顶空固相微萃取-气相色谱/质谱法分析鉴定畜禽粪便中的挥发性有机化合物

采用顶空固相微萃取(HS-SPME)-气相色谱/质谱法(GC/MS)测定了牛粪、猪粪以及鸡粪中的挥发性有机化合物(VOCs)。在优化HS-SPME条件的基础上,通过GC/MS分析,从牛粪中分离鉴定出44种VOCs,从猪粪中分离鉴定出40种VOCs,从鸡粪中分离鉴定出41种VOCs。HS-SPME-GC/MS具有简单、快速、无需有机溶剂等特点,适合于畜禽粪便中挥发性有机化合物的分析与鉴定。同时,该研究揭示了畜禽养殖场臭味物质的来源,为治理其环境污染提供了科学依据。     

Solid phase microextraction/isothermal GC for rapid analysis of complex organic samples

Solid phase microextraction (SPME) was used as the sample introduction technique for high-speed isothermal GC. An injector dedicated for SPME fiber injection was designed and built. The injector was operated in two modes, continuously heated and flash heated. The latter mode proved to be better for high-speed separations. The injector was then used for sample introduction in separation of BTEX. When sampling directly from water with a fiber having a 56 μm thick poly(dimethylsiloxane) coating, the BTEX components were separated under isothermal conditions in ca. 18 s. A fiber with a thinner coating (15 μm) enabled the separation to be completed in ca. 12 s when sampling from headspace. In both cases the results were highly reproducible, as measured by the estimated values of the relative standard deviation.     

固相微萃取-气相色谱法测定红葡萄酒中残留的有机磷农药

采用溶胶-凝胶包埋技术制备了耐高温固相微萃取头(SPME),用该萃取头与气相色谱-热离子化检测器联用对红葡萄酒中的12种有机磷农药残留进行了测定。实验中对搅拌速度、萃取时间、盐浓度等条件进行了优化。结果表明,在样品用量25 mL,搅拌速度1250 r/min,盐浓度 150 g/L,萃取时间30 min的条件下,绝大多数组分峰面积的相对标准偏差（RSD）在5%以下,各种有机磷农药的检测限为5 ng/L到0.38 μg/L。     

微孔有机聚合物固相微萃取纤维的制备及在有机氯农药检测中的应用

利用1,3,6,8-四(4-醛基)芘和三聚氰胺为单体合成微孔有机聚合物(MOP),并将其固定在不锈钢丝上,制备成固相微萃取纤维涂层。将其用于顶空固相微萃取(HS-SPME),结合气相色谱-电子捕获检测手段,建立了对大米中有机氯农药的在线检测方法。实验考察了4种实验参数对富集能力的影响,得到了最优的实验条件:萃取温度80℃、萃取时间25 min、NaCl质量浓度200 g/L、解吸时间6 min。在此实验条件下,对有机氯农药的富集倍数达到115~318倍。方法在0.05~50μg/kg范围内具有良好的线性关系,检出限为2.4~11.3 ng/kg。同一纤维及不同纤维富集后测定结果的相对标准偏差范围分别为1.3%~13.1%和2.3%~13.6%。该方法简单、快速,可以实现对实际样品中有机氯农药的痕量分析。     

广东不同地区产柠檬的果肉中挥发性风味物质的比较

采用顶空固相微萃取―气相色谱质谱联用(HS-SPME-GC-MS)的方法比较广东省内番禺产和连南产柠檬的果肉中挥发性风味物质的异同。实验采用7μmPDMS(聚二甲基硅氧烷)的萃取头进行吸附。气相色谱分析采用DB-5MS气相色谱柱,柱温采取程序升温,进样口温度250℃,分流比20∶1。质谱采用EI源为离子源,电子能量70 eV,离子源温度200℃;接口温度230℃。结果表明,番禺柠檬和连南柠檬果肉中的主要风味物质均为D-柠檬烯,但连南柠檬中风味物质的种类更多,这可能是连南柠檬香气更为浓郁的原因之一。     

微波蒸馏-固相微萃取-气相色谱-质谱-嗅觉检测器联用分析鳙鱼鱼肉中的挥发性成分

用微波蒸馏(MD)-固相微萃取装置(SPME)提取鳙鱼鱼肉中的挥发性成分,利用气相色谱-质谱联用仪(GC-MS)对气味化合物成分进行了定性分析,同时利用嗅觉检测器鉴别了部分挥发性物质的气味特征。实验中优化了MD的操作条件(加热功率、加热时间及载气流速等)、SPME参数(萃取头种类、萃取温度、萃取时间、无机盐离子浓度及搅拌速率等)。通过NIST 02质谱数据库检索共定性确定出鳙鱼鱼肉挥发性成分中的53种化合物,其中主要为 C6~C9 的羰基化合物和挥发性醇类。经过嗅觉检测器分析,这些成分分别具有青草味、鱼腥味、泥土味等气味特征,其协同作用构成了鳙鱼鱼肉特殊的鱼腥味、泥腥味。该方法可用于水产品中挥发性成分的分析,并可为不良风味化合物的定量研究提供参考。     

