超临界CO_2萃取用于有机锡污染物检测和党参中有效成分提取的研究
|
摘要
超临界流体萃取(supercritical fluid extraction, SFE)是一种环境友好的新型化工分离技术,近年来在分析领域作为生物样品的痕量药检前处理方法正在逐步代替某些传统方法,展示了诱人的应用前景。同时,SFE被视为先进的关键技术在天然产物和中药有效成分的提取中得到广泛研究与应用。有机锡是人类带入海洋最毒的污染物之一,本文采用分析型超临界萃取等技术对食品安全中亟待解决的有机锡污染物的检测进行了研究;同时也对采用SFE提取中药党参中的有效成分进行了探讨。该研究对提高食品安全检测技术水平以及促进中药生产现代化具有重要意义。
本文建立了高效的SFE/HS-SPME/GC-MS测定海产品中有机锡含量的检测技术,即采用分析型SFE结合顶空固相微萃取(HS-SPME)为样品前处理技术,对海产品中六种不同形态有机锡(即:三甲基一氯化锡(TMT)、一丁基三氯化锡(MBT)、二丁基二氯化锡(DBT)、三丁基一氯化锡(TBT)、一苯基三氯化锡(MPT)、三苯基一氯化锡(TPT) )污染物进行提取与净化,而后采用GC-MS进行检测。通过实验研究多种因素对检测效果的影响,得到优化的操作条件为:0.5g蛤肉样品经含5% (mol)甲醇的超临界CO2在温度为45℃、压力为30 MPa条件下萃取15分钟(流速1.2 L·min-1以常压CO2计),然后用0.02 g·mL-1的四乙基硼化钠(NaBEt4)进行衍生化处理,并用聚二甲基硅氧烷/二乙烯基苯(PDMS/DVB)纤维进行固相微萃取富集后,进行GC-MS分析。整个分析过程仅需1小时,消耗有机溶剂还不到10mL。结果表明,该方法对于DBT、MPT、TBT和TPT四种有机锡的回收率在79 % ~ 90 %之间,最低检出限在0.04 ng.g-1(Sn) ~ 0.26 ng.g-1(Sn),满足定量回收的要求。精密度、最低检出限和线性范围也满足海产品中痕量有机锡检测的要求。但该方法用于TMT和MBT检测时的回收率较低(分别为26%和63%),而不适宜作为这两种有机锡的定量检测技术。
本文建立了一套动态法测定溶质在超临界流体中溶解度的实验装置。通过测定苯甲酸在超临界CO2中的溶解度对设备的可靠性进行了验证,实测值与文献值偏差在5%以内。利用该设备测定了在温度35.0℃~ 65.0℃、压力15.0 MPa ~ 40.0 MPa的范围内三苯基一氯化锡(TPT)和三苯基一氯甲烷(TPC)两种化合物在超临界CO2中的溶解度。结果表明,TPT的溶解度在4.12×10-4 ~1.10×10-3范围内,TPC的溶解度在3.82×10-4 ~ 2.70×10-3范围内。分别用Gordillo方程、Christil方程和改进的Christil经验方程对TPT和TPC在超临界CO2中的溶解度数据进行了关联,结果良好。对于TPT各方程计算值与实验值的AARD分别为5.0%、8.6%和7.1 %,对于TPC,各方程计算值与实验值的平均相对偏差(AARD)分别为11.4%、6.4%和7.3%。
在对常用中药党参进行超临界CO2萃取工艺研究中,首先以收膏率和总皂苷元为目标函数,通过单因素实验研究了超临界CO2萃取党参中脂溶性成分的适宜工艺条件。结果表明,在原料粒度40目~ 60目,萃取压力30MPa,萃取温度65℃的优化条件下得到的收膏率和总皂苷元得率分别为0.0111 g.g-1和2.23 mg.g-1。党参炔苷是党参中的一种重要的有效成分,采用中心实验设计和二次响应曲面法,系统考察温度、压力、夹带剂用量和时间等因素对收膏率和党参炔苷的萃取结果的影响及其相互作用。确定了夹带剂用量是提高党参炔苷生产效率最有效的控制因素,增加夹带剂用量可同时提高收膏率和党参炔苷得率。进一步优化了含动态夹带剂的党参炔苷超临界萃取工艺。实验结果表明,中药党参在动态夹带剂乙醇流速为1 mL·min-1,CO2流速为2 L·min-1,30 MPa,60℃下萃取100 min,党参炔苷得率为0.078 6 mg·g-1,优于超声萃取法。研究结果为建立一种党参炔苷提取的绿色工艺提供了基础数据。
Supercritical fluid extraction (SFE) is environmentally friendly and high effective technology. It has been presently considered as analytical extraction method and has been proposed as an alternative approach for analyzing harmful chemical residues in biological samples. It has been also considered as one of the most attractive technology for processing natural product and traditional China medicines (TCM). In this thesis, analytical SFE was used for determination of the harmful organotin compounds (OTCs) in foods, and industrial SFE was used for extraction of active components from codonopsis pilosula. The two kinds of projects are important in the fields of food safety and modernization of TCM.
A rapid and green method for the determination of six OTCs, namely trimethyltin chloride (TMT), butyltin trichloride (MBT), dibutyltin dichloride (DBT), tributyltin chloride(TBT), triphenyltin chloride (MPT) and phenyltin trichloride(TPT), in clam samples was established by combining SFE and headspace solid-phase microextraction (HS-SPME) as pretreatment method and then by gas chromatography with mass spectrometry (GC-MS) analysis. Effect of some factors on extraction efficiency was investigated and the optimal operation parameters were obtained as follows. The clam sample was first extracted at 45℃and 30 MPa with supercritical carbon dioxide in presence of 5% (mol) methanol at 1.2 L·min-1 (as carbon dioxide in ambient pressure) for 15 min. The SFE extract was then ethylated with 0.02 g·mL-1 sodium tetraethylborate (NaBEt4) in pH 4 buffer solution and simultaneously adsorbed by HS-SPME with polydimethylsiloxane / divinylbenzene (PDMS/DVB) fiber at 50℃for 30 min. And then GC-MS was performed. The whole process for sampling and analyzing was within 1h, and only less than 10 milliliters of organic solvent was used. Six OTCs in the spiked clam sample were determined with the established method, in which the recoveries of DBT、MPT、TBT and TPT were from 79 % ~ 90 % with LOD ranging from 0.04 to 0.26 ng/g, which indicate that the established procedure in this paper should be reliable and accurate for the determination the four OTCs in biotic sample. However, the established method may not suitable for determination of TMT and MBT as their recoveries were between 26% and 63%.
A semiflow-type, dynamic apparatus was established for determinating the solubility of compounds in supercritical fluid. An equipment reliability proof test was made with the benzoic acid-carbon dioxide system. Comparing the measured benzoic acid solubility data with literature data, the average deviation is within 5%. The solubility of TPT and triphenylmethyl chloride (TPC) in supercritical CO2 were measured at a temperature ranging from 308.15 K to 338.15 K and various pressures in the range of 15 MPa to 40 MPa. The mole fraction solubilities ranged from 4.12×10-4 ~1.10×10-3 for TPT, and 3.82×10-4 ~ 2.70×10-3 for TPC. The experimental data of the solubility of TPT and TPC were correlated by Gordillo equation, Chrastil equation and modified Chrastil models separately, and good fit results were obtained. The correlation errors of the three models for TPT are 5.0%, 8.6% and 7.1 % respectively. And the correlation errors of the three models for TPC are 11.4%, 6.4% and 7.3% respectively.
Finally, supercritical extraction of active compounds from Codonopsis pilosula with CO2 was studied. The influences of particle size, pressure and temperature on yield together with the yield of total sapogenins were discussed, Based on one-factor-at-a-time experiments. The optimal yield of 0.0111g·g-1 and yield of total sapogenins 2.23 mg·g-1 were obtained, when Codonopsis was extracted at 30 MPa, 65℃and 2 L·min-1 (as CO2 in normal pressure and temperature) for 2 hours with pure supercritical Carbon Dioxide. To develop a green and rapid method for extraction of lobetyolin from Codonopsis pilosula, extraction of lobetyolin from Codonopsis pilosula with supercritical carbon dioxide in the presence of ethanol was studied. The effect of pressure, temperature, volume of cosolvent and extraction time on efficiency and their interactive relationships were discussed, based on central composite design and response surface methodology (RSM). The key factor, volume of cosolvent was found. The extraction yield of lobetyolin was 0.0786 mg·g-1 when Codonopsis pilosula was extracted at 30 MPa, 60℃and 2 L·min-1(as CO2 in normal pressure and temperature) for 100 minutes with supercritical CO2 and 1 mL·min-1 ethanol as dynamic cosolvent. This result is better than that obtained from ultrasonic method. Therefore, the optimized process is a valuable method for extraction of lobetyolin from Codonopsis pilosula.
