WO2016026286A1 - 用于农产品农药残留检测程序的快速萃取套件及从农产样品取得检液原液的方法 - Google Patents

用于农产品农药残留检测程序的快速萃取套件及从农产样品取得检液原液的方法 Download PDF

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WO2016026286A1
WO2016026286A1 PCT/CN2015/074011 CN2015074011W WO2016026286A1 WO 2016026286 A1 WO2016026286 A1 WO 2016026286A1 CN 2015074011 W CN2015074011 W CN 2015074011W WO 2016026286 A1 WO2016026286 A1 WO 2016026286A1
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sample
powder layer
mixed powder
solution
column
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PCT/CN2015/074011
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English (en)
French (fr)
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林韶凯
庄玮臻
陈柔文
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行政院农业委员会农业药物毒物试验所
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Priority claimed from CN201410409684.0A external-priority patent/CN105259276B/zh
Application filed by 行政院农业委员会农业药物毒物试验所 filed Critical 行政院农业委员会农业药物毒物试验所
Priority to JP2016571305A priority Critical patent/JP6377182B2/ja
Priority to EP15833958.0A priority patent/EP3184157B1/en
Publication of WO2016026286A1 publication Critical patent/WO2016026286A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/60—Construction of the column
    • G01N30/6052—Construction of the column body
    • G01N30/6069—Construction of the column body with compartments or bed substructure
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Definitions

  • the invention relates to a rapid extraction kit for the pesticide residue detection procedure for agricultural products.
  • pesticide residue testing standards are established in countries around the world to establish acceptable pesticide residues.
  • the existing test method is to first sample the test object to obtain the sample for inspection, and then use the QuEChERS method.
  • test liquid is processed into a test liquid capable of performing instrument detection, and then the liquid is further detected by a liquid chromatograph/tandem mass spectrometer (LC/MS-MS) or a gas chromatograph/tandem mass spectrometer (GC/MS-MS). Finally, data processing is performed according to the aforementioned instrument detection results to obtain a pesticide residue test result.
  • LC/MS-MS liquid chromatograph/tandem mass spectrometer
  • GC/MS-MS gas chromatograph/tandem mass spectrometer
  • the sample pretreatment step takes a lot of time to obtain the required liquid sample from the sample, because the QuEChERS method needs to perform the following steps:
  • the sample particles are refined using a Blender to increase the sample contact area
  • the homogenized sample is added with an extraction solvent such as acetonitrile and shaken vigorously for a period of time to form an extract.
  • the ratio of sample to extraction solvent is 1:1, for example, 10 g of sample needs to be added with 10 ml of acetonitrile;
  • the component of the buffer salt mixture comprises 4 grams of anhydrous magnesium sulfate, 1 gram of each of sodium chloride and sodium citrate, and 0.5 grams of disodium hydrogen citrate;
  • the extract having been added to the buffer salt mixture is vigorously shaken for a period of time by a high-speed tissue grinding and oscillating homogenizer, and then centrifuged by a centrifuge to stratify the extract;
  • the adsorbent component to be added is 150 mg of PSA (primary secondary amine, N-propylethylenediamine) and 900 mg of anhydrous magnesium sulfate; if the sample is tea, it is required to be added.
  • the adsorbent component is 450 mg of PSA and 900 mg of anhydrous magnesium sulfate; if the sample contains carotenoids, the adsorbent component to be added is 150 mg of PSA, 885 mg of anhydrous magnesium sulfate and 15 mg of graphite.
  • GCB Graphitic Carbon Black
  • the adsorbent component to be added is 150 mg of PSA, 855 mg of anhydrous magnesium sulfate, and 45 mg of GCB.
  • the supernatant liquid to which the adsorbent has been added is vigorously shaken for a while using a high-speed tissue-grinding and oscillating homogenizer, and then centrifuged in a centrifuge, and then the centrate is obtained as a liquid sample.
  • test liquid stock still needs to undergo some processing steps (for example, a step of blowing to a micro-dry, a step of adding methanol or acetone or n-hexane, a step of adding formic acid, and a step of filtering with a filter) to become available.
  • processing steps for example, a step of blowing to a micro-dry, a step of adding methanol or acetone or n-hexane, a step of adding formic acid, and a step of filtering with a filter.
  • the solid phase extraction column in the patent case is filled with two layers of different materials (the upper layer is a mixed filler composed of aminated silica gel NH 2 and amidated polyethylene divinylbenzene, and the lower layer is a graphitized carbon filler. ), but it still takes a lot of time to process the sample and the solid phase extraction column to take the liquid sample from the sample using the solid phase extraction column.
  • the upper layer is a mixed filler composed of aminated silica gel NH 2 and amidated polyethylene divinylbenzene
  • the lower layer is a graphitized carbon filler.
  • the CN202631493 patent discloses a solid phase extraction cartridge filled with three layers of PSA, HBL and GCB. Since the three layers of materials are all adsorbents, if the solid phase extraction cartridge is used in the above QuEChERS method, After the sample is added to the extraction solvent, it is still necessary to add a buffer salt mixture, shaking, centrifugation, etc., before the liquid phase extraction column can be used to obtain the liquid sample from the sample.
  • a purification column filled with a single layer of adsorbent filler is disclosed, which is N-propyl ethylenediamine and anhydrous magnesium sulfate.
