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WO2017121061A1 - 一种果蔬中三硫磷残留快速检测方法 - Google Patents

一种果蔬中三硫磷残留快速检测方法 Download PDF

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Publication number
WO2017121061A1
WO2017121061A1 PCT/CN2016/083706 CN2016083706W WO2017121061A1 WO 2017121061 A1 WO2017121061 A1 WO 2017121061A1 CN 2016083706 W CN2016083706 W CN 2016083706W WO 2017121061 A1 WO2017121061 A1 WO 2017121061A1
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Prior art keywords
trisulfide
eluent
fruits
time
detection
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French (fr)
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康怀志
刘国坤
曾勇明
陈启振
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Xiamen University
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Xiamen University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

Definitions

  • the invention relates to the detection of pesticide residues in fruits and vegetables, in particular to a rapid detection method of trisulfide residues in fruits and vegetables.
  • organophosphorus pesticides which are highly toxic, mainly entering the human body through skin contact, breathing and direct consumption.
  • organophosphorus pesticides registered in the world, which are widely used in China.
  • organophosphorus pesticides There are dozens of organophosphorus pesticides.
  • Organophosphorus pesticides When organophosphorus pesticides enter the nervous system and combine with the acetylcholinesterase active center to form phosphorylcholinesterase, phosphorylated cholinesterase is more difficult to hydrolyze, destroying the activity of cholinesterase. It causes acetylcholine to accumulate on the synapses, interferes with the normal conduction of nerve impulses, and finally leads to the death of the animal. Organophosphorus pesticides have the advantages of broad spectrum, high efficiency, easy degradation, and low price. It is the preferred pesticide variety for controlling a variety of pests in China.
  • QuEChERS and chromatographic combined detection of organic phosphorus is widely used in the laboratory, which is extracted by acetic acid acidified acetonitrile and purified by dispersive solid phase extraction. Compared with the existing domestic standards, although the pre-processing process is simplified and no professional technicians are needed, it still uses chromatographic detection. The terminal test still requires professionals and cannot leave the laboratory.
  • organophosphorus pesticides on the market, which is made of cholinesterase and chromogenic reagent which are highly sensitive to organic phosphorus.
  • this method is easy to operate, it is prone to false positives and can only be used. Determination of organophosphorus, which is highly sensitive to cholinesterase, does not identify which organophosphorus is specifically.
  • the object of the present invention is to provide a rapid detection method for trisulfide residues in fruits and vegetables.
  • the invention comprises the following steps:
  • the fruit and vegetable sample may adopt 2g; the fruit and vegetable include vegetables, cabbage, pear, apple, orange, etc.; the ratio of the extracting agent to the water storage agent may be 5-10 ml: 0.5-2 g , preferably 8 ml: 1 g, wherein the extracting agent is calculated by volume, the water storage agent is calculated by mass; the extracting agent may be acetonitrile or acetonitrile and acetic acid, and the acetic acid may be 0.1% to 1% by volume of acetonitrile;
  • the water storage agent may be selected from one of anhydrous magnesium sulfate, anhydrous sodium sulfate, and the like; the ultrasonic extraction may be carried out for 2 to 10 minutes, preferably 5 minutes.
  • the extract obtained in the step 1) is placed in a container with a lid, anhydrous magnesium sulfate, graphitized carbon and bonded silica PSA are added, shaken, left to stand, and the supernatant is placed in another container with a lid, and added.
  • Low-polar organic solvent after the second shaking, it is allowed to stand for the second time. Take 0.5 ⁇ 4ml into the test tube, blow dry with nitrogen, add the eluent, shake for the third time, and take the eluent in the detection tank. Then, the metal sol and the inorganic salt flocculant are added and mixed, and placed in a Raman spectrometer for detection.
  • the ratio of the extract, anhydrous magnesium sulfate, graphitized carbon, bonded silica PSA and low-polar organic solvent may be 3-8 ml: 0.05-0.2 g: 5-50 mg: 0.02- 0.2g: 2 to 5ml, the ratio of the extract, anhydrous magnesium sulfate, graphitized carbon, bonded silica PSA and low polar organic solvent may preferably be 5ml: 0.1g: 20mg: 0.1g: 3ml, wherein , the extract, the low-polarity organic solvent is calculated by volume, the anhydrous magnesium sulfate, the graphitized carbon and the bonded silica PSA are calculated by mass; the shaking time may be 5-30 s, preferably 20 s; the standing time It may be 0.5 to 5 min, preferably 1 min; the low polar organic solvent may be selected from one of petroleum ether, n-hexane, cyclohexane, heptane, etc.; the second oscil