本文建立了高效的SFE/HS-SPME/GC-MS测定海产品中有机锡含量的检测技术,即采用分析型SFE结合顶空固相微萃取(HS-SPME)为样品前处理技术,对海产品中六种不同形态有机锡(即:三甲基一氯化锡(TMT)、一丁基三氯化锡(MBT)、二丁基二氯化锡(DBT)、三丁基一氯化锡(TBT)、一苯基三氯化锡(MPT)、三苯基一氯化锡(TPT) )污染物进行提取与净化,而后采用GC-MS进行检测。通过实验研究多种因素对检测效果的影响,得到优化的操作条件为:0.5g蛤肉样品经含5% (mol)甲醇的超临界CO2在温度为45℃、压力为30 MPa条件下萃取15分钟(流速1.2 L·min-1以常压CO2计),然后用0.02 g·mL-1的四乙基硼化钠(NaBEt4)进行衍生化处理,并用聚二甲基硅氧烷/二乙烯基苯(PDMS/DVB)纤维进行固相微萃取富集后,进行GC-MS分析。整个分析过程仅需1小时,消耗有机溶剂还不到10mL。结果表明,该方法对于DBT、MPT、TBT和TPT四种有机锡的回收率在79 % ~ 90 %之间,最低检出限在0.04 ng.g-1(Sn) ~ 0.26 ng.g-1(Sn),满足定量回收的要求。精密度、最低检出限和线性范围也满足海产品中痕量有机锡检测的要求。但该方法用于TMT和MBT检测时的回收率较低(分别为26%和63%),而不适宜作为这两种有机锡的定量检测技术。
本文建立了一套动态法测定溶质在超临界流体中溶解度的实验装置。通过测定苯甲酸在超临界CO2中的溶解度对设备的可靠性进行了验证,实测值与文献值偏差在5%以内。利用该设备测定了在温度35.0℃~ 65.0℃、压力15.0 MPa ~ 40.0 MPa的范围内三苯基一氯化锡(TPT)和三苯基一氯甲烷(TPC)两种化合物在超临界CO2中的溶解度。结果表明,TPT的溶解度在4.12×10-4 ~1.10×10-3范围内,TPC的溶解度在3.82×10-4 ~ 2.70×10-3范围内。分别用Gordillo方程、Christil方程和改进的Christil经验方程对TPT和TPC在超临界CO2中的溶解度数据进行了关联,结果良好。对于TPT各方程计算值与实验值的AARD分别为5.0%、8.6%和7.1 %,对于TPC,各方程计算值与实验值的平均相对偏差(AARD)分别为11.4%、6.4%和7.3%。
在对常用中药党参进行超临界CO2萃取工艺研究中,首先以收膏率和总皂苷元为目标函数,通过单因素实验研究了超临界CO2萃取党参中脂溶性成分的适宜工艺条件。结果表明,在原料粒度40目~ 60目,萃取压力30MPa,萃取温度65℃的优化条件下得到的收膏率和总皂苷元得率分别为0.0111 g.g-1和2.23 mg.g-1。党参炔苷是党参中的一种重要的有效成分,采用中心实验设计和二次响应曲面法,系统考察温度、压力、夹带剂用量和时间等因素对收膏率和党参炔苷的萃取结果的影响及其相互作用。确定了夹带剂用量是提高党参炔苷生产效率最有效的控制因素,增加夹带剂用量可同时提高收膏率和党参炔苷得率。进一步优化了含动态夹带剂的党参炔苷超临界萃取工艺。实验结果表明,中药党参在动态夹带剂乙醇流速为1 mL·min-1,CO2流速为2 L·min-1,30 MPa,60℃下萃取100 min,党参炔苷得率为0.078 6 mg·g-1,优于超声萃取法。研究结果为建立一种党参炔苷提取的绿色工艺提供了基础数据。
Supercritical fluid extraction (SFE) is environmentally friendly and high effective technology. It has been presently considered as analytical extraction method and has been proposed as an alternative approach for analyzing harmful chemical residues in biological samples. It has been also considered as one of the most attractive technology for processing natural product and traditional China medicines (TCM). In this thesis, analytical SFE was used for determination of the harmful organotin compounds (OTCs) in foods, and industrial SFE was used for extraction of active components from codonopsis pilosula. The two kinds of projects are important in the fields of food safety and modernization of TCM.
A rapid and green method for the determination of six OTCs, namely trimethyltin chloride (TMT), butyltin trichloride (MBT), dibutyltin dichloride (DBT), tributyltin chloride(TBT), triphenyltin chloride (MPT) and phenyltin trichloride(TPT), in clam samples was established by combining SFE and headspace solid-phase microextraction (HS-SPME) as pretreatment method and then by gas chromatography with mass spectrometry (GC-MS) analysis. Effect of some factors on extraction efficiency was investigated and the optimal operation parameters were obtained as follows. The clam sample was first extracted at 45℃and 30 MPa with supercritical carbon dioxide in presence of 5% (mol) methanol at 1.2 L·min-1 (as carbon dioxide in ambient pressure) for 15 min. The SFE extract was then ethylated with 0.02 g·mL-1 sodium tetraethylborate (NaBEt4) in pH 4 buffer solution and simultaneously adsorbed by HS-SPME with polydimethylsiloxane / divinylbenzene (PDMS/DVB) fiber at 50℃for 30 min. And then GC-MS was performed. The whole process for sampling and analyzing was within 1h, and only less than 10 milliliters of organic solvent was used. Six OTCs in the spiked clam sample were determined with the established method, in which the recoveries of DBT、MPT、TBT and TPT were from 79 % ~ 90 % with LOD ranging from 0.04 to 0.26 ng/g, which indicate that the established procedure in this paper should be reliable and accurate for the determination the four OTCs in biotic sample. However, the established method may not suitable for determination of TMT and MBT as their recoveries were between 26% and 63%.
A semiflow-type, dynamic apparatus was established for determinating the solubility of compounds in supercritical fluid. An equipment reliability proof test was made with the benzoic acid-carbon dioxide system. Comparing the measured benzoic acid solubility data with literature data, the average deviation is within 5%. The solubility of TPT and triphenylmethyl chloride (TPC) in supercritical CO2 were measured at a temperature ranging from 308.15 K to 338.15 K and various pressures in the range of 15 MPa to 40 MPa. The mole fraction solubilities ranged from 4.12×10-4 ~1.10×10-3 for TPT, and 3.82×10-4 ~ 2.70×10-3 for TPC. The experimental data of the solubility of TPT and TPC were correlated by Gordillo equation, Chrastil equation and modified Chrastil models separately, and good fit results were obtained. The correlation errors of the three models for TPT are 5.0%, 8.6% and 7.1 % respectively. And the correlation errors of the three models for TPC are 11.4%, 6.4% and 7.3% respectively.
Finally, supercritical extraction of active compounds from Codonopsis pilosula with CO2 was studied. The influences of particle size, pressure and temperature on yield together with the yield of total sapogenins were discussed, Based on one-factor-at-a-time experiments. The optimal yield of 0.0111g·g-1 and yield of total sapogenins 2.23 mg·g-1 were obtained, when Codonopsis was extracted at 30 MPa, 65℃and 2 L·min-1 (as CO2 in normal pressure and temperature) for 2 hours with pure supercritical Carbon Dioxide. To develop a green and rapid method for extraction of lobetyolin from Codonopsis pilosula, extraction of lobetyolin from Codonopsis pilosula with supercritical carbon dioxide in the presence of ethanol was studied. The effect of pressure, temperature, volume of cosolvent and extraction time on efficiency and their interactive relationships were discussed, based on central composite design and response surface methodology (RSM). The key factor, volume of cosolvent was found. The extraction yield of lobetyolin was 0.0786 mg·g-1 when Codonopsis pilosula was extracted at 30 MPa, 60℃and 2 L·min-1(as CO2 in normal pressure and temperature) for 100 minutes with supercritical CO2 and 1 mL·min-1 ethanol as dynamic cosolvent. This result is better than that obtained from ultrasonic method. Therefore, the optimized process is a valuable method for extraction of lobetyolin from Codonopsis pilosula.
