Determination of urinary 8-hydroxy-2′-deoxyguanosine by capillary electrophoresis with molecularly imprinted monolith in-tube solid phase microextraction

Urinary 8-hydroxy-2 -deoxyguanosine(8-OHdG) is an excellent marker of oxidative DNA damage.In this study,employing guanosine as dummy template a novel molecularly imprinted(MIP) monolithic capillary column had been synthesized,and that was used as medium of in-tube solid phase microextraction(SPME).Coupled with capillary electrophoresis-electrochemical detection(CE-ECD),the system of extraction and detection of 8-OHdG in urinary sample had been developed.Because of its greater phase ratio combined with conv...

Analysis of α, β, γ-hexachlorocyclohexanes in water by novel activated carbon fiber-solid phase microextraction coupled with gas chromatography—mass spectrometry

A fast and simple method for determination of α, β, γ-hexachlorocyclohexanes (HCHs) in water using activated carbon fiber-solid phase microextraction(ACF-SPME) were studied. Results showed the performance of adsorption and desorption of three HCHs on ACF were excellent. A wide linear range from 10 to 100 μg/L and detection limits of the ng/L level were obtained using ACF-SPME with GC-MS in selected ion monitoring(SIM) acquisition mode. The proposed method was also successfully applied for determination of three HCHs in tap water. Compared to commercial fibers, ACF showed some advantages such as better resistance to solvents, higher thermal stability, longer lifetime and lower cost. The data demonstrated that GC-MS with ACF-SPME is well suitable for the analysis of HCHs in water.

Determination of Aromatic Components of Rosa davurica Pall. by Headspace Solid Phase Microextraction Combined with GC-MS

[Objectives] To determine the aromatic components of Rosa davurica Pall. [Methods] 42 kinds of aromatic components were identified from the flowers of R. davurica by headspace solid phase microextraction( HS-SPME) combined with gas chromatography-mass spectrometry( GC-MS). The main compounds were alcohols( 54. 88%) and aldehydes( 19. 55%). [Results] The top five components with the highest relative content were phenylethyl alcohol( 12. 69%),geraniol( 9. 85%),citronellol( 8. 80%),nerol( 7. 84%) and 2-n-pentylfuran( 7. 45%). [Conclusions] Headspace solid phase microextraction( HS-SPME) combined with gas chromatography-mass spectrometry( GC-MS) can provide basis for further development and utilization of R. davurica.

Solid phase microextraction chemical biopsy tool for monitoring of doxorubicin residue during in vivo lung chemo-perfusion

Development of a novel in vivo lung perfusion(IVLP)procedure allows localized delivery of high-dose doxorubicin(DOX)for targeting residual micrometastatic disease in the lungs.However,DOX delivery via IVLP requires careful monitoring of drug level to ensure tissue concentrations of this agent remain in the therapeutic window.A small dimension nitinol wire coated with a sorbent of biocompatible morphology(Bio-SPME)has been clinically evaluated for in vivo lung tissue extraction and determination of DOX and its key metabolites.The in vivo Bio-SPME-IVLP experiments were performed on pig model over various(150 and 225 mg/m^(2))drug doses,and during human clinical trial.Two patients with metastatic osteosarcoma were treated with a single 5 and 7 μg/mL(respectively)dose of DOX during a 3-h IVLP.In both pig and human cases,DOX tissue levels presented similar trends during IVLP.Human lung tissue concentrations of drug ranged between 15 and 293 μg/g over the course of the IVLP procedure.In addition to DOX levels,Bio-SPME followed by liquid chromatography-mass spectrometry analysis generated 64 metabolic features during endogenous metabolite screening,providing information about lung status during drug administration.Real-time monitoring of DOX levels in the lungs can be performed effectively throughout the IVLP procedure by in vivo Bio-SPME chemical biopsy approach.Bio-SPME also extracted various endogenous molecules,thus providing a real-time snapshot of the physiology of the cells,which might assist in the tailoring of personalized treatment strategy.