固相微萃取-气相色谱/质谱测定植物叶片中的挥发性物质

采用固相微萃取（SPME)方法吸附植物叶片中的挥发性物质,然后采用气相色谱/质谱法（GC/MS）分析了挥发性物 质的成分。在45 ℃水浴温度下,采用Polyacrylate(85 μm)固相微萃取头,在广口瓶中植物叶片的上方顶空吸附60 min,然后进行GC/MS分析。结果表明,植物叶片中的挥发性物质得到了很好的分离,受山楂叶螨(Tetraychus vienneis) 危害严重的植物的完好叶片中的挥发性物质均含有顺-3-己烯-1-醇乙酸酯、顺-3-己烯-1-醇丁酸酯和α-法呢烯,且含量 较大。初步确定这些物质是对山楂叶螨具有引诱作用的主要物质,从而为利用天然生物活性物质防治山楂叶螨提供了理论 依据。     

QSRR Study of GC Retention Indices of Volatile Compounds Emitted from Mosla chinensis Maxim by Multiple Linear Regression

The volatile compounds emitted from Mosla chinensis Maxim were analyzed by headspace solid‐phase microextraction (HS‐SPME) and headspace liquid‐phase microextraction (HS‐LPME) combined with gas chromatography‐mass spectrometry (GC‐MS). The main volatiles from Mosla chinensis Maxim were studied in this paper. It can be seen that 61 compounds were separated and identified. Forty‐nine volatile compounds were identified by SPME method, mainly including myrcene, α‐terpinene, p‐cymene, (E)‐ocimene, thymol, thymol acetate and (E)‐β‐farnesene. Forty‐five major volatile compounds were identified by LPME method, including α‐thujene, α‐pinene, camphene, butanoic acid, 2‐methylpropyl ester, myrcene, butanoic acid, butyl ester, α‐terpinene, p‐cymene, (E)‐ocimene, butane, 1,1‐dibutoxy‐, thymol, thymol acetate and (E)‐β‐farnesene. After analyzing the volatile compounds, multiple linear regression (MLR) method was used for building the regression model. Then the quantitative structure‐retention relationship (QSRR) model was validated by predictive‐ability test. The prediction results were in good agreement with the experimental values. The results demonstrated that headspace SPME‐GC‐MS and LPME‐GC‐MS are the simple, rapid and easy sample enrichment technique suitable for analysis of volatile compounds. This investigation provided an effective method for predicting the retention indices of new compounds even in the absence of the standard candidates.     

环境样品中双酚类化合物的固相萃取研究进展

双酚类化合物作为一类内分泌干扰物广泛存在于环境介质中,经过多种途径迁移至人体后,可对人体产生内分泌毒性、细胞毒性、基因毒性、生殖毒性、二噁英毒性和神经毒性,已被加拿大政府风险评估识别为进一步优先控制名录。随着环境领域对双酚类化合物的广泛关注,相关研究工作逐渐向水、沉积物、灰尘和生物样品等多介质开拓。但是,由于不同环境样品在基质复杂性和污染物浓度水平等方面存在显著差异,开发提取效率高、净化选择性好、普适性强、操作简单、高通量的提取和净化方法,有助于实现环境介质中双酚类化合物的高灵敏、批量检测。近年来,新型前处理技术发展迅速,尤其是固相萃取技术,在双酚类化合物提取与净化方面取得了长足的发展,不仅在一定程度上克服了传统提取净化方法存在的耗时、耗力和耗溶剂等不足,而且为新型污染物分析提供了更多的技术支持。该文简述了典型双酚类化合物的理化性质、用途用量和环境危害,重点围绕新型固相萃取吸附剂开发和固相萃取模式转变两个方面,总结了固相萃取在双酚类化合物提取净化方法方面取得的进展。商品化固相萃取产品普适性强,在环境监测领域应用范围较广,适用于双酚类化合物的产品种类有限;新型吸附剂研发聚焦吸附容量(如介孔硅材料、碳纳米材料、金属-有机框架材料、环糊精)和选择性(如分子印迹聚合物和混合模式离子交换聚合物)两个方面,种类多样化可满足不同检测需求;越来越多的高灵敏分析仪器不断推向市场,为适应新的发展形势,固相萃取模式正逐渐向微型化、自动化、简易化等方向发展,如QuEChERS、固相微萃取、磁固相萃取等。     