引文
[1].Chester T L,Pinkston J D,Raynie D E,Supercritical fluid chromatographyand extraction,Analytical Chemistry,1998,70(12):301-319.
[2].Supercritical Fluids:Encyclopedia of chemical technology(3rd),supplement,p 872-893.
[3].King M B,Kassim K,Bott T R,Mass transfer into near-critical extractants,Fluid Phase Equilibria,1983,10(2-3):249-260.
[4].Paulaitis M E,Krukonis V J,Kurnik R T et al,Supercritical fluid extraction,Reviews in Chemical Engineering,1983,1(2):179-250.
[5].Stephan K,Lucas K,Viscosity of dense fluids,1979:281.
[6].Carbon Dioxide:Encyclopedia of chemical technology(3rd),supplement.
[7].陈维纽,超临界流体萃取的原理和应用,北京:化学工业出版社,1998.
[8].McHugh M,Krukonis V,Supercritical fluid extraction:Principles andpractice,2nd ed,Butterworth-Heinemann Series in Chemical Engineering,1994:101.
[9].李淑芬,姜忠义,高等制药分离工程,北京:化学工业出版社,2004.
[10].Krukonis V J,Kurnik R T,Solubility of solid aromatic isomers in carbondioxide,Journal of Chemical and Engineering Data,1985,30(3):247-249.
[11].Schneider G M,Physicochemical principles of extraction with supercriticalgases,Angew Chem(Int Ed Engl),1978,17(10):716-727.
[12].King J W,Fundamentals and applications of supercritical fluid extraction inchromatographic science,Journal of Chromatographic Science,1989,27(7):355-364.
[13].King J W,Applications of capillary supercritical fluid chromatography-supercritical fluid extraction to natural products,Journal of Chromatographic Science,1990,28(1):9-14.
[14].Zosel K,Separation with supercritical gases:practical applications,AngewChem(Int Ed Engl),1978,17(10):702-709.
[15].Camel V,The determination of pesticide residues and metabolites usingsupercritical fluid extraction,TrAC-Trends in Analytical Chemistry,1997,16(6):351-369.
[16].Quan C,Li S,Tian S et al,Supercritical fluid extraction and clean-up oforganochlorine pesticides in ginseng,Journal of Supercritical Fluids,2004,31(2):149-157.
[17].Beyer A,Biziuk M,Applications of sample preparation techniques in theanalysis of pesticides and PCBs in food,Food Chemistry,2008,108(2):669-680.
[18].Zuin V G,Yariwake J H,Bicchi C,Fast supercritical fluid extraction andhigh-resolution gas chromatography with electron-capture and flame photometricdetection for multiresidue screening of organochlorine and organophosphoruspesticides in Brazil's medicinal plants,Journal of Chromatography A,2003,985(1-2):159-166.
[19].Garimella U I,Stearman G K,Wells M J M,Comparison among soil seriesand extraction methods for the analysis of trifluralin,Journal of Agricultural and FoodChemistry,2000,48(12):5874-5880.
[20].Rissato S R,Galhiane M S,Knoll F R N et al,Supercritical fluid extractionfor pesticide multiresidue analysis in honey:Determination by gas chromatographywith electron-capture and mass spectrometry detection,Journal of Chromatography A,2004,1048(2):153-159.
[21].Terfloth G J,Pirkle W H,Lynam K G et al,Broadly applicable polysiloxane-based chiral statio nary phase for high-performance liquid chromatography and supercritical fluid chromatography,Journal of Chromatography A,1995,705(2):185-194.
[22].刘志敏,赵庆,王仁安等.超临界流体色谱法测定银杏叶提取物中的黄酮类化合物[J].分析化学,1999,27(2):214~216.
[23].元英进,刘明言,董岸杰,中药现代化生产关键技术,北京:化学工业出版社,2002.
[24].葛发欢,辉国钧,李菁等,中药现代化与超临界CO2流体技术的应用.In第二届全国超临界流体技术学术及应用研讨会论文集,张镜澄，曾健青,Ed.中国化工学会:北京,1998.
[25].张定安,陆志禹,时钧,超临界流体及超临界萃取（Ⅰ）（Ⅱ）,南京化工学院学报,1992,14(2):79~93.
[26].Mehr C B,Biswal R N,Collins J L e t al,Sup ercritical carbon dioxide extraction of caffeine from guarana,Journal of Supercritical Fluids,1996,9(3):185-191.
[27].Park H S,Choi H K,Lee S J et al,Effect of mass transfer on the removal of caffe ine from green tea by supercritical carbon dioxide,Journal of Supercritical Fluids,2007,42(2):205-211.
[28].Park H S,Lee H J,Shin M H et al,Effects of cosolvents on the decaffeination of green tea by supercritical carbon dioxide,Food Chemistry,2007,105(3):1011-1017.
[29].张冲，李嘉诚，周雪晴等，超临界CO2萃取迷迭香精油及其化学成分分析，精细化工，2008，25（1）：62~67.
[30].巫华美，陈训，何香银，超临界二氧化碳萃取宽叶缬草油的化学成分研究，张镜澄，曾健青，第二届全国超临界流体技术学术及应用研讨会论文集，北京：中国化工学会，1998，115-118.
[31].Guan W,Li S,Yan R et al,Comparison of essential oils of clove buds extracted with supercritical carbon dioxide and other three traditional extraction methods,Food Chemistry,2007,101(4):1558-1564.
[32].韩布兴，超临界流体科学与技术，北京：中国石化出版社，2005，1~4.
[33].樊文乐,武文洁,超临界萃取中夹带剂的概述,食品科技,2005,(2):39~42.
[34].赵东胜，刘桂敏，吴兆亮，超临界流体萃取技术研究与应用进展，天津化工，2007，21（3）：10~12.
[35].李淑芬,中药现代化生产关键技术,北京:2002.
[36].Casas L,Mantell C,Rodriguez M et al,Effect of the addition of cosolvent on the supercritical fluid extraction of bioactive compounds from Helianthus annuus L,Journal of Supercritical Fluids,2007,41(1):43-49.
[37].Macias-Sanchez M D,Serrano C M,Rodriguez M R et al,Extraction of carotenoids and chlorophyll from microalgae with supercritical carbon dioxide and ethanol as cosolvent,Journal of Separation Science,2008,31(8):1352-1362.
[38].Murga R,Ruiz R,Beltran S et al,Extraction of natural complex phenols and tannins from grape seeds by using supercritical mixtures of carbon dioxide and alcohol,Journal of Agricultural and Food Chemistry,2000,48(8):3408-3412.
[39].Ting S S T,Macnaughton S J,Tomasko D L et al,Solubility of naproxen insupercritical carbon dioxide with and without cosolvents,Industrial and Engineering Chemistry Research,1993,32(7):1471-1481.
[40].Zhang Y,Li S f,Wu X w,Pressurized liquid extraction of flavonoids from Houttuynia cordata Thunb,Separation and Purification Technology,2008,58(3):305-310.
[41].Pasquini D,Pimenta M T B,Ferreira L H et al,Sugar cane bagasse pulping using supercritical CO2 associated with co-solvent 1-butanol/water,Journal of Supercritical Fluids,2005,34(2 SPEC.ISS.):125-131.
[42].Johnston K P,Harrison K L,Clarke M J et al,Water-in-carbon dioxide microemulsions: An on envir ment for hydrophiles including proteins,Science,1996,271(5249):624-626.
[43].罗登林,丘泰球,王睿瑞,不同强化方法对超临界CO2萃取人参皂甙的影响,精细化工,2006,23(3):269~272.
[44].Arthur C L,Killam L M,Buch holz K D et al,Automation and optimization of solid-phase microextraction,Analytical Chemistry,1992,64(17):1960-1966.
[45].Potter D W,Pawliszyn J,Detection of substituted benzenes in water at the pg/ml level using solid-phase microextraction and gas chromatography-ion trap mass spectrometry,Journal of Chromatography,1992,625(2):247-255.
[46].Zhang Z,Pawliszyn J,Headspace solid-phase microextraction,Analytical Chemistry,1993,65(14):1843-1852.
[47].刘绍从,吕刚,赵好力宝等,固相微萃取-气相色谱法测定食品添加剂中有害有机挥发杂质,分析试验室,2006,25(3):17~20.
[48].Alzaga R,Bayona J M,Supercritical fluid extraction of tributyltin and its degradation products from seawater via liquid--solid phase extraction,Journal of Chromatography A,1993,655(1):51-56.