  • the above-mentioned QuEChERS method requires too much time to obtain a sample liquid sample from the sample, resulting in a problem that the test result cannot be obtained quickly, and this problem is clearly difficult to solve in the prior art various solid phase extraction columns.
  • the present invention provides a pesticide residue for agricultural products.
  • the rapid extraction kit for the agricultural product pesticide residue detection program of the present invention comprises a tubular string, a first mixed powder layer and a second mixed powder layer; the tubular string has an outlet at the bottom thereof and a top portion thereof
  • the input port and the input port are used for inputting the sample solution, and the sample solution is a mixed solution of the agricultural product sample after the homogenization, and the mixed solution of the extracting agent is oscillated;
  • the first mixed powder layer is in the form of powder and is filled in the column, and can Absorbing most of the moisture in the sample solution and buffering the pH of the sample solution as the sample solution passes;
  • the second mixed powder layer is in powder form and filled in the column and below the first mixed powder layer And above the output port, and can absorb the residual moisture in the sample solution and the impurities that may interfere with the detection result of the instrument when the sample solution passes.
  • the first mixed powder layer has a density in the column of 0.7 to 1.3 g/cm 3 .
  • the porosity of the first mixed powder layer in the column is 35% to 70%.
  • the first mixed powder layer has a weight of 0.4 g to 5 g, and the second mixture The weight of the powder layer is from 0.2 g to 1.6 g and less than the weight of the first mixed powder layer.
  • the first mixed powder layer has an area of 0.6 to 7.1 cm 2 in the column and a height of 1 to 8 cm, and the area of the second mixed powder layer in the column is 0.6 to 7.1 cm 2 , height is 0.23 to 3 cm and lower than the height of the first mixed powder layer.
  • the composition of the first mixed powder layer comprises 0.2 to 2 g of anhydrous magnesium sulfate powder, 0.1 to 1 g of sodium chloride powder, 0.1 to 1 g of sodium citrate powder, and 0.5 to 1 g. Disodium hydrogen citrate powder.
  • the composition of the second mixed powder layer comprises 0.01 to 0.5 g of PSA powder and 0.2 to 1 g of anhydrous magnesium sulfate powder.
  • the component of the second mixed powder layer contains 0.01 to 0.5 g of PSA powder, 0.2 to 1 g of anhydrous magnesium sulfate powder, and 0.001 to 0.1 g of graphitized carbon black powder.
  • the method for obtaining the liquid sample from the agricultural sample using the rapid extraction kit comprises: homogenizing the agricultural sample to obtain the broken sample of the agricultural product; adding the extraction solvent to the agricultural sample and oscillating To obtain a sample solution in which 1 to 10 mL of extraction solvent per 1 ⁇ 0.03 g of the agricultural sample is added; the sample solution is added to the column of the rapid extraction kit described above; and the column is driven The sample solution sequentially flows through the first mixed powder layer and the second mixed powder layer in the column and is outputted from the output port of the column into a liquid sample.
  • the flow rate of the sample solution is controlled to be 0.01 to 0.2 mL/second.
  • the extraction solvent is an acetonitrile solution or an acetic acid-containing acetonitrile solution.
  • the rapid extraction kit of the present invention and the method for obtaining the liquid sample from the agricultural sample using the rapid extraction kit can greatly reduce the liquid sample obtained from the sample. Time, and therefore the speed of the entire pesticide residue inspection program, to solve the problem that the prior art cannot quickly obtain the test results.
  • Figure 1 is a schematic view showing the structure of a preferred embodiment of the rapid extraction kit of the present invention.
  • Figure 2 is a schematic illustration of the operation of a preferred embodiment of the present invention.
  • Figure 3 is a schematic view showing the structure of another preferred embodiment of the rapid extraction kit of the present invention.
  • Figure 4 is a schematic illustration of the operation of another preferred embodiment of the present invention.
  • the rapid extraction kit 1 in this embodiment includes a column 10, and a first mixed powder layer 12 and a second mixture filled in the column 10.
  • the present invention preferably further includes two filter mats 11, wherein one filter mat 11 is fixed to the top surface of the first mixed powder layer 12, and the other filter mat 11 is fixed to the bottom surface of the second mixed powder layer 13.
  • the top surface of the second mixed powder layer 13 is in direct contact with the first mixed powder layer 12, but a layer of filter mat (not shown) may be further added at the junction of the two.
  • the above rapid extraction kit 1 is used for the pesticide residue detection procedure in agricultural products.
  • this procedure there is included a method of obtaining a stock solution from an agricultural sample using the rapid extraction kit 1 of the present invention, which comprises the following steps a to d.
  • the agricultural product sample taken is homogenized by using a stirring homogenizer to process the agricultural product sample into the agricultural product sample.
  • Agricultural samples were taken from fruits and vegetables, cereals, dried beans, teas, spice plants and other herbs for use as samples for pesticide residue testing.
  • the extraction solvent is added to the agricultural sample fines and shaken vigorously to obtain a sample solution S.
  • 1 mL to 10 mL of the extraction solvent is added per 1 ⁇ 0.03 g of the agricultural sample, and the extraction solvent is acetonitrile or an acid-containing acetonitrile solution, and the agricultural product sample per 1 ⁇ 0.03 g is preferably added 5 mL.