镍钛合金纤维/有机硅-聚氨酯固相微萃取头的制备及其在水中7种取代苯化合物检测中的应用

以2,4-甲苯二异氰酸酯、聚酯多元醇、羟基硅油为原料,辛酸亚锡为催化剂,环己酮为溶剂,合成有机硅-聚酯型聚氨酯。将此聚合物涂于经氢氧化钾水热处理的镍钛合金纤维丝表面作为固相微萃取涂层,制得固相微萃取头。利用红外光谱法分析了聚合物结构;热重分析法确定了涂层最高使用温度;扫描电子显微镜观察了萃取头的表面形貌。以顶空萃取-固相微萃取-气相色谱法（HS-SPME-GC）测定了水中甲苯、二甲苯、间二氯苯、邻二氯苯、苯甲酸乙酯、硝基苯、苯甲醇7种取代苯化合物的含量。各被测物的色谱峰面积与其质量浓度呈良好的线性关系,相关系数（R²）为0.9926~0.9998,方法的检出限为0.08~0.24 μg/L。实际样品测定的加标回收率为95.9%~105.4%,相对标准偏差为1.4%~5.0%。通过对实际样品的分析,说明制备的固相微萃取头涂层不易脱落、性质稳定,对于水中取代苯类化合物具有很强的吸附能力。     

固相微萃取-气相色谱法测定白洋淀水样中的邻苯二甲酸酯类化合物

建立了固相微萃取(SPME)-气相色谱法(GC)分析环境水样中痕量邻苯二甲酸酯类化合物(PAEs)的方法。选用100 μm聚二甲基硅烷(PDMS)萃取纤维,在磁力搅拌条件下,对水样中的PAEs萃取富集60 min,然后直接注入GC进样口,在250 ℃温度下解吸4 min后进行分析测定,13种PAEs能得到充分提取和分离。方法的重现性(以相对标准偏差(RSD)计为0.2%～9.7%,检出限为0.02～0.83 μg/L。将本方法应用于白洋淀水样中PAEs的分析检测发现,样品中邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)检出率相对较高。对水样进行两个浓度水平(2.5 μg/L和5.0 μg/L)的加标试验,加标回收率为75.3%～111.0%,RSD为2.1%～8.0%(n=3),能够满足环境水样中痕量PAEs的测定要求。     

微波辅助萃取-固相微萃取-气相色谱法同时测定茶叶中的有机氯和拟除虫菊酯农药残留

建立了微波辅助萃取-固相微萃取-气相色谱(MAE-SPME-GC)同时测定茶叶中六六六(α-BHC,β-BHC,γ-BHC,δ-BHC 4种异构体)、滴滴涕类(DDD,DDE,o,p′-DDT,p,p′-DDT)、氯氰菊酯(cypermethrin)和氰戊菊酯(fenvalerate)等10种农药残留的方法。采用外标法定量,除氰戊菊酯外,农药的质量浓度与其色谱峰面积在一定范围内有较好的线性关系,相关系数为0.9705～0.9984。10种组分的加标回收率为64%～121%,相对标准偏差为10.4%～22.9%,检测限为1～50 ng/L。应用该方法测定了市场上3种茶叶中上述农药残留的含量。     

Potential of solid phase microextraction and gas chromatography for quarantine-required detection of wood packaging in shipping containers

Solid phase microextraction (SPME) coupled with gas chromatography (GC) was used to detect terpene hydrocarbons inside shipping containers entering New Zealand. The utility of this system for the rapid detection of undeclared wood packaging for quarantine purposes was demonstrated. A portable dynamic air-sampling device was built to house a SPME fibre and allow the air from shipping containers to be sampled. The effects of sample flow rate and sampling time were investigated and sampling conditions of 100 mL/min for 30 s were chosen to keep sampling within the linear range. A CV of less than 15% (n = 12) was obtained for all the compounds analysed under these conditions. To obtain an estimate for the limit of detection (LOD) for the terpene hydrocarbons of interest, small quantities of lime oil were placed in an empty shipping container and the air inside was analysed. LOD (S/N = 3) was estimated to be in the order of 50-100 ng/L of air using GC with flame ionisation detection (GC-FID). Finally, the device was tested in fully laden containers and was shown to be effective for trapping terpene hydrocarbons indicative of wood packaging.     

Accurate analysis of trace earthy-musty odorants in water by headspace solid phase microextraction gas chromatography-mass spectrometry

A simple and sensitive method was developed for the simultaneous separation and determination of trace earthy-musty compounds including geosmin, 2-methylisoborneol, 2-isobutyl-3-methoxypyrazine, 2-isopropyl-3-methoxypyrazine, 2,3,4-trichloroanisole, 2,4,6-trichloroanisole, and 2,3,6-trichloroanisole in water samples. This method combined headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry and used naphthalene-d(8) as internal standard. A divinylbenzene/carboxen/polydimethylsiloxane fiber exposing at 90°C for 30 min provided effective sample enrichment in HS-SPME. These compounds were separated by a DB-1701MS capillary column and detected in selected ion monitoring mode within 12 min. The method showed a good linearity from 1 to 100 ng L(-1) and detection limits within (0.25-0.61 ng L(-1)) for all compounds. Using naphthalene-d(8) as the internal standard, the intra-day relative standard deviation (RSD) was within (2.6-3.4%), while the inter-day RSD was (3.5-4.9%). Good recoveries were obtained for tap water (80.5-90.6%), river water (81.5-92.4%), and lake water (83.5-95.2%) spiked at 10 ng L(-1). Compared with other methods using HS-SPME for determination of odor compounds in water samples, this present method had more analytes, better precision, and recovery. This method was successfully applied for analysis of earthy-musty odors in water samples from different sources.     