[49].Zorita S,Westbom R,Thorneby L et al,Development of a combined solid-phase extraction-supercritical fluid extraction procedure for the determination of polychlorinated biphenyls in wastewater,Analytical Sciences:The International Journal Of The Japan Society For Analytical Chemistry,2006,22(11):1455-1459.
[50].Karasek P,Planeta J,Varad'ova Ostra E et al,Direct continuous supercritical fluid extraction as a novel method of wine analysis.Comparison with conventional indirect extraction and implications for wine variety identification, Journal Of Chromatography.A,2003,1002(1-2):13-23.
[51].Batlle R,Carlsson H,Tollback P et al,Enhanced detection of nitroaromatic explosive vapors combining solid-phase extraction-air sampling,supercritical fluid extraction,and large-volume injection-GC,Analytical Chemistry,2003,75(13):3137-3144.
[52].全灿,超临界流体萃取技术检测/脱除中药材种有机氯农残的研究,[博士论文].天津大学,2005.
[53].Quan C,Li S,Tian S et al,Supercritical fluid extraction and clean-up of organochlorine pesticides in ginseng,The Journal of Supercritical Fluids,2004,31(2):149-157.
[54].Mathiasson L,Turner C,Berg H et al,Development of methods for the determination of vitamins A,E and beta-carotene in processed foods based on supercritical fluid extraction:a collaborative study,Food Additives And Contaminants,2002,19(7):632-646.
[55].Mannila M,Koistinen J,Vartiainen T,Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment,Journal Of Environmental Monitoring:JEM,2002,4(6):1047-1053.
[56].Mannila M, Koistinen J, Vartiainen T, Development of supercritical fluid extraction with a solid-phase trapping for fast estimation of toxic load of polychlorinated dibenzo-p-dioxins-dibenzofurans in sawmill soil, Journal of Chromatography A, 2002, 975 (1): 189-198.
[57].Rodil R, Carro A M, Lorenzo R A et al, Selective extraction of trace levels of polychlorinated and polybrominated contaminants by supercritical fluid-solid-phase microextraction and determination by gas chromatography/mass spectrometry. Application to aquaculture fish feed and cultured marine species, Analytical Chemistry, 2005, 77 (7): 2259-2265.
[58].Salleh S H, Saito Y, Jinno K, An approach to solventless sample preparation procedure for pesticides analysis using solid phase microextraction/supercritical fluid extraction technique, Analytica Chimica Acta, 2000, 418 (1): 69-77.
[59].Salleh S H, Saito Y, Kiso Y et al, Solventless sample preparation procedure for organophosphorus pesticides analysis using solid phase microextraction and on-line supercritical fluid extraction/high performance liquid chromatography technique, Analytica Chimica Acta, 2001, 433 (2): 207-215.
[60].王珊珊,冯流,有机锡化合物的毒性效应及其影响因素,安全与环境学报,2005,5(3):12~15．.
[61].江桂斌,国内外有机锡污染研究现状,卫生研究,2001,30(1):1~3.
[62].Fent K, Looser P W, Bioavailability and bioconcentration of organotin compounds in aquatic organisms, Abstracts of Papers of the American Chemical Society, 1998, 215: U588-U588.
[63].Takahashi S, Tanabe S, Kawaguchi K, Organochlorine and butyltin residues in mesopelagic myctophid fishes from the western North Pacific, Environmental Science & Technology, 2000, 34 (24): 5129-5136.
[64].Ohji M, Arai T, Miyazaki N, Chronic effects of tributyltin on the caprellid amphipod Caprella danilevskii, Marine Pollution Bulletin, 2003, 46 (10): 1263-1272.
[65].Ohji M, Takeuchi I, Takahashi S et al, Differences in the acute toxicities of tributyltin between the Caprellidea and the Gammaridea (Crustacea : Amphipoda), Marine Pollution Bulletin, 2002, 44 (1): 16-24.
[66].El-Menif N T, Lahbib Y, Ramdani M et al, Imposex in the marine neogastropod Hexaplex trunculus from Tunisian coasts: geographical distribution and development intensity, Vie Et Milieu-Life and Environment, 2007, 57 (1-2): 37-42.
[67].Horiguchi T, Li Z, Uno S et al, Contamination of organotin compounds and imposex in molluscs from Vancouver, Canada, Marine Environmental Research, 2004, 57 (1-2): 75-88.
[68].Shintani N, Ogita K, Hashimoto H et al, Recent studies on the trimethyltin actions in central nervous systems, Yakugaku Zasshi-Journal of the Pharmaceutical Society of Japan, 2007, 127 (3): 451-461.
[69].Carfi M, Gennari A, Malerba I et al, In vitro tests to evaluate immunotoxicity: A preliminary study, Toxicology, 2007, 229 (1-2): 11-22.
[70].Hagger J A, Depledge M H, Galloway T S, Toxicity of tributyltin in the marine mollusc Mytilus edulis, Marine Pollution Bulletin, 2005, 51 (8-12): 811-816.
[71].Hagger J A, Fisher A S, Hill S J et al, Genotoxic, cytotoxic and ontogenetic effects of tri-n-butyltin on the marine worm, Platynereis dumerilii (Polychaeta: Nereidae), Aquatic Toxicology, 2002, 57 (4): 243-255.
[72].Heroult J, Zuliani T, Bueno M et al, Analytical advances in butyl-, phenyl-and octyltin speciation analysis in soil by GC-PFPD, Talanta, 2008, 75 (2): 486-493.
[73].周群芳,江桂斌,吴迪靖,猪油样品中有机锡化合物的气相色谱-火焰光度法及气相色谱-质谱联用分析,分析化学,2001,29(04):453~456.
[74].C. Carlier-Pinasseau G L M A, Determination of Butyltin and Phenyltin by GC-FPD Following Ethylation by NaBEt4, Applied Organometallic Chemistry, 1996, 10(7): 505-512.
[75].Pereiro I R, Schmitt V O, Szpunar J et al, Speciation Analysis for Organotin Compounds in Biomaterials after Integrated Dissolution, Extraction, and Derivatization in a Focused Microwave Field, Analytical Chemistry, 1996, 68 (23): 4135-4140.
[76].Campillo N, Aguinaga N, Vinas P et al, Speciation of organotin compounds in waters and marine sediments using purge-and-trap capillary gas chromatography with atomic emission detection, Analytica Chimica Acta, 2004, 525 (2): 273-280.
[77].Moens L, De Smaele T, Dams R et al, Sensitive, Simultaneous Determination of Organomercury, -lead, and -tin Compounds with Headspace Solid Phase Microextraction Capillary Gas Chromatography Combined with Inductively Coupled Plasma Mass Spectrometry, Analytical Chemistry, 1997, 69 (8): 1604-1611.
[78].刘稷燕,江桂斌,固相微萃取技术及其在有机锡和有机汞分析中的应用,分析化学,1999,27(10):1226~1230.
[79].黄长江,雷瓒,董巧香,海产腹足类有机锡化合物的检测方法,海洋学报(中文版),2005,27(04):174~180.
[80].程慧琼,刘稷燕,江桂斌等,顶空固相微萃取技术用于海产品中丁基锡化合物的测定,色谱,2003,21(4):418~420.
[81].Blake E, Raynor M W, Cornell D, Determination of organotin compounds by capillary supercritical fluid chromatography with inductively coupled plasma mass spectrometric detection, Journal of Chromatography A, 1994, 683 (1): 223-231.
[82].Cai Y, Alzaga R, Bayona J M, In situ Derivatization and Supercritical Fluid Extraction for the Simultaneous Determination of Butyltin and Phenyltin Compounds in Sediment, Analytical Chemistry, 1994, 66 (7): 1161-1167.
[83].Liu Y, Lopez-Avila V, Alcaraz M et al, Off-Line Complexation/ Supercritical Fluid Extraction and Gas Chromatography with Atomic Emission Detection for the Determination and Speciation of Organotin Compounds in Soils and Sediments, Analytical Chemistry, 1994, 66 (21): 3788-3796.
[84] .Lopez-Avila V, Liu Y, Beckert W F, Interlaboratory evaluation of an off-line supercritical fluid extraction and gas chromatography with atomic emission detection method for the determination of organotin compounds in soil and sediments, Journal of Chromatography A, 1997, 785 (1-2): 279-288.
[85].Segovia-Garc E, Garc-Alonso J I, Sanz-Medel A, Determination of Butyltin Compounds in Sediments by Means of Hydride Generation/Cold Trapping Gas Chromatography Coupled to Inductively Coupled Plasma Mass Spectrometric Detection, Journal of Mass Spectrometry, 1997, 32 (5): 542-549.