  • the aforementioned extraction solvent, and the extraction solvent is preferably an acetonitrile solution containing 1% acetic acid.
  • the sample solution S in the column 10 is driven to sequentially flow through the first mixed powder layer 12 and the second mixed powder layer 13 in the column 10 to be output from the output port 101 of the column 10 to be a liquid sample.
  • One of the preferred ways of driving the sample solution S to flow through the column 10 is to directly drive the sample solution S through the first mixed powder layer 12 and the second mixture in the column 10 by means of the piston rod 2 in direct pressure. Powder layer 13.
  • the pumping method may also be used to drive the sample solution S to sequentially flow through the first mixed powder layer 12 and the second mixed powder layer 13, and the pumping method is to use an extracting device including a vacuum pump (not shown).
  • the output port 101 of the column 10 is connected, and the vacuum solution is used to draw the sample solution S in the column 10 out to the output port 101.
  • the flow rate of the sample solution S is preferably controlled at 0.01 to 0.2 mL/sec, more preferably at 0.05. mL/sec.
  • the filter mat 11 should be selected from filter mats that do not affect the aforementioned flow rate.
  • the mixed powder in the first mixed powder layer 12 can adsorb most of the moisture in the sample solution S while the sample solution S passes, and provides a buffering effect on the pH of the sample solution S, the sample solution S flows through the first After the powder layer 12 is mixed, most of its moisture is left in the first mixed powder layer 12, and its pH is in the range of about 4 to 8 without being too acidic or too alkali.
  • the mixed powder in the second mixed powder layer 13 can adsorb the residual moisture in the sample solution S and impurities which may interfere with the detection result of the instrument, such as organic acids, pigments and the like, when the sample solution S passes, the sample is After the solution S continues to flow through the second mixed powder layer 13, it becomes a liquid-test stock solution S1 which is free from impurities or impurities. Among them, the test liquid solution S1 is collected by the test tube 3.
  • the liquid test solution S1 can be directly detected by liquid chromatography tandem mass spectrometry or gas chromatography tandem mass spectrometry to determine whether the pesticide residue on the sample meets the standard.
  • the liquid test solution S1 may also be subjected to a step of blowing to a microdry, a step of adding methanol or acetone or n-hexane, a step of adding formic acid, and a step of filtering with a filter, followed by a liquid chromatography tandem mass spectrometer or Gas chromatography tandem mass spectrometry was used for detection.
  • the total volume of the powder used in the first mixed powder layer 12 is 0.87 cm 3 and the total weight is 2 g. Since the first mixed powder layer 12 is not compacted and is in a loose or bulky state during filling in the inner diameter of the selected column 10, the first mixed powder layer 12 is in the tube. area within the column 10 is about 1.13cm 2, a height of about 2.05cm, so that the total volume of the first mixed powder layer 12 in the column 10 is about 2.317cm 3, and a density of about 0.863g / cm 3, and The total porosity is approximately 50% to 62%.
  • the sample solution S flowing through the layer is less prone to blockage or excessive flow rate, so that the flow rate of the sample solution S flowing through the layer is more easily controlled within the expected range, and most of the moisture in the sample solution S is made. Can be removed at this layer.
  • the weight of the first mixed powder layer 12 is preferably 0.4 to 5 g, which is filled in
  • the density in the column 10 is preferably 0.7 to 1.3 g/cm 3 .
  • the area of the first mixed powder layer 12 when filled in the column 10 is preferably 0.6 to 7.1 cm 2 and the height is preferably 1 to 8 cm.
  • the total porosity of the first mixed powder layer 12 when packed in the column 10 is preferably from 35% to 70%.
  • the above total porosity (the total volume of the first mixed powder layer 12 in the column 10 - the actual volume of the powder of the first mixed powder layer 12) ⁇ (the first mixed powder layer 12 is in the column 10) Total volume) ⁇ 100%.
  • the powder component used in the first mixed powder layer 12 contains anhydrous magnesium sulfate, chlorinated Sodium, sodium citrate and disodium hydrogen citrate.
  • the first mixed powder layer 12 is preferably composed of 1.23 g of anhydrous magnesium sulfate powder, 0.31 g of sodium chloride powder, 0.31 g of sodium citrate powder and 0.15 g of disodium hydrogen citrate powder.
  • 0.2 to 2 g of anhydrous magnesium sulfate powder, 0.1 to 1 g of sodium chloride powder, 0.1 to 1 g of sodium citrate powder, and 0.05 to 1 g of disodium hydrogen citrate powder are preferred. .
  • the weight of the second mixed powder layer 13 is preferably 0.7 g and less than the first mixed powder layer 12, but 0.2 to 1.6 g is also the preferred weight of the second mixed powder layer 13.
  • the area of the second mixed powder layer 13 in the column 10 is 1.13 cm 2 and the height is 0.8 cm, but the area is 0.6 to 7.1 cm 2 and the height is 0.23 to 3 cm.
  • the height of the second mixed powder layer 13 in the column 10 is lower than that of the first mixed powder layer 12.