Comparison of Headspace Solid-Phase Microextraction with Simultaneous Steam Distillation Extraction for the Analysis of the Volatile Constituents in Chinese Apricot

Volatile constituents in fully mature fruits of apricot （Prunus armeniaca L.） cultivar Xinshiji were extracted using headspace solid-phase microextraction （HS-SPME） and simultaneous steam distillation extraction （SSDE） and then analyzed using capillary gas chromatography and gas chromatography-mass spectrometry. A total of 70 components were identified by HSSPME, including 20 esters, 19 hydrocarbons, 5 alcohols, 5 ketones, 4 acids, 4 lactones, 3 aldehydes, and 10 miscellaneous components, with the esters being the dominant constituent. On the basis of the odor unit values, it is believed that the following compounds probably contributed to the fresh apricot odor： hexyl acetate, β-ionone, butyl acetate, （E）-2-hexenal, linalool, limonene, γ-decalactone, and hexanal. A total of 49 components were also detected by SSDE, including 13 hydrocarbons, 9 alcohols, 7 aldehydes, 9 esters, 4 ketones, 4 lactones, 2 acids, and 1 miscellaneous component, of which the monoterpene alcohols were the dominant constituents. It could be judged from the odor unit values that the following compounds were the major contributors to boiled apricot aroma： β-ionone, linalool, hexyl acetate, γ-dodecalactone, γ- decalactone, （E）-2-hexenal, hexanal, γ-octalactone, phenylacetaldehyde, butyl acetate, limonene, α-terpineol, and δ-decalactone. The results show that HS-SPME is a simple, rapid, and solvent-free method, which is an alternative to the classical SSDE.

A novel fiber coating for solid phase microextraction and its application for the extraction of n-alkane from aqueous sample

Base on the previous work in laboratory, a novel polyaniline doped with polydimethylsiloxane coating was developed on a stainless steel wire for solid phase microextraction（SPME） by electroplating method. This electroplating method not only has advantages of ease preparation and simple equipments required, but also increases the lifetime of the SPME fiber. The composite fiber（polyaniline/ polydimethylsiloxane（PANI/PDMS）） was evaluated by analyzing n-tridecane, n-tetradecane and n-pentadecane in aqueous sample. The new fiber coating showed comprehensive abilities to extract alkanes compounds. The relative standard deviations were found to be 6.8%-10.33%.

Solid phase microextraction(SPME) sampling under turbulent conditions and for the simultaneous collecting of tracer gases

Solid phase microextraction （SPME） is a solvent-flee method of sample collection. SPME is an appealing method for sample collection because it is designed for the sampling of trace level analytes with short sampling times in a variety of environments. Additionally, SPME can be used to directly deliver a sample to a gas chromatograph （GC） for analysis by means of thermal desorption. In this paper, the performance of SPME under dynamic conditions was investigated. Additionally, the competence of SPME sampling for the simultaneous analysis of multiple trace analytes was also evaluated. This work is discussed in the context of underground mine ventilation surveys but is applicable to any industry in which ventilation circuits must be evaluated. The results of this paper showed that the performance of the 100 ~m PDMS SPME fiber was both precise and rapid under dynamic conditions. This SPME fiber was also able to simultaneously collect sulfur hexafluoride （SF6） and perfluoromethylcyclohexane （PMCH） with adequate sensitivity.

Preparation of polypyrrole/nanosilica composite for solid-phase microextraction of bisphenol and phthalates migrated from containers to eye drops and injection solutions