[86].Jiang G B, Liu J Y, Determination of butyltin compounds in aqueous samples by gas chromatography with flame photometric detector and headspace solid-phase microextraction after in-situ hydride derivatization, Analytical Sciences, 2000, 16 (6): 585-588.
[87].Birjandi A P, Bidari A, Rezaei F et al, Speciation of butyl and phenyltin compounds using dispersive liquid-liquid microextraction and gas chromatography-flame photometric detection, Journal of Chromatography A, 2008, 1193 (1-2): 19-25.
[88].Bravo M, Lespes G, De Gregori I et al, Determination of organotin compounds by headspace solid-phase microextraction-gas chromatograph-pulsed flame-photometric detection (HS-SPME-GC-PFPD), Analytical and BioanalyticalChemistry, 2005, 383 (7-8): 1082-1089.
[89].Kaur V, Malik A K, Verma N, Applications of solid phase microextraction for the determination of metallic and organometallic species, Journal of Separation Science, 2006, 29 (3): 333-345.
[90].Chou C C, Lee M R, Determination of organotin compounds in water by headspace solid phase microextraction with gas chromatography-mass spectrometry, Journal of Chromatography A, 2005, 1064 (1): 1-8.
[91].Centineo G, Rodriguez-Gonzalez P, Gonzalez E B et al, Isotope dilution GC-MS routine method for the determination of butyltin compounds in water, Analytical and Bioanalytical Chemistry, 2006, 384 (4): 908-914.
[92].Almeida C, Serodio P, Florencio M H et al, New strategies to screen for endocrine-disrupting chemicals in the Portuguese marine environment utilizing large volume injection-capillary gas chromatography-mass spectrometry combined with retention time locking libraries (LVI-GC-MS-RTL), Analytical and Bioanalytical Chemistry, 2007, 387 (7): 2569-2583.
[93].中华人民共和国药典委员会,中华人民共和国药典[M],北京:化学工业出版社,2005.
[94].张雅君,梁忠岩,赵伟等,党参水溶性多糖的分离、纯化及诸成分析,中国药学杂志,2005,40(14):1107~110
[95].韩凤梅,程玲丽,陈勇,党参多糖的分离和纯化研究,中国药学杂志,2005,40(18):1381-1383.
[96].叶冠,李晨,黄成钢等,党参果聚糖的化学结构,中国药学杂志,2005,30(17):1380~1340.
[97].贺庆,朱恩圆,王峥涛等,党参化学成分的研究,中国药学杂志,2006,41(1):10~12．
[98].陈敏,李晓瑾,姜林,新疆党参挥发油成分的研究,中草药,2000,31(4):254.
[99].谢君,张义正,顾永祚,党参挥发油及脂溶性化学成分的研究,中国药学杂志,2000,35(9):583-586．
[100].杨荣平,王宾豪,励娜,GC-MS法分析大宁党参挥发油化学成分,中国实用医药,2007,2(25):33~34.
[101].朱恩圆,贺庆,王峥涛等,党参化学成分研究,中国药科大学学报,2001,32(2):94~95.
[102].阎永红,党参地上部分的基础研究,江西中医学院学报,2002,14(1):30.
[103].李艳,孙萍,刘霞等,新疆党参多糖的提取、含量分析及免疫功能的初步研究,中成药,2005,27(7):839-840.
[104].杨光,李发胜,刘辉,党参多糖对小鼠免疫功能的影响,中药药理与临床,2005,21(4):39~40.
[105].徐爱霞,张振明,葛斌等,党参多糖抗衰老作用机制的实验研究,中国现代应用药学杂志,2006,23(8):729~731.
[106].Ng T B, Liu F, Wang H X, The antioxidant effects of aqueous and organic extracts of Panax quinquefolium, Panax notoginseng, Codonopsis pilosula, Pseudostellaria heterophylla and Glehnia littoralis, Journal of Ethnopharmacology, 2004, 93 (2-3): 285-288.
[107] .Wang Z T, Du Q, Xu G J et al, Investigations on the protective action of Condonopsis pilosula (Dangshen) extract on experimentally-induced gastric ulcer inrats, General Pharmacology, 1997, 28 (3): 469-473.
[108].郑天珍,李伟,张英福等,党参对动物小肠推进运动的实验研究,甘肃中医学院学报,2001,18(1):19~20.
[109].Sui F, Wang R, Wang J et al, Effects of Dangshen root extract serum on intracellular free calcium in gastric parietal cells of dissociated rats, Zhong yao cai = Zhongyaocai = Journal of Chinese medicinal materials., 2005, 28 (10): 900-903.
[110].崔兴日,南极星,吕慧子等,党参提取物对急性肝损伤小鼠肝脏的保护作用,延边大学医学学报,2004,27(4):262~264.
[111].张天红,张馨,耿爱萍,潞党参药理实验研究,时珍国医国药,2001,12(6):488~489.
[112].方明,石云峰,焦炬焰,中药党参抗应激作用的研究,辽宁药物与临床,2002,5(1):32~33.
[113].闫彦芳,张壮,韦颖等,党参总皂苷抗缺氧缺糖再給氧诱导大鼠星形胶质细胞损伤的作用,北京中医药大学学报,2006,29(12):826~830.
[114].赵晓华,刘养清,裴晓丽,党参中党参炔苷的HPLC分析,山西中医学院学报2006,07(5):49~50.
[115].Johnston K P, Peck D G, Kim S, Modeling supercritical mixtures: How predictive is it?, Industrial and Engineering Chemistry Research, 1989, 28 (8): 1115-1125.
[116].朱自强,超临界流体萃取中的相平衡进展,高校化学工程学报,1994,8(1):1~10.
[117].Chrastil J, Solubility of solids and liquids in supercritical gases, Journal of Physical Chemistry, 1982, 86 (15): 3016-3021.
[118].Del Valle J M, Aguilera J M, An improved equation for predicting the solubility of vegetable oils in supercritical CO2, Industrial and Engineering Chemistry Research, 1988,27(8): 1551-1553.
[119].Gordillo M D, Blanco M A, Molero A et al, Solubility of the antibiotic Penicillin G in supercritical carbon dioxide, Journal of Supercritical Fluids, 1999, 15 (3): 183-190.
[120] .Mills G A, Walker V, Mughal H, Headspace solid-phase microextraction with 1-pyrenyldiazomethane in-fibre derivatisation for analysis of faecal short-chain fatty acids, Journal of Chromatography B: Biomedical Sciences and Applications, 1999,730(1): 113-122.
[121].Cai Y, Abalos M, Bayona J M, Effects of complexing agents and acid modifiers on the supercritical fluid extraction of native phenyl- and butyl-tins from sediment, Applied Organometallic Chemistry, 1998, 12 (8-9): 577-584.
[122] .Liu. Y, Lopez-Avila. V, Alcaraz. M et al, Determination of organotin compounds in environmental samples by supercritical fluid extraction and gas chromatography with atomic emission detection, Journal of High Resolution Chromatography, 1993, 16 (2): 106-112.
[123].Bayona J M, Cai Y, The role of supercritical fluid extraction and chromatography in organotin speciation studies, TrAC Trends in Analytical Chemistry, 1994, 13 (8): 327-332.
[124].Tang C H, Wang W H, Optimization of an analytical method for determining organotin compounds in fish tissue by base-hydrolysis pretreatment and simultaneous ethylation-extraction procedures, Analytica Chimica Acta, 2007, 581 (2): 370-376.
[125].Chau Y K, Yang F, Brown M, Supercritical fluid extraction of butyltin compounds from sediment, Analytica Chimica Acta, 1995, 304 (1): 85-89.
[126].Wasik A, Ciesielski T, Determination of organotin compounds in biological samples using accelerated solvent extraction, sodium tetraethylborate ethylation, and multicapillary gas chromatography-flame photometric detection, Analytical and Bioanalytical Chemistry, 2004, 378 (5): 1357-1363.
[127].Kurnik R T, Holla S J, Reid R C, Solubility of solids in supercritical carbon dioxide and ethylene, Journal of Chemical and Engineering Data, 1981, 26 (1): 47-51.
[128].周海涛,党参活脑有效物质基础研究,[硕士论文],中医药大学,2004.
[129].贺英,朱恩园,王峥涛等,党参中党参炔苷HPLC分析,中国药学杂志,2005,1(3):56.~57
[130].王雷,超临界流体-固体系统相平衡的模型化研究,[硕士学位论文],贵州大学,2005.