  • the powder component used in the second mixed powder layer 13 contains PSA (primary secondary amine) powder and anhydrous magnesium sulfate powder, and further, the second mixed powder layer 13 It is composed of 0.1 g of PSA powder and 0.6 g of anhydrous magnesium sulfate powder, but it is not limited thereto, and for example, 0.01 to 0.5 g of PSA powder and 0.2 to 1 g of anhydrous magnesium sulfate powder are preferred.
  • the powder component used in the second mixed powder layer 13 contains PSA powder, anhydrous magnesium sulfate powder and graphitized carbon black (GCB) powder, and further,
  • the mixed powder layer 13 is composed of 0.1 g of PSA powder, 0.5925 g of anhydrous magnesium sulfate powder and 0.0075 g of GCB powder, but is not limited thereto, for example, 0.01 to 0.5 g of PSA powder, 0.2 to 1 g.
  • Anhydrous magnesium sulfate powder and 0.001 to 0.1 g of GCB powder are preferred.
  • the weight of the GCB powder and the anhydrous magnesium sulfate powder is preferably about 1/79. Further, the anhydrous magnesium sulfate powder in the second mixed powder layer 13 is less than the anhydrous magnesium sulfate powder in the first mixed powder layer 12.
  • the column 10a of the rapid extraction kit 1a in this embodiment is slightly different in shape from the above-mentioned column 1, but also has an input port 100a and an output.
  • the above-described two spacers 11 and the first mixed powder layer 12 and the second mixed powder layer 13 are also provided in the port 101a.
  • the difference is that the sample solution S described above is added to the barrel 40 of the syringe 4, and the bottom end ejection port of the barrel 40 is connected to the input port 100a.
  • the sample solution S is directly pressurized by the piston rod 41 of the syringe 4
  • the sample solution S is injected into the column 10a and sequentially flows through the first mixed powder layer 12 and the second mixed powder layer 13 to become the above.
  • the test liquid solution S1 is collected by the above test tube 3.
  • the sample solution S composed of the sample powder and the extraction solvent can be directly extracted by using the rapid extraction kit 1 or 1a of the present invention to obtain a liquid sample.