This paper describes the electrodeposition of polyphosphate-doped polypyrrole/nanosilica nano-composite coating on steel wire for direct solid-phase microextraction of bisphenol A and five phthalates. We optimized influencing parameters on the extraction efficiency and morphology of the nanocomposite such as deposition potential, concentration of pyrrole and polyphosphate, deposition time and the nanosilica amount. Under the optimized conditions, characterization of the nanocomposite was inves-tigated by scanning electron microscopy and Fourier transform infra-red spectroscopy. Also, the factors related to the solid-phase microextraction method including desorption temperature and time, extrac-tion temperature and time, ionic strength and pH were studied in detail. Subsequently, the proposed method was validated by gas chromatography-mass spectrometry by thermal desorption and acceptable figures of merit were obtained. The linearity of the calibration curves was between 0.01 and 50 ng/mL with acceptable correlation coefficients (0.9956-0.9987) and limits of detection were in the range 0.002-0.01 ng/mL. Relative standard deviations in terms of intra-day and inter-day by five replicate analyses from aqueous solutions containing 0.1 ng/mL of target analytes were in the range 3.3%-5.4% and 5%-7.1%, respectively. Fiber-to-fiber reproducibilities were measured for three different fibers prepared in the same conditions and the results were between 7.3% and 9.8%. Also, extraction recoveries at two different concentrations were ≥96%. Finally, the suitability of the proposed method was demonstrated through its application to the analysis of some eye drops and injection solutions.

Integration of GC-MS Based Non-Targeted Metabolic Profiling with Headspace Solid Phase Microextraction Enhances the Understanding of Volatile Differentiation in Tobacco Leaves from North Carolina, India and Brazil

In this report, gas chromatography-mass spectrometry (GC-MS) based non-targeted metabolomics is used to develop appropriate headspace solid phase microextractions (HS-SPME) to enhance the understanding of volatile complexity of flue-cured tobacco leaves. Non-targeted metabolic profiling of GC-MS shows that the extraction condition of HS-SPME at 100?C for 30 min provides a better metabolite profile than other extraction conditions tested. GC-MS and principal component analyses (PCA) show that among five types of fibers tested, 100 μm polydimethylsiloxane (PMDS), 65 μm polydimethylsiloxane/divinylbenzene (PMDS/DVB) and 75 μm carboxen/polydimethylsiloxane (CAR/ PMS) provide a better reproducible metabolite profile. Based on an appropriate PDMS extraction condition optimized, we use GC-MS analysis and PCA to compare metabolite profiles in flue-cured leaves of tobacco plants grown in North Carolina, India and Brazil, respectively. The resulting data of PCA show that the global metabolic profiles in North Carolina samples are separated from those in Brazil and India samples, two groups of which are characterized by a partially overlapped pattern. Several peaks that were differentially accumulated in samples were annotated to known metabolites by deconvolution analysis, such as norsolanadione, solavetivone and rishtin. Norsolanadione is detected only in Brazil samples. Solavetivone is detected in samples of India and Brazil but not in those of North Carolina. Rishtin is detected in samples of North Carolina and India but not in Brazil samples. These data indicate that not only can a non-targeted metabolic profiling approach enhance the understanding of volatile complexity, but also can identify marker volatile metabolites in tobacco leaves produced in different growth regions.

Flash Evaporation and Headspace Solid-phase Microextraction for the Analysis of the Essential Oils in Traditional Chinese Medicine,Houttuynia Cordata Thunb

We have investigated the use of flash evaporation, headspace solid-phase microextraction (HS-SPME) and steam distillation (SD) as sample concentration and preparation techniques for the analysis of volatile constituents present in Houttuynia cordata Thunb. The samples were analyzed by gas chromatography (GC) and identified by mass spectrometry (MS). Comparison studies were performed. It was found that the results obtained between Headspace solid-phase microextraction HS-SPME and SD techniques were in good agreement. Seventy-nine compounds in Houttuynia cordata Thunb were identified by MS. In flash evaporation, thirty-nine compounds were identified. Discrimination in the response for many constituents studied was not observed, which can be clearly observed in SD and HS-SPME techniques. As a conclusion, HS-SPME is a powerful tool for determining the volatile constitutes present in the Houttuynia cordata.

