP, AT-1000, yielded the best results. Better results were obtained with two wide-bore thick-film fused-silica open tubular (FSOT) columns, one of which was suitable for aqueous injections (Superox-FA) and the other for benzene or toluene (RSL-300). With these FSOT columns, absolute detection limits at the sub-picogram level were reached. A new HS-GC-MIP system was then constructed, which was adapted for the use of FSOT columns. As more sensitive measurements were obtained with a Superox-FA FSOT column than with an AT-1000 packed column using the GC-ECD system in the first part of this study, the FSOT column was evaluated in this HS-GC-MIP system for the determination of methylmercury in real tissue samples. It was demonstrated that the use of an FSOT column gives only a small decrease in the detection limit compared with a packed column; reconditioning of the FSOT column is, however, a disadvantage in routine measurements.     

聚醚砜酮涂层纤维顶空固相微萃取-气相色谱法分析水中痕量的酚类化合物

应用自制的聚醚砜酮(PPESK,30 μm)涂层纤维,采用顶空固相微萃取-气相色谱法测定水中痕量的酚类化合物。优化了固相微萃取温度、萃取时间、pH值和离子强度。方法的检出限为0.003～0.041 μg/L,相对标准偏差低于16%(n=5)。将PPESK涂层纤维与商品化的聚丙烯酸酯涂层纤维对比,结果表明PPESK萃取酚类化合物有较高的萃取富集倍数。用所制备的PPESK萃取头分析自来水、海水等实际水样,20 μg/L添加水平下的回收率分别为100.5%～111.8%和94.8%～117.3%。