  • the rapid extraction kit 1 or 1a of the present invention since the use of the rapid extraction kit 1 or 1a of the present invention to obtain a liquid sample stock solution is significantly less than two oscillation treatments and two centrifugation treatments, therefore, by using the rapid extraction kit 1 or 1a of the present invention, The time for obtaining the liquid sample from the sample can be greatly reduced, and thus the speed of the entire pesticide residue inspection program can be improved, and the problem that the prior art cannot quickly obtain the test result can be solved.
  • the dilution factor of the diluted sample of the QuEChERS method is 1, and the dilution factor of the diluted sample of the method of the present invention is 5, so the unit sample content (about 0.2 g/mL) of the liquid sample obtained by the method of the present invention is low.
  • the unit sample content (about 1 g/mL) of the test liquid stock obtained by the QuEChERS method makes the matrix effect of the test liquid stock obtained by the method of the present invention lower than that of the test liquid stock obtained by the QuEChERS method, which means The detection result obtained by the instrumental analysis of the liquid sample obtained by the method of the present invention is significantly disturbed by the matrix effect to a degree lower than that of the liquid solution obtained by the QuEChERS method.

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Abstract

一种用于农产品农药残留检测程序的快速萃取套件及从农产样品取得检液原液的方法。所述快速萃取套件包括管柱、第一混合粉体层及第二混合粉体层。第一混合粉体层能吸附样品溶液水分及对样品溶液的pH值提供缓冲作用，第二混合粉体层能吸附样品溶液中的剩余水分及杂质。所述方法包括先取得农产样品碎末，将萃取溶剂加入农产样品碎末得到样品溶液，再将样品溶液加入快速萃取套件的管柱中，最后驱使管柱内的样品溶液流经管柱内并从管柱中输出成为检液原液。通过上述快速萃取套件及其使用方法，解决现有技术无法快速取得农药残留检验结果的问题。

Description

用于农产品农药残留检测程序的快速萃取套件及从农产样品取得检液原液的方法 技术领域
本发明与用于农产品农药残留检测程序的快速萃取套件有关。
背景技术
为了清除害虫以提高农产品产量，对农作物施予农药至今仍旧普遍。基于食品安全考虑，世界各国均订有农药残留检验标准来确立可接受的最高农药残留剂量。针对蔬果类、谷类、干豆类、茶类、香辛植物及其他草本植物的农药残留检验，现有的检验方法是先对受检验对象进行采样，以取得供检验的样品，然后，利用QuEChERS方法(Quick，Easy，Cheap，Effective，Rugged，Safe)进行样品前处理，以取得经除水、净化后的检液原液，接着，将该检液原液处理成可进行仪器检测的检液，然后，再利用液相色谱串联质谱仪(liquid chromatograph/tandem mass spectrometer，LC/MS-MS)或气相色谱串联质谱仪(gas chromatograph/tandem mass spectrometer，GC/MS-MS)对该检液进行仪器检测，最后根据前述仪器检测结果进行数据处理，以得出农药残留检验结果。
在上述的农药残留检验方法中，样品前处理步骤需花费很多时间，才能从样品中取得所需要检液原液，因为，QuEChERS方法需执行以下步骤：
利用搅拌均质器(Blender)将样品颗粒细化，以增加样品接触面积；
称取适量的样品，例如10克；
对均质后的样品加入萃取溶剂，例如乙腈，并剧烈振荡一段时间，以形成萃取液。样品与萃取溶剂的比例是1∶1，例如10克的样品需加入10毫升的乙腈；
对萃取液加入适量的缓冲盐混合剂，例如6.5克。缓冲盐混合剂的成分包含4克的无水硫酸镁、各1克的氯化钠与柠檬酸钠、及0.5克的柠檬酸氢二钠；
利用高速组织研磨振荡均质机将已加入缓冲盐混合剂的萃取液剧烈振荡一段时间之后，再以离心机(Centrifuge)进行离心处理，以使前述萃取液分层；
从经过上述处理的萃取液中取出适量的上层液，例如6mL；及