Application of Phenyl Bonded Mesoporous Silica as A Novel Coating Layer of Solid-phase Microextraction for Determination of Benzo[a]pyrene in Water Samples

Phenyl bonded mesoporous silica (C6H5-MCM-41) was applied as the fiber coating of solid-phase microextraction (SPME). The performance of the fiber coating was discussed coupling to HPLC. Applicability of mesoporous fiber coating was examined for the determination of benzo[a]pyrene (B[a]P) in water samples. The limit of detection (LOD) is 0.28μg·L-1. Good recovery and relative standard deviation (RSD) were obtained.

Sol-Gel-Coated Calix[4]arene Fiber for Solid-Phase Microextraction

5, 11, 17, 23-tetra-tert-butyl-25, 27-diethoxy-26, 28-dihydroxycalix \ arene /hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction with sol-gel technology. The properties of the new coating were investigated by analysis of benzene derivatives, polycyclic aromatic hydrocarbons and aromatic amines. The fiber is characterized by good sensitivity and selectivity to these aromatics. The fiber has stable performance at a high temperature of 380℃ and after a long solvent immersing, thus its lifetime is very long. It shows good fiber-to-fiber and batch-to-batch reproducibility. Furthermore, broad linear ranges and low detection limits are also its characteristics.

Solid-phase Microextraction with Benzoxy-calix[6]arene Fiber Coupled to Gas Chromatography for the Analysis of Polycyclic Aromatic Hydrocarbons in Water

Headspace solid-phase microextraction（HS-SPME） with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seven polycyclic aromatic hydrocarbons（PAHs） in water. The novel SPME fiber exhibited higher extraction efficiency to PAHs compared with poly（dimethylsiloxane） and other calixarene-containing fibers. Extraction/retention mechanism based on the interactions between calixarenes and PAHs was discussed. Owing to the good selectivity and high extraction capability of this calixarene fiber, low detection limits were obtained in a range of 0.34―6.50 ng/L and the relative standard deviation values were ≤12.3% for all of the analytes. The linear ranges of the proposed method were five orders of magnitude for the tested compounds, with linear correlation coefficients（r） greater than 0.998. The method was applied to the determination of polycyclic aromatic hydrocarbons in nine water sources in Wuhan City, China. Standard addition method was selected for the quantification and the recovery values were in a satisfactory range. Total PAHs concentrations in the nine surface water samples were found to vary between undetectable and 8.840 μg/L with two- and three-ring PAHs predominating.

Preparation of A New Fiber by Sol-gel Technology in Solid-phase Microextraction (SPME)

The sol-gel technology is applied for the preparation of solid-phase microextraction (SPME) fiber. The fiber demonstrates high thermal stability, efficient extraction rate and the selectivity for non-polar or low-polar analytes. Efficient SPME-GC-FID analyses of benzene- toluene-ethylbenzene-xylenes (BTEXs) and low-polar halocarbon were achieved by the sol-gel coated DSDA-DDBT-TiO2 fiber. Some parameters of the SPME fiber for the determination of halocarbon in aqueous sample were investigated.

Determination of organochlorine pesticides from juice samples using magnetic biochar-based dispersive micro-solid phase extraction in combination with dispersive liquid-liquid microextraction

Analysis of pesticide residue levels in juice beverages is important to ensure safe consumption and avoid global trade concerns associated to pesticide contaminations.A simple,inexpensive and effective method was developed for the determination of organochlorine pesticides(OCPs)in bottled juice drinks using GC-MS.Sample pretreatment was performed using dispersive solid-phase microextraction(D-μ-SPE)for matrix desorption and dispersive liquid-liquid microextraction(DLLME)for analyte enrichment.In this study,an affordable and effective sorbent for the adsorption of OCPs from juice samples was synthesized from avocado seeds mixed with magnetic precursors for D-μSPE.The ground avocado seeds combined with a magnetic precursor nanocomposite were characterized using various instruments including scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and Brunauer-Emmett-Teller(BET)analysis.The solution obtained from D-μ-SPE desorption was used as a dispersant for the subsequent DLLME,which made the combination of D-μ-SPE with DLLME much easier.The effectiveness of the method was enhanced by optimizing the influential parameters in both D-μ-SPE and DLLME.Then after,the optimal values were determined for the real sample analysis.Accordingly,there was good linear dynamic range with a coefficient of determination(r2)≥0.9989.The limit of detection and quantification were 0.02–0.69 and 0.06–2.10 ng/L respectively.The method showed high enrichment factors ranging from 96 to 313 with recoveries of 87–100%.Intraday and interday precisions were≤4%.Compared with other reported methods,this method is a one-step,simple,cheap,fast,and environmentally friendly alternative and straightforward method for adsorbing organochlorine pesticides from sample solutions.These results demonstrates the high potential of the proposed method for the extraction and cleanup of contaminants in selected juices and other related samples.