气相色谱/电感耦合等离子体质谱测定植物中挥发性硒化合物

Severalinstrumentalmethodscanbeusedforthedetectionanddeterminationofvolatileselenium(Se)andsulfur (S)compounds .Theserelyprimari lyongaschromatography (GC)forseparationanddifferentdetectiontechniques ,includingatomice missiondetection (AED ) ,massspectrom…     

Speciation of Volatile Selenium Species in Plants Using Gas Chromatography/Inductively Coupled Plasma Mass Spectrometry

 Gas chromatography/inductively coupled plasma mass spectrometry (GC/ICP MS) coupled with solid phase micro extraction can provide a simple, extremely selective and sensitive technique for the analysis of volatile sulfur and selenium compounds in the hea     

固相微萃取―气相色谱―质谱联用方法分析人参中的挥发性物质

采用固相微萃取―气相色谱―质谱联用(SPME-GC-MS)的方法测定了人参中的挥发性物质,并对萃取头类型、萃取温度、萃取时间进行了优化。结果表明,当采用100μm聚二甲基硅氧烷(PDMS)的萃取头(非极性),80℃萃取30 min时,萃取效果最好。结果显示,人参中主要的挥发性物质为γ-榄香烯和β-古芸烯等。     

顶空固相微萃取-气相色谱-质谱法分离鉴定金华火腿的挥发性风味物质

采用顶空固相微萃取法(HS-SPME)制备样品,利用气相色谱-质谱法（GC-MS）分离鉴定了金华火腿的挥发性风味物质。实验中筛选了固相微萃取纤维头,优化了固相微萃取的操作条件。用75 μm碳分子筛/聚二甲基硅氧烷（CAR-PDMS）纤维头,于60 ℃下对金华火腿样品顶空吸附40 min,于250　℃下解吸2 min,采用GC-MS对解吸物进行分离鉴定。金华火腿样品的分析结果表明,其挥发性风味物质中含量较高的是醛、酸和酮类化合物,还有一些含硫或杂环化合物。     

Round-robin evaluation of a solid-phase microextraction-gas chromatographic method for reliable determination of trace level ethylene oxide in sterilized medical devices

Medical devices that are sterilized with ethylene oxide (EtO) retain small quantities of EtO residuals, which may cause negative systemic and local irritating effects, and must be accurately quantified to ensure non-toxicity. The goal of this round-robin study is to investigate the capability of a novel solid-phase microextraction-gas chromatographic (SPME-GC) method for trace-level EtO residuals analysis: three independent laboratories conducted a guided experiment using this SPME-GC method, in assessing method performance, ruggedness and the feasibility of SPME fibers. These were satisfactory across the independent laboratories, at the 0.05-5.00 ppm EtO range. This method was then successfully applied to analyze EtO residuals in several sterilized/aerated medical devices of various polymeric composition, reliably detecting and quantifying the trace levels of EtO residuals present ( approximately 0.05 ppm EtO). SPME is a feasible alternative for quantifying trace-level EtO residuals in sterilized medical devices, thereby lowering the limit of quantification (LOQ) by as much as two to three orders of magnitude over the current GC methodology of direct liquid injection.     

管内硼亲和固相微萃取-高效液相色谱全自动在线联用检测茶饮料中的顺式二羟基化合物

自动化联用分析技术对于降低人力强度、提高效率和保证数据重现性等具有重要意义。硼亲和固相微萃取(BA-SPME)是近十年出现的用于富集顺式二羟基化合物的独特工具,但BA-SPME与高效液相色谱(HPLC)的自动化在线联用还未见报道。该文报道了一种新颖的管内BA-SPME-HPLC全自动在线联用方法,用于分析茶饮料中的顺式二羟基化合物。该自动化在线联用方法利用自动进样器通过六通阀的切换实现流路连接。制备了管内BA-SPME毛细管,考察了涂层柱的柱容量,并对其形貌进行了表征,考察并优化了影响实际样品分离效果的因素。最后,利用该联用方法对3种不同品牌的茶饮料进行了分析,并对沏茶温度对茶水中顺式二羟基化合物含量的影响进行了评价。