视样品种类不同，在所取出的上层液加入不同的吸附剂。例如，若样品为一 股蔬果及谷类，则所需加入的吸附剂成分为150毫克的PSA(primary secondary amine，N-丙基乙二胺)及900毫克的无水硫酸镁；若样品为茶叶，则所需加入的吸附剂成分为450毫克的PSA及900毫克的无水硫酸镁；若样品含类胡萝卜素，则所需加入的吸附剂成分为150毫克的PSA、885毫克的无水硫酸镁与15毫克的石墨化碳黑(Graphitized Carbon Black，GCB)。此外，若样品的叶绿素含量高，则所需加入的吸附剂成分为150毫克的PSA、855毫克的无水硫酸镁与45毫克的GCB。
接着，利用高速组织研磨振荡均质机将已加入上述吸附剂的上层液剧烈振荡一段时间之后，再以离心机进行离心处理，然后取得离心液作为检液原液。
该检液原液尚需经过一些处理步骤(例如依序经过吹至微干的步骤、加入甲醇或丙酮或正己烷的步骤、加入甲酸的步骤及以滤膜过滤的步骤)，才能变成可进行仪器检测的上述检液。
利用该QuEChERS方法大约需花费2个小时，才能从样品中取得所需要的检液原液，这显然会拖慢整个农药残留检验程序进行，导致无法快速取得检验结果的问题。因此，如何提供一种更简易、更快速的方式从样品中取得所需要的检液原液，以解前述问题，显为当务之急。
在CN103111091专利案中，虽然提出利用一种固相萃取柱从样品中取得检液原液，然而，该样品必需先经过振荡、两次离心处理及水浴旋转蒸发处理，以取得浓缩液，且需先添加无水硫酸钠于该固相萃取柱，并使用乙腈-甲苯来清洗该固相萃取柱，然后，才能将该浓缩液加入经前述处理之后的固相萃取柱中，以萃取得到检液原液。由此可见，该专利案中的固相萃取柱中虽然充填有两层不同材料(上层为由氨基化硅胶NH2与酰胺化聚乙烯二乙烯苯所构成的混合填料，下层为石墨化碳填料)，但仍需要花费很多时间对样品及该固相萃取柱进行一些处理，才能利用该固相萃取柱从样品中取得检液原液。
CN202631493专利案揭露一种固相萃取小柱，其中充填有PSA、HBL及GCB三层，由于此三层材料都是吸附剂，因此，若将该固相萃取小柱运用于上述QuEChERS方法中，则样本在加入萃取溶剂之后，仍需要进行添加缓冲盐混合剂、振荡及离心等处理，然后才能使用该固相萃取小柱从该样本中取得检液原液。
类似前段所述的技术也见于CN103055540专利案。在此专利案中揭露一种内部充填有单层吸附填料的净化柱，该吸附填料为N-丙基乙二胺与无水硫酸镁 的混合填料，或多壁碳纳米管与无水硫酸镁的混合填料，或PSA、无水硫酸镁、多壁碳纳米管与石墨化碳黑的混合填料，同样地，这些混合填料都是作为吸附剂，因此，跟CN202631493专利案一样，即使运用于上述QuEChERS方法中，仍需要花费许多时间先进行添加缓冲盐混合剂、振荡及离心等处理之后，才能使用该净化柱从样本中取得检液原液。
此外，在US6541273专利案虽揭露一种内部充填有多层吸附剂的固相萃取柱，然而，使用该固相萃取柱从样品中取得检液原液之前，仍必需花费许多时间对样品进行离心处理。
从上述说明可知，关于上述QuEChERS方法需要花费太多时间才能从样品中取得检液原液样品，导致无法快速取得检验结果的问题，而此问题现有技术中各种固相萃取柱显然难以解决。
发明内容
为解决现有技术中各种固相萃取柱以及上述QuEChERS方法需要花费太多时间才能从样品中取得检液原液样品，导致无法快速取得检验结果的问题，本发明提供一种用于农产品农药残留检测程序的快速萃取套件及使用该快速萃取套件从农产样品取得检液原液的方法。
更详细而言，本发明用于农产品农药残留检测程序的快速萃取套件包括管柱、第一混合粉体层及第二混合粉体层；管柱具有位于其底部的输出口及位于其顶部的输入口，输入口供输入样品溶液，样品溶液为均质后的农产样品碎末加入萃取剂经振荡处理后的混合溶液；第一混合粉体层为粉末形态且充填于管柱内，并能在样品溶液经过时吸附样品溶液中大部分的水分及对样品溶液的pH值提供缓冲作用；第二混合粉体层为粉末形态且充填于管柱内，并位于第一混合粉体层的下方及输出口的上方，及能在样品溶液经过时吸附样品溶液中的剩余水分及会干扰仪器检测结果的杂质。
较佳地，在快速萃取套件中，第一混合粉体层位于管柱中的密度为0.7～1.3g/cm3。
较佳地，在快速萃取套件中，第一混合粉体层位于管柱中的孔隙率为35％～70％。
较佳地，在快速萃取套件中，第一混合粉体层的重量为0.4g～5g，第二混 合粉体层的重量为0.2g～1.6g且少于第一混合粉体层的重量。
较佳地，在快速萃取套件中，第一混合粉体层位于管柱中的面积为0.6～7.1cm2，高度为1～8cm，第二混合粉体层位于管柱中的面积为0.6～7.1cm2，高度为0.23～3cm且低于第一混合粉体层的高度。
较佳地，在快速萃取套件中，第一混合粉体层的成分包含0.2～2g的无水硫酸镁粉末、0.1～1g的氯化钠粉末、0.1～1g的柠檬酸钠粉末与0.5～1g的柠檬酸氢二钠粉末。
较佳地，在快速萃取套件中，第二混合粉体层的成分包含0.01～0.5g的PSA粉末与0.2～1g的无水硫酸镁粉末。
较佳地，在快速萃取套件中，第二混合粉体层的成分包含0.01～0.5g的PSA粉末、0.2～1g的无水硫酸镁粉末与0.001～0.1g的石墨化碳黑粉末。
再者，使用快速萃取套件从农产样品取得检液原液的方法包括：对农产样品进行均质处理，以得到成农产样品碎末；将萃取溶剂加入农产样品碎末并进行振荡处理，以得到样品溶液，其中，每1±0.03g的农产样品碎末需添加1～10mL的萃取溶剂；将样品溶液加入上文所述的快速萃取套件的管柱中；及驱使管柱内的样品溶液依序流经管柱内的第一混合粉体层与第二混合粉体层而从管柱的输出口输出成为检液原液。
较佳地，在所述方法中，样品溶液的流速控制在0.01～0.2mL/秒。
较佳地，在所述方法中，萃取溶剂为乙腈溶液或含醋酸的乙腈溶液。
相较于现有技术中各种固相萃取柱以及前述QuEChERS方法，本发明的快速萃取套件及使用该快速萃取套件从农产样品取得检液原液的方法可以大幅缩减从样品取得检液原液的时间，并因此提高整个农药残留检验程序的速度，解决现有技术无法快速取得检验结果的问题。