  • the second resting time may be 0.5 to 5 min, preferably 1 min;
  • the volume ratio of the eluent, eluent, metal sol and inorganic salt flocculant may be from 200 to 1000:200:10 to 100:10, and the eluent, eluent, metal sol and inorganic salt flocculate.
  • the volume ratio of the agent may preferably be 400:200:10:10;
  • the eluent may be a water-miscible organic solvent aqueous solution, and the water-miscible organic solvent may be selected from the group consisting of acetonitrile, ethanol, methanol, acetone, and One of methyl sulfoxide and the like;
  • the mass ratio of the water-miscible organic solvent may be 10% to 30%, preferably 20%; and the time of the third oscillation may be 5 to 30 s, preferably 10 s.
  • the metal sol may be selected from 55 nm Au, 55nm Ag, 55nm with pinhole SHINERS, 120nm Au, 120 nm has one of pinhole SHINERS, etc.;
  • the inorganic salt flocculant may have a molar ratio of 0.01 to 5 M, preferably 0.08 M;
  • the inorganic salt flocculating agent may be selected from the group consisting of barium chloride, potassium iodide, sodium iodide, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride, potassium sulfate, sodium sulfate, magnesium sulfate, potassium phosphate, sodium phosphate, One of potassium carbonate, sodium carbonate, etc.;
  • the Raman spectrometer can have a power of 280 mW, a laser wavelength of 785 nm, and a scanning range of 200 to 2000 nm.
  • the present invention Compared with the existing method for detecting trisulfide residues in fruits and vegetables, the present invention has the following outstanding advantages:
  • Figure 1 is a test curve of trithiophos in the cabbage of Example 1.
  • Sample source commercially available cabbage plus standard trisulfide sample, Raman spectrometer power 280mW, laser wavelength 785nm, integration time 5s;
  • Sample source commercially available cabbage plus standard trisulfide sample, Raman spectrometer power 280mW, laser wavelength 785nm, integration time 5s;
  • Figure 3 is a trithiophos test curve for the orange of Example 3.
  • Sample source commercially available orange peel plus trisulfide sample, Raman spectrometer power 180mW, laser wavelength 785nm, integration time 5s;
  • Sample source Commercially available apple spiked trisulfide sample, Raman spectrometer power 280mW, laser wavelength 785nm, integration time 5s.
  • the cabbage sample is 2 g; the ratio of the extracting agent to the water storage agent may be 5 to 10 ml. : 0.5 ⁇ 2g, preferably 8ml : 1g, wherein the extractant is calculated by volume, the water storage agent is calculated by mass; the extracting agent may be acetonitrile or acetonitrile and acetic acid, and the acetic acid may be 0.1% to 1% by volume of acetonitrile.
  • the water storage agent may be selected from one of anhydrous magnesium sulfate, anhydrous sodium sulfate, and the like; the ultrasonic extraction may be carried out for 2 to 10 minutes, preferably 5 minutes.
  • the source of the cabbage sample the commercially available cabbage is spiked with the sample of trisulfide.
  • the extract obtained in the step 1) is placed in a container with a lid, anhydrous magnesium sulfate, graphitized carbon and bonded silica PSA are added, shaken, left to stand, and the supernatant is placed in another container with a lid, and added.
  • Low-polar organic solvent after the second shaking, it is allowed to stand for the second time. Take 0.5 ⁇ 4ml into the test tube, blow dry with nitrogen, add the eluent, shake for the third time, and take the eluent in the detection tank. Then, the metal sol and the inorganic salt flocculant are added and mixed, and placed in a Raman spectrometer for detection.
  • the ratio of the extract, anhydrous magnesium sulfate, graphitized carbon, bonded silica PSA and low polar organic solvent may be 3-8 ml: 0.05-0.2 g: 5-50 mg: 0.02-0.2 g: 2-5 ml.
  • the ratio of the extract, the anhydrous magnesium sulfate, the graphitized carbon, the bonded silica PSA and the low polar organic solvent may preferably be 5 ml: 0.1 g: 20 mg: 0.1 g: 3 ml, wherein the extract, the low pole
  • the organic solvent is calculated by volume, anhydrous magnesium sulfate, graphitized carbon and bonded silica PSA are calculated by mass;
  • the shaking time may be 5-30 s, preferably 20 s;
  • the standing time may be 0.5-5 min,
  • the low polar organic solvent may be selected from one of petroleum ether, n-hexane, cyclohexane, heptane, etc.;
  • the second oscillation may be carried out for 5 to 30 s, preferably 10 s;
  • the second standing time may be 0.5 to 5 min, preferably 1 