[2].Supercritical Fluids:Encyclopedia of chemical technology(3rd),supplement,p 872-893.
[3].King M B,Kassim K,Bott T R,Mass transfer into near-critical extractants,Fluid Phase Equilibria,1983,10(2-3):249-260.
[4].Paulaitis M E,Krukonis V J,Kurnik R T et al,Supercritical fluid extraction,Reviews in Chemical Engineering,1983,1(2):179-250.
[5].Stephan K,Lucas K,Viscosity of dense fluids,1979:281.
[6].Carbon Dioxide:Encyclopedia of chemical technology(3rd),supplement.
[7].陈维纽,超临界流体萃取的原理和应用,北京:化学工业出版社,1998.
[8].McHugh M,Krukonis V,Supercritical fluid extraction:Principles andpractice,2nd ed,Butterworth-Heinemann Series in Chemical Engineering,1994:101.
[9].李淑芬,姜忠义,高等制药分离工程,北京:化学工业出版社,2004.
[10].Krukonis V J,Kurnik R T,Solubility of solid aromatic isomers in carbondioxide,Journal of Chemical and Engineering Data,1985,30(3):247-249.
[11].Schneider G M,Physicochemical principles of extraction with supercriticalgases,Angew Chem(Int Ed Engl),1978,17(10):716-727.
[12].King J W,Fundamentals and applications of supercritical fluid extraction inchromatographic science,Journal of Chromatographic Science,1989,27(7):355-364.
[13].King J W,Applications of capillary supercritical fluid chromatography-supercritical fluid extraction to natural products,Journal of Chromatographic Science,1990,28(1):9-14.
[14].Zosel K,Separation with supercritical gases:practical applications,AngewChem(Int Ed Engl),1978,17(10):702-709.
[15].Camel V,The determination of pesticide residues and metabolites usingsupercritical fluid extraction,TrAC-Trends in Analytical Chemistry,1997,16(6):351-369.
[16].Quan C,Li S,Tian S et al,Supercritical fluid extraction and clean-up oforganochlorine pesticides in ginseng,Journal of Supercritical Fluids,2004,31(2):149-157.
[17].Beyer A,Biziuk M,Applications of sample preparation techniques in theanalysis of pesticides and PCBs in food,Food Chemistry,2008,108(2):669-680.
[18].Zuin V G,Yariwake J H,Bicchi C,Fast supercritical fluid extraction andhigh-resolution gas chromatography with electron-capture and flame photometricdetection for multiresidue screening of organochlorine and organophosphoruspesticides in Brazil's medicinal plants,Journal of Chromatography A,2003,985(1-2):159-166.
[19].Garimella U I,Stearman G K,Wells M J M,Comparison among soil seriesand extraction methods for the analysis of trifluralin,Journal of Agricultural and FoodChemistry,2000,48(12):5874-5880.
[20].Rissato S R,Galhiane M S,Knoll F R N et al,Supercritical fluid extractionfor pesticide multiresidue analysis in honey:Determination by gas chromatographywith electron-capture and mass spectrometry detection,Journal of Chromatography A,2004,1048(2):153-159.
[21].Terfloth G J,Pirkle W H,Lynam K G et al,Broadly applicable polysiloxane-based chiral statio nary phase for high-performance liquid chromatography and supercritical fluid chromatography,Journal of Chromatography A,1995,705(2):185-194.
[22].刘志敏,赵庆,王仁安等.超临界流体色谱法测定银杏叶提取物中的黄酮类化合物[J].分析化学,1999,27(2):214~216.
[23].元英进,刘明言,董岸杰,中药现代化生产关键技术,北京:化学工业出版社,2002.
[24].葛发欢,辉国钧,李菁等,中药现代化与超临界CO2流体技术的应用.In第二届全国超临界流体技术学术及应用研讨会论文集,张镜澄，曾健青,Ed.中国化工学会:北京,1998.
[25].张定安,陆志禹,时钧,超临界流体及超临界萃取（Ⅰ）（Ⅱ）,南京化工学院学报,1992,14(2):79~93.
[26].Mehr C B,Biswal R N,Collins J L e t al,Sup ercritical carbon dioxide extraction of caffeine from guarana,Journal of Supercritical Fluids,1996,9(3):185-191.
[27].Park H S,Choi H K,Lee S J et al,Effect of mass transfer on the removal of caffe ine from green tea by supercritical carbon dioxide,Journal of Supercritical Fluids,2007,42(2):205-211.
[28].Park H S,Lee H J,Shin M H et al,Effects of cosolvents on the decaffeination of green tea by supercritical carbon dioxide,Food Chemistry,2007,105(3):1011-1017.
[29].张冲，李嘉诚，周雪晴等，超临界CO2萃取迷迭香精油及其化学成分分析，精细化工，2008，25（1）：62~67.
[30].巫华美，陈训，何香银，超临界二氧化碳萃取宽叶缬草油的化学成分研究，张镜澄，曾健青，第二届全国超临界流体技术学术及应用研讨会论文集，北京：中国化工学会，1998，115-118.
[31].Guan W,Li S,Yan R et al,Comparison of essential oils of clove buds extracted with supercritical carbon dioxide and other three traditional extraction methods,Food Chemistry,2007,101(4):1558-1564.
[32].韩布兴，超临界流体科学与技术，北京：中国石化出版社，2005，1~4.
[33].樊文乐,武文洁,超临界萃取中夹带剂的概述,食品科技,2005,(2):39~42.
[34].赵东胜，刘桂敏，吴兆亮，超临界流体萃取技术研究与应用进展，天津化工，2007，21（3）：10~12.
[35].李淑芬,中药现代化生产关键技术,北京:2002.
[36].Casas L,Mantell C,Rodriguez M et al,Effect of the addition of cosolvent on the supercritical fluid extraction of bioactive compounds from Helianthus annuus L,Journal of Supercritical Fluids,2007,41(1):43-49.
[37].Macias-Sanchez M D,Serrano C M,Rodriguez M R et al,Extraction of carotenoids and chlorophyll from microalgae with supercritical carbon dioxide and ethanol as cosolvent,Journal of Separation Science,2008,31(8):1352-1362.
[38].Murga R,Ruiz R,Beltran S et al,Extraction of natural complex phenols and tannins from grape seeds by using supercritical mixtures of carbon dioxide and alcohol,Journal of Agricultural and Food Chemistry,2000,48(8):3408-3412.
[39].Ting S S T,Macnaughton S J,Tomasko D L et al,Solubility of naproxen insupercritical carbon dioxide with and without cosolvents,Industrial and Engineering Chemistry Research,1993,32(7):1471-1481.
[40].Zhang Y,Li S f,Wu X w,Pressurized liquid extraction of flavonoids from Houttuynia cordata Thunb,Separation and Purification Technology,2008,58(3):305-310.
[41].Pasquini D,Pimenta M T B,Ferreira L H et al,Sugar cane bagasse pulping using supercritical CO2 associated with co-solvent 1-butanol/water,Journal of Supercritical Fluids,2005,34(2 SPEC.ISS.):125-131.
[42].Johnston K P,Harrison K L,Clarke M J et al,Water-in-carbon dioxide microemulsions: An on envir ment for hydrophiles including proteins,Science,1996,271(5249):624-626.
[43].罗登林,丘泰球,王睿瑞,不同强化方法对超临界CO2萃取人参皂甙的影响,精细化工,2006,23(3):269~272.
[44].Arthur C L,Killam L M,Buch holz K D et al,Automation and optimization of solid-phase microextraction,Analytical Chemistry,1992,64(17):1960-1966.
[45].Potter D W,Pawliszyn J,Detection of substituted benzenes in water at the pg/ml level using solid-phase microextraction and gas chromatography-ion trap mass spectrometry,Journal of Chromatography,1992,625(2):247-255.
[46].Zhang Z,Pawliszyn J,Headspace solid-phase microextraction,Analytical Chemistry,1993,65(14):1843-1852.
[47].刘绍从,吕刚,赵好力宝等,固相微萃取-气相色谱法测定食品添加剂中有害有机挥发杂质,分析试验室,2006,25(3):17~20.
[48].Alzaga R,Bayona J M,Supercritical fluid extraction of tributyltin and its degradation products from seawater via liquid--solid phase extraction,Journal of Chromatography A,1993,655(1):51-56.