附图说明
图1是本发明的快速萃取套件的一个较佳实施例的结构示意图。
图2是本发明的较佳实施例的动作示意图。
图3是本发明的快速萃取套件的另一较佳实施例的结构示意图。
图4是本发明另一较佳实施例的动作示意图。
具体实施方式
本发明将可由以下的实施例的说明而得到充分了解，使得本领域技术人员可据以完成，然而本发明的实施方式并不限制于此。请参阅图1，其显示本发明的一个较佳实施例，在此实施例中的快速萃取套件1包括管柱10、及充填于管柱10内的第一混合粉体层12及第二混合粉体层13，其中，管柱10较佳为圆管，其具有位于底部的输出口101，及位于顶部的输入口100，第一混合粉体层12位于输入口100的下方，第二混合粉体层13位于第一混合粉体层12的下方及输出口101的上方。此外，本发明较佳还包括两滤垫11，其中一只滤垫11固定在第一混合粉体层12的顶面，另一只滤垫11固定在第二混合粉体层13的底面。第二混合粉体层13的顶面是直接接触第一混合粉体层12，但也可以在此二者的交界处再加入一层滤垫(图中未示出)。
将上述快速萃取套件1用于农产品中农药残留检测程序。在此程序中包括使用本发明快速萃取套件1从农产样品取得检液原液的方法，该方法包括以下a～d步骤。
a)先利用搅拌均质器对所采取到的农产样品进行均质处理，以将农产样品处理成农产样品碎末。农产样品是从蔬果类、谷类、干豆类、茶类、香辛植物及其他草本植物上采取到的，以供作为进行农药残留检测的待测样品。
b)接着，将萃取溶剂加入农产样品碎末并进行剧烈的振荡，以得到样品溶液S。其中，每1±0.03克的农产样品碎末需添加1mL～10mL的萃取溶剂，萃取溶剂选用乙腈或含酸的乙腈溶液，且每1±0.03克的农产样品碎末较佳是添加5mL的前述萃取溶剂，而此萃取溶剂较佳是选用含1％醋酸的乙腈溶液。
c)然后，再将样品溶液S加入快速萃取套件1的管柱10内，如图2所示。
d)最后，驱使管柱10内的样品溶液S依序流经管柱10内的第一混合粉体层12与第二混合粉体层13而从管柱10的输出口101输出成为检液原液。前述驱使样品溶液S流经管柱10的较佳方式之一是通过活塞杆2以直接加压的方式，驱使样品溶液S依序流经管柱10内的第一混合粉体层12与第二混合粉体层13。另外，也可以使用抽气法来驱使样品溶液S依序流经第一混合粉体层12与第二混合粉体层13，抽气法是使用包含真空泵的抽取装置(图中未示出)连接管柱10的输出口101，并利用该真空泵来抽引管柱10内的样品溶液S往输出口101流出。其中，样品溶液S的流速较佳是控制在0.01～0.2mL/秒，更佳是控制在0.05 mL/秒。上述滤垫11应选用不致于影响前述流速的滤垫。
由于第一混合粉体层12中的混合粉末能在样品溶液S经过时吸附样品溶液S中的大部分水分，并对样品溶液S的pH值提供缓冲作用，因此，样品溶液S流经第一混合粉体层12之后，其大部分的水分都被留在第一混合粉体层12中，且其pH值在大约4～8的范围中而不致于太酸或太碱。再者，由于第二混合粉体层13中的混合粉末能在样品溶液S经过时吸附样品溶液S中的剩余水分及会干扰仪器检测结果的杂质，例如有机酸、色素等杂质，因此，样品溶液S在继续流经第二混合粉体层13之后，就会变成没有杂质或杂质很少的检液原液S1。其中，检液原液S1是由试管3予以收集。
检液原液S1可直接以液相色谱串联质谱仪或气相色谱串联质谱仪进行检测，以确定样品上的农药残留是否符合标准。然而，检液原液S1也可以先依次经过吹至微干的步骤、加入甲醇或丙酮或正己烷的步骤、加入甲酸的步骤及以滤膜过滤的步骤之后，再以液相色谱串联质谱仪或气相色谱串联质谱仪进行检测。
较佳地，第一混合粉体层12所使用的粉剂的总体积为0.87cm3，总重量为2g。由于第一混合粉体层12在充填于内径大小经过选择的管柱10内的过程中，并没有被压得紧实而处于松散或膨松状况，因此，第一混合粉体层12在管柱10内的面积约为1.13cm2，高度约为2.05cm，故第一混合粉体层12在管柱10内的总体积约为2.317cm3，且密度约为0.863g/cm3，而总孔隙率大约在50％～62％。如此，流经此层的样品溶液S就较不易发生阻塞或流速过快的问题，从而使得样品溶液S流经此层的流速较易于控制在预期范围内，让样品溶液S中大部分的水分得以在此层被去除。
上面所述仅是本发明第一混合粉体层12的一个较佳例子，实际上并不此为限，进一步言之，第一混合粉体层12的重量较佳为0.4～5g，装填在管柱10内时的密度较佳为0.7～1.3g/cm3。另从体积的观点来看，第一混合粉体层12充填在管柱10内时的面积较佳为0.6～7.1cm2，高度较佳为1～8cm。此外，从孔隙率的观点来看，第一混合粉体层12装填在管柱10内时的总孔隙率较佳为35％～70％。
上述的总孔隙率＝(第一混合粉体层12在管柱10中的总体积-第一混合粉体层12的粉剂实际体积)÷(第一混合粉体层12在该管柱10中的总体积)×100％。
在本发明中，第一混合粉体层12所使用的粉剂成分包含无水硫酸镁、氯化 钠、柠檬酸钠与柠檬酸氢二钠。进一步言之，第一混合粉体层12较佳是由1.23g的无水硫酸镁粉末、0.31g的氯化钠粉末、0.31g的柠檬酸钠粉末与0.15g柠檬酸氢二钠粉末所构成，但不以此为限，例如0.2～2g的无水硫酸镁粉末、0.1～1g的氯化钠粉末、0.1～1g的柠檬酸钠粉末与0.05～1g的柠檬酸氢二钠粉末均为优选。
在本发明中，第二混合粉体层13的重量较佳为0.7g，且少于第一混合粉体层12，但0.2～1.6g亦为第二混合粉体层13的优选重量。从体积方面来看，第二混合粉体层13位于管柱10中的面积为1.13cm2，高度为0.8cm，但面积为0.6～7.1cm2，高度为0.23～3cm均为优选。其中，第二混合粉体层13位于管柱10中的高度是低于第一混合粉体层12。