不同产地沃柑挥发性成分的差异分析

该研究旨在分析4个主产地(四川、重庆、云南和广西)的沃柑果皮中挥发性成分的差异性,并为沃柑的产地溯源和深加工提供数据支撑。利用顶空固相微萃取-气相色谱-质谱联用技术测定了沃柑果皮挥发性成分,共鉴定出50种挥发性成分,其中萜烯类18种、醇类11种、醛类10种、酯类8种、酮类1种、其他类2种。柠檬烯是主要的挥发性物质,月桂烯、α-蒎烯、芳樟醇、正辛醇、正辛醛、香茅醇、己醛、反式-2-己烯醛、桧烯、香芹酮和α-松油醇等次之。基于挥发性成分半定量结果,建立四川和重庆,云南和广西沃柑的正交偏最小二乘法判别分析模型,进而筛选出潜在生物标志物。结果表明,柠檬烯、芳樟醇和香茅醇可作为区分重庆和四川的潜在生物标志物,醋酸辛酯和α-松油醇可作为区分广西和云南的潜在生物标志物。

基于HS-GC-IMS和HS-SPME-GC-MS的蛋白酶对豆粕挥发性风味的影响分析

为研究不同蛋白酶酶解对豆粕挥发性风味成分的影响,选用4种蛋白酶(碱性蛋白酶、中性蛋白酶、木瓜蛋白酶、风味蛋白酶)对豆粕进行酶解,采用顶空-气相色谱-离子迁移谱(Headspace-gas chromatography-ion mobility spectroscopy,HS-GC-IMS)和顶空固相微萃取-气相色谱-质谱(Headspace solid phase microextraction-gas chromatography-mass spectrometry,HS-SPME-GC-MS)联用技术分析不同豆粕酶解物(Soybean meal hydrolysates,SMH)的挥发性风味成分,并结合主成分分析(Principal component analysis,PCA)、热图聚类和正交偏最小二乘判别法(Orthogonal partial least squares-discriminant analysis,OPLS-DA)对不同SMH进行分析。结果表明:碱性蛋白酶、中性蛋白酶、木瓜蛋白酶和风味蛋白酶酶解豆粕的挥发性风味成分存在较大差异。HS-GC-IMS鉴定出84种挥发性成分,筛选得到33种差异风味物质,发现酶解后酮类物质显著降低而醛类、醇类和酯类物质含量明显增加。PCA结果表明不同SMH之间的风味存在显著差异。最终通过OPLS-DA筛选出贡献较大的挥发性化合物,同时构建出可靠的用以鉴别SMH的模型。HS-SPME-GC-MS检测出103种差异风味物质,可用于区分不同SMH,被检出的挥发性组分中醛类、醇类和酮类等化合物为SMH风味的形成做出主要贡献,明晰了部分风味化合物形成的原因。PCA和聚类热图结果表明不同蛋白酶酶解对豆粕的挥发性风味物质的种类和含量有显著影响,其中,风味蛋白酶和木瓜蛋白酶对豆粕的风味改善最为显著。