[49].Zorita S,Westbom R,Thorneby L et al,Development of a combined solid-phase extraction-supercritical fluid extraction procedure for the determination of polychlorinated biphenyls in wastewater,Analytical Sciences:The International Journal Of The Japan Society For Analytical Chemistry,2006,22(11):1455-1459.
[50].Karasek P,Planeta J,Varad'ova Ostra E et al,Direct continuous supercritical fluid extraction as a novel method of wine analysis.Comparison with conventional indirect extraction and implications for wine variety identification, Journal Of Chromatography.A,2003,1002(1-2):13-23.
[51].Batlle R,Carlsson H,Tollback P et al,Enhanced detection of nitroaromatic explosive vapors combining solid-phase extraction-air sampling,supercritical fluid extraction,and large-volume injection-GC,Analytical Chemistry,2003,75(13):3137-3144.
[52].全灿,超临界流体萃取技术检测/脱除中药材种有机氯农残的研究,[博士论文].天津大学,2005.
[53].Quan C,Li S,Tian S et al,Supercritical fluid extraction and clean-up of organochlorine pesticides in ginseng,The Journal of Supercritical Fluids,2004,31(2):149-157.
[54].Mathiasson L,Turner C,Berg H et al,Development of methods for the determination of vitamins A,E and beta-carotene in processed foods based on supercritical fluid extraction:a collaborative study,Food Additives And Contaminants,2002,19(7):632-646.
[55].Mannila M,Koistinen J,Vartiainen T,Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment,Journal Of Environmental Monitoring:JEM,2002,4(6):1047-1053.
[56].Mannila M, Koistinen J, Vartiainen T, Development of supercritical fluid extraction with a solid-phase trapping for fast estimation of toxic load of polychlorinated dibenzo-p-dioxins-dibenzofurans in sawmill soil, Journal of Chromatography A, 2002, 975 (1): 189-198.
[57].Rodil R, Carro A M, Lorenzo R A et al, Selective extraction of trace levels of polychlorinated and polybrominated contaminants by supercritical fluid-solid-phase microextraction and determination by gas chromatography/mass spectrometry. Application to aquaculture fish feed and cultured marine species, Analytical Chemistry, 2005, 77 (7): 2259-2265.
[58].Salleh S H, Saito Y, Jinno K, An approach to solventless sample preparation procedure for pesticides analysis using solid phase microextraction/supercritical fluid extraction technique, Analytica Chimica Acta, 2000, 418 (1): 69-77.
[59].Salleh S H, Saito Y, Kiso Y et al, Solventless sample preparation procedure for organophosphorus pesticides analysis using solid phase microextraction and on-line supercritical fluid extraction/high performance liquid chromatography technique, Analytica Chimica Acta, 2001, 433 (2): 207-215.
[60].王珊珊,冯流,有机锡化合物的毒性效应及其影响因素,安全与环境学报,2005,5(3):12~15．.
[61].江桂斌,国内外有机锡污染研究现状,卫生研究,2001,30(1):1~3.
[62].Fent K, Looser P W, Bioavailability and bioconcentration of organotin compounds in aquatic organisms, Abstracts of Papers of the American Chemical Society, 1998, 215: U588-U588.
[63].Takahashi S, Tanabe S, Kawaguchi K, Organochlorine and butyltin residues in mesopelagic myctophid fishes from the western North Pacific, Environmental Science & Technology, 2000, 34 (24): 5129-5136.
[64].Ohji M, Arai T, Miyazaki N, Chronic effects of tributyltin on the caprellid amphipod Caprella danilevskii, Marine Pollution Bulletin, 2003, 46 (10): 1263-1272.
[65].Ohji M, Takeuchi I, Takahashi S et al, Differences in the acute toxicities of tributyltin between the Caprellidea and the Gammaridea (Crustacea : Amphipoda), Marine Pollution Bulletin, 2002, 44 (1): 16-24.
[66].El-Menif N T, Lahbib Y, Ramdani M et al, Imposex in the marine neogastropod Hexaplex trunculus from Tunisian coasts: geographical distribution and development intensity, Vie Et Milieu-Life and Environment, 2007, 57 (1-2): 37-42.
[67].Horiguchi T, Li Z, Uno S et al, Contamination of organotin compounds and imposex in molluscs from Vancouver, Canada, Marine Environmental Research, 2004, 57 (1-2): 75-88.
[68].Shintani N, Ogita K, Hashimoto H et al, Recent studies on the trimethyltin actions in central nervous systems, Yakugaku Zasshi-Journal of the Pharmaceutical Society of Japan, 2007, 127 (3): 451-461.
[69].Carfi M, Gennari A, Malerba I et al, In vitro tests to evaluate immunotoxicity: A preliminary study, Toxicology, 2007, 229 (1-2): 11-22.
[70].Hagger J A, Depledge M H, Galloway T S, Toxicity of tributyltin in the marine mollusc Mytilus edulis, Marine Pollution Bulletin, 2005, 51 (8-12): 811-816.
[71].Hagger J A, Fisher A S, Hill S J et al, Genotoxic, cytotoxic and ontogenetic effects of tri-n-butyltin on the marine worm, Platynereis dumerilii (Polychaeta: Nereidae), Aquatic Toxicology, 2002, 57 (4): 243-255.
[72].Heroult J, Zuliani T, Bueno M et al, Analytical advances in butyl-, phenyl-and octyltin speciation analysis in soil by GC-PFPD, Talanta, 2008, 75 (2): 486-493.
[73].周群芳,江桂斌,吴迪靖,猪油样品中有机锡化合物的气相色谱-火焰光度法及气相色谱-质谱联用分析,分析化学,2001,29(04):453~456.
[74].C. Carlier-Pinasseau G L M A, Determination of Butyltin and Phenyltin by GC-FPD Following Ethylation by NaBEt4, Applied Organometallic Chemistry, 1996, 10(7): 505-512.
[75].Pereiro I R, Schmitt V O, Szpunar J et al, Speciation Analysis for Organotin Compounds in Biomaterials after Integrated Dissolution, Extraction, and Derivatization in a Focused Microwave Field, Analytical Chemistry, 1996, 68 (23): 4135-4140.
[76].Campillo N, Aguinaga N, Vinas P et al, Speciation of organotin compounds in waters and marine sediments using purge-and-trap capillary gas chromatography with atomic emission detection, Analytica Chimica Acta, 2004, 525 (2): 273-280.
[77].Moens L, De Smaele T, Dams R et al, Sensitive, Simultaneous Determination of Organomercury, -lead, and -tin Compounds with Headspace Solid Phase Microextraction Capillary Gas Chromatography Combined with Inductively Coupled Plasma Mass Spectrometry, Analytical Chemistry, 1997, 69 (8): 1604-1611.
[78].刘稷燕,江桂斌,固相微萃取技术及其在有机锡和有机汞分析中的应用,分析化学,1999,27(10):1226~1230.
[79].黄长江,雷瓒,董巧香,海产腹足类有机锡化合物的检测方法,海洋学报(中文版),2005,27(04):174~180.
[80].程慧琼,刘稷燕,江桂斌等,顶空固相微萃取技术用于海产品中丁基锡化合物的测定,色谱,2003,21(4):418~420.
[81].Blake E, Raynor M W, Cornell D, Determination of organotin compounds by capillary supercritical fluid chromatography with inductively coupled plasma mass spectrometric detection, Journal of Chromatography A, 1994, 683 (1): 223-231.
[82].Cai Y, Alzaga R, Bayona J M, In situ Derivatization and Supercritical Fluid Extraction for the Simultaneous Determination of Butyltin and Phenyltin Compounds in Sediment, Analytical Chemistry, 1994, 66 (7): 1161-1167.
[83].Liu Y, Lopez-Avila V, Alcaraz M et al, Off-Line Complexation/ Supercritical Fluid Extraction and Gas Chromatography with Atomic Emission Detection for the Determination and Speciation of Organotin Compounds in Soils and Sediments, Analytical Chemistry, 1994, 66 (21): 3788-3796.
[84] .Lopez-Avila V, Liu Y, Beckert W F, Interlaboratory evaluation of an off-line supercritical fluid extraction and gas chromatography with atomic emission detection method for the determination of organotin compounds in soil and sediments, Journal of Chromatography A, 1997, 785 (1-2): 279-288.
[85].Segovia-Garc E, Garc-Alonso J I, Sanz-Medel A, Determination of Butyltin Compounds in Sediments by Means of Hydride Generation/Cold Trapping Gas Chromatography Coupled to Inductively Coupled Plasma Mass Spectrometric Detection, Journal of Mass Spectrometry, 1997, 32 (5): 542-549.