当农产样品取自于一股蔬果时，第二混合粉体层13所使用的粉剂成分包含PSA(primary secondary amine)粉末与无水硫酸镁粉末，进一步言之，第二混合粉体层13是由0.1g的PSA粉末与0.6g的无水硫酸镁粉末所构成，但不以此为限，例如0.01～0.5g的PSA粉末与0.2～1g的无水硫酸镁粉末均为优选。当农产样品取自于叶绿素含量高的蔬果时，第二混合粉体层13所使用的粉剂成分包含PSA粉末、无水硫酸镁粉末与石墨化碳黑(GCB)粉末，进一步言之，第二混合粉体层13是由0.1g的PSA粉末、0.5925g的无水硫酸镁粉末与0.0075g的GCB粉末所构成，但不以此为限，例如0.01～0.5g的PSA粉末、0.2～1g的无水硫酸镁粉末、0.001～0.1g的GCB粉末均为优选。其中，GCB粉末与无水硫酸镁粉末的重量比较佳约为1/79。另，第二混合粉体层13中的无水硫酸镁粉末是少于第一混合粉体层12中的无水硫酸镁粉末。
图3、图4显示本发明的另一较佳实施例，在此实施例中的快速萃取套件1a的管柱10a在形态上略不同上述的管柱1，但同样都有输入口100a、输出口101a，且管柱10a内也设置上述的两垫片11及第一混合粉体层12与第二混合粉体层13。不同之处在于，上述的样品溶液S是被加到注射筒4的筒体40内，筒体40的底端射出口是连接输入口100a。当以注射筒4的活塞杆41直接加压样品溶液S时，样品溶液S即注入管柱10a并依序流经第一混合粉体层12与第二混合粉体层13而变成上述的检液原液S1，由上述的试管3予以收集。
从上述说明可知，由样品碎末与萃取溶剂所构成的样品溶液S，可以直接使用本发明的快速萃取套件1或1a来进行萃取，取得检液原液。相对现有的 QuEChERS方法，由于使用本发明的快速萃取套件1或1a来取得检液原液的过程中明显少了两次振荡处理与两次离心处理，因此，通过本发明的快速萃取套件1或1a的使用，可以大幅缩减从样品取得检液原液的时间，并因此提高整个农药残留检验程序的速度，解决现有技术无法快速取得检验结果的问题。
此外，在现有的QuEChERS方法中，每1g的均质后样品需加入1mL的萃取剂(乙腈)，但在本发明一较佳例子中，每1g的均质后样品需加入5mL萃取剂，也就是说，QuEChERS方法稀释样品的稀释倍数为1，而本发明方法稀释样品的稀释倍数为5，故依本发明方法所取得的检液原液的单位样品含量(约0.2g/mL)是低于依QuEChERS方法所取得的检液原液的单位样品含量(约1g/mL)，使得依本发明方法所取得的检液原液的基质效应低于依QuEChERS方法所取得的检液原液，这意味着依本发明方法所取得的检液原液经仪器分析所得的检测结果受基质效应干扰的程度明显低于依QuEChERS方法所取得的检液原液。
以上所述的实施例仅为说明本发明的最佳实施例原理及其功效，而非用以限制本发明。因此，本领域技术人员可在不违背本发明的精神对上述实施例进行修改及变化，均不会脱离本发明的保护范围。

Claims (11)

  1. 一种用于农产品农药残留检测程序的快速萃取套件，其包括：
    管柱，具有位于其底部的输出口，及位于其顶部的输入口，输入口供输入样品溶液，样品溶液为均质后的农产样品碎末加入萃取剂经振荡处理后的混合溶液；
    第一混合粉体层，为粉末形态且充填于管柱内，并能在样品溶液经过时吸附样品溶液中大部分的水分及对样品溶液的pH值提供缓冲作用；及
    第二混合粉体层，为粉末形态且充填于管柱内，并位于第一混合粉体层的下方及输出口的上方，并能在样品溶液经过时吸附样品溶液中的剩余水分及会干扰仪器检测结果的杂质。
  2. 根据权利要求1所述的快速萃取套件，其中第一混合粉体层位于管柱中的密度为0.7～1.3g/cm3。
  3. 根据权利要求1所述的快速萃取套件，其中第一混合粉体层位于管柱中的孔隙率为35％～70％。
  4. 根据权利要求1所述的快速萃取套件，其中第一混合粉体层的重量为0.4g～5g，第二混合粉体层的重量为0.2g～1.6g且少于第一混合粉体层的重量。
  5. 根据权利要求1所述的快速萃取套件，其中第一混合粉体层位于管柱中的面积为0.6～7.1cm2，高度为1～8cm，第二混合粉体层位于管柱中的面积为0.6～7.1cm2，高度为0.23～3cm且低于第一混合粉体层的高度。
  6. 根据权利要求1至5中任一项所述的快速萃取套件，其中第一混合粉体层的成分包含0.2～2g的无水硫酸镁粉末、0.1～1g的氯化钠粉末、0.1～1g的柠檬酸钠粉末与0.5～1g的柠檬酸氢二钠粉末。
  7. 根据权利要求6所述的快速萃取套件，其中第二混合粉体层的成分包含0.01～0.5g的PSA粉末与0.2～1g的无水硫酸镁粉末。
  8. 根据权利要求6所述的快速萃取套件，其中第二混合粉体层的成分包含0.01～0.5g的PSA粉末、0.2～1g的无水硫酸镁粉末与0.001～0.1g的石墨化碳黑粉末。
  9. 一种从农产样品取得检液原液的方法，其包括：
    对农产样品进行均质处理，以得到成农产样品碎末；
    将萃取溶剂加入农产样品碎末并进行振荡处理，以得到样品溶液，其中，每1±0.03g的农产样品碎末需添加1～10mL的萃取溶剂；
    将样品溶液加入根据权利要求1至8中任一项所述的快速萃取套件的管柱中；及
    驱使管柱内的样品溶液依序流经管柱内的第一混合粉体层与第二混合粉体层而从管柱的输出口输出成为检液原液。
  10. 根据权利要求9所述的方法，其中样品溶液的流速控制在0.01～0.2mL/秒。
  11. 根据权利要求9所述的方法，其中萃取溶剂为乙腈溶液或含醋酸的乙腈溶液。
PCT/CN2015/074011 2014-07-18 2015-03-11 用于农产品农药残留检测程序的快速萃取套件及从农产样品取得检液原液的方法 WO2016026286A1 (zh)

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