共价有机框架衍生多孔碳固相微萃取纤维结合气相色谱法测定水样中的邻苯二甲酸酯

以4-甲酰基苯硼酸(FPBA)和2,4,6-三(4-氨基苯基)-1,3,5-三嗪(TAPT)为单体,通过溶剂热法制备了共价有机框架(COF)FPBA-TAPT,将其直接热解后获得衍生多孔碳材料(PC)FTPC.傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、拉曼光谱及扫描电子显微镜(SEM)表征结果显示,该材料呈球形,表面呈褶皱结构,比表面积为499 m2/g.利用溶胶-凝胶法将其涂覆在不锈钢丝表面制得固相微萃取纤维,结合气相色谱法建立了测定水样中邻苯二甲酸酯(PAEs)的方法.对萃取和解吸条件进行优化后,该方法具有较宽的线性范围(0.5~100μg/L)、较低的检测限(0.018~0.106μg/L)和良好的稳定性(相对标准偏差,RSD≤7.8%).将该方法用于3种水样中PAEs的检测,低(5μg/L)、中(10μg/L)及高(50μg/L)加标回收率为79.5%~123.9%,RSD为1.1%~12.2%,表明该方法具有良好的准确性,可实现水体中PAEs的有效定量分析.

基于壳聚糖改性的磁性氧化石墨烯的半自动化管尖固相微萃取技术在环境水中痕量铅快速测定中的应用

以戊二醛为交联剂,采用壳聚糖(CS)和四氧化三铁(Fe_(3)O_(4))修饰氧化石墨烯(GO),制备了Fe_(3)O_(4)-GO/CS复合物(吸附剂)。将20 mg Fe_(3)O_(4)-GO/CS填装于200μL微型枪头中,两端填上少量玻璃棉,枪头旁边放置磁铁。将12 mL塑料注射器和枪头连接,用塑料注射器吸取1 mL水冲洗Fe_(3)O_(4)-GO/CS表面可能吸附的杂质。环境水样经0.22μm滤膜过滤后,将滤液酸度调至pH6.0,用塑料注射器吸取10 mL,固定在注射泵上,将水样以0.8 mL·min^(-1)流量通过枪头;再吸取1 mL 0.010 mol·L^(-1)盐酸溶液(洗脱剂),以0.5 mL·min^(-1)流量洗脱吸附在Fe_(3)O_(4)-GO/CS上的铅。收集洗脱液,用电感耦合等离子体质谱法测定。结果显示:Fe_(3)O_(4)-GO/CS对铅的平衡吸附容量为126 mg·g^(-1),可重复使用50次,吸附过程符合朗缪尔(Langmuir)等温吸附模型;铅的质量浓度在0.01~10.00μg·L^(-1)内和响应值呈线性关系,检出限为0.005μg·L^(-1)。对实际水样进行3个浓度水平的加标回收试验,回收率为84.7%~105%,测定值的相对标准偏差(n=5)为0.90%~3.9%。

基于多元统计学分析^(60)Co-γ射线辐照对川芎挥发性成分的影响

川芎挥发性成分是其主要活性成分之一,也是评价川芎药用品质的重要指标。为探究^(60)Co-γ射线辐照对川芎挥发性成分的影响,本研究以不同吸收剂量处理川芎样品,采用电子鼻结合顶空固相微萃取-气相色谱-质谱技术(HS-SPME-GC-MS),通过主成分分析、线性判别分析、正交偏最小二乘法和聚类分析的多元统计学方法分析数据,以期了解川芎辐照前后挥发性成分的变化。电子鼻与GC-MS结果都表明:川芎气味主要由烷烃类、醇类、醛类、酮类贡献,10 kGy剂量以下的辐照处理对川芎挥发性气味成分影响不大;川芎经0 kGy(对照组)、3 kGy、7 kGy、10 kGy剂量辐照处理后,共鉴定出60种化合物,其中烃类23种,醇类12种,脂类10种,醛酮类4种,其他类11种;筛选到21种辐照前后的差异特征性指标物,它们在川芎挥发性成分中只占约12.92%,不是川芎的主要挥发性成分。经10 kGy剂量以下的辐照处理后,川芎中没有新生成的物质被鉴定出来。研究结果提示经10 kGy以下剂量处理川芎不会影响其主要挥发性成分。