[86].Jiang G B, Liu J Y, Determination of butyltin compounds in aqueous samples by gas chromatography with flame photometric detector and headspace solid-phase microextraction after in-situ hydride derivatization, Analytical Sciences, 2000, 16 (6): 585-588.
[87].Birjandi A P, Bidari A, Rezaei F et al, Speciation of butyl and phenyltin compounds using dispersive liquid-liquid microextraction and gas chromatography-flame photometric detection, Journal of Chromatography A, 2008, 1193 (1-2): 19-25.
[88].Bravo M, Lespes G, De Gregori I et al, Determination of organotin compounds by headspace solid-phase microextraction-gas chromatograph-pulsed flame-photometric detection (HS-SPME-GC-PFPD), Analytical and BioanalyticalChemistry, 2005, 383 (7-8): 1082-1089.
[89].Kaur V, Malik A K, Verma N, Applications of solid phase microextraction for the determination of metallic and organometallic species, Journal of Separation Science, 2006, 29 (3): 333-345.
[90].Chou C C, Lee M R, Determination of organotin compounds in water by headspace solid phase microextraction with gas chromatography-mass spectrometry, Journal of Chromatography A, 2005, 1064 (1): 1-8.
[91].Centineo G, Rodriguez-Gonzalez P, Gonzalez E B et al, Isotope dilution GC-MS routine method for the determination of butyltin compounds in water, Analytical and Bioanalytical Chemistry, 2006, 384 (4): 908-914.
[92].Almeida C, Serodio P, Florencio M H et al, New strategies to screen for endocrine-disrupting chemicals in the Portuguese marine environment utilizing large volume injection-capillary gas chromatography-mass spectrometry combined with retention time locking libraries (LVI-GC-MS-RTL), Analytical and Bioanalytical Chemistry, 2007, 387 (7): 2569-2583.
[93].中华人民共和国药典委员会,中华人民共和国药典[M],北京:化学工业出版社,2005.
[94].张雅君,梁忠岩,赵伟等,党参水溶性多糖的分离、纯化及诸成分析,中国药学杂志,2005,40(14):1107~110
[95].韩凤梅,程玲丽,陈勇,党参多糖的分离和纯化研究,中国药学杂志,2005,40(18):1381-1383.
[96].叶冠,李晨,黄成钢等,党参果聚糖的化学结构,中国药学杂志,2005,30(17):1380~1340.
[97].贺庆,朱恩圆,王峥涛等,党参化学成分的研究,中国药学杂志,2006,41(1):10~12．
[98].陈敏,李晓瑾,姜林,新疆党参挥发油成分的研究,中草药,2000,31(4):254.
[99].谢君,张义正,顾永祚,党参挥发油及脂溶性化学成分的研究,中国药学杂志,2000,35(9):583-586．
[100].杨荣平,王宾豪,励娜,GC-MS法分析大宁党参挥发油化学成分,中国实用医药,2007,2(25):33~34.
[101].朱恩圆,贺庆,王峥涛等,党参化学成分研究,中国药科大学学报,2001,32(2):94~95.
[102].阎永红,党参地上部分的基础研究,江西中医学院学报,2002,14(1):30.
[103].李艳,孙萍,刘霞等,新疆党参多糖的提取、含量分析及免疫功能的初步研究,中成药,2005,27(7):839-840.
[104].杨光,李发胜,刘辉,党参多糖对小鼠免疫功能的影响,中药药理与临床,2005,21(4):39~40.
[105].徐爱霞,张振明,葛斌等,党参多糖抗衰老作用机制的实验研究,中国现代应用药学杂志,2006,23(8):729~731.
[106].Ng T B, Liu F, Wang H X, The antioxidant effects of aqueous and organic extracts of Panax quinquefolium, Panax notoginseng, Codonopsis pilosula, Pseudostellaria heterophylla and Glehnia littoralis, Journal of Ethnopharmacology, 2004, 93 (2-3): 285-288.
[107] .Wang Z T, Du Q, Xu G J et al, Investigations on the protective action of Condonopsis pilosula (Dangshen) extract on experimentally-induced gastric ulcer inrats, General Pharmacology, 1997, 28 (3): 469-473.
[108].郑天珍,李伟,张英福等,党参对动物小肠推进运动的实验研究,甘肃中医学院学报,2001,18(1):19~20.
[109].Sui F, Wang R, Wang J et al, Effects of Dangshen root extract serum on intracellular free calcium in gastric parietal cells of dissociated rats, Zhong yao cai = Zhongyaocai = Journal of Chinese medicinal materials., 2005, 28 (10): 900-903.
[110].崔兴日,南极星,吕慧子等,党参提取物对急性肝损伤小鼠肝脏的保护作用,延边大学医学学报,2004,27(4):262~264.
[111].张天红,张馨,耿爱萍,潞党参药理实验研究,时珍国医国药,2001,12(6):488~489.
[112].方明,石云峰,焦炬焰,中药党参抗应激作用的研究,辽宁药物与临床,2002,5(1):32~33.
[113].闫彦芳,张壮,韦颖等,党参总皂苷抗缺氧缺糖再給氧诱导大鼠星形胶质细胞损伤的作用,北京中医药大学学报,2006,29(12):826~830.
[114].赵晓华,刘养清,裴晓丽,党参中党参炔苷的HPLC分析,山西中医学院学报2006,07(5):49~50.
[115].Johnston K P, Peck D G, Kim S, Modeling supercritical mixtures: How predictive is it?, Industrial and Engineering Chemistry Research, 1989, 28 (8): 1115-1125.
[116].朱自强,超临界流体萃取中的相平衡进展,高校化学工程学报,1994,8(1):1~10.
[117].Chrastil J, Solubility of solids and liquids in supercritical gases, Journal of Physical Chemistry, 1982, 86 (15): 3016-3021.
[118].Del Valle J M, Aguilera J M, An improved equation for predicting the solubility of vegetable oils in supercritical CO2, Industrial and Engineering Chemistry Research, 1988,27(8): 1551-1553.
[119].Gordillo M D, Blanco M A, Molero A et al, Solubility of the antibiotic Penicillin G in supercritical carbon dioxide, Journal of Supercritical Fluids, 1999, 15 (3): 183-190.
[120] .Mills G A, Walker V, Mughal H, Headspace solid-phase microextraction with 1-pyrenyldiazomethane in-fibre derivatisation for analysis of faecal short-chain fatty acids, Journal of Chromatography B: Biomedical Sciences and Applications, 1999,730(1): 113-122.
[121].Cai Y, Abalos M, Bayona J M, Effects of complexing agents and acid modifiers on the supercritical fluid extraction of native phenyl- and butyl-tins from sediment, Applied Organometallic Chemistry, 1998, 12 (8-9): 577-584.
[122] .Liu. Y, Lopez-Avila. V, Alcaraz. M et al, Determination of organotin compounds in environmental samples by supercritical fluid extraction and gas chromatography with atomic emission detection, Journal of High Resolution Chromatography, 1993, 16 (2): 106-112.
[123].Bayona J M, Cai Y, The role of supercritical fluid extraction and chromatography in organotin speciation studies, TrAC Trends in Analytical Chemistry, 1994, 13 (8): 327-332.
[124].Tang C H, Wang W H, Optimization of an analytical method for determining organotin compounds in fish tissue by base-hydrolysis pretreatment and simultaneous ethylation-extraction procedures, Analytica Chimica Acta, 2007, 581 (2): 370-376.
[125].Chau Y K, Yang F, Brown M, Supercritical fluid extraction of butyltin compounds from sediment, Analytica Chimica Acta, 1995, 304 (1): 85-89.
[126].Wasik A, Ciesielski T, Determination of organotin compounds in biological samples using accelerated solvent extraction, sodium tetraethylborate ethylation, and multicapillary gas chromatography-flame photometric detection, Analytical and Bioanalytical Chemistry, 2004, 378 (5): 1357-1363.
[127].Kurnik R T, Holla S J, Reid R C, Solubility of solids in supercritical carbon dioxide and ethylene, Journal of Chemical and Engineering Data, 1981, 26 (1): 47-51.
[128].周海涛,党参活脑有效物质基础研究,[硕士论文],中医药大学,2004.
[129].贺英,朱恩园,王峥涛等,党参中党参炔苷HPLC分析,中国药学杂志,2005,1(3):56.~57
[130].王雷,超临界流体-固体系统相平衡的模型化研究,[硕士学位论文],贵州大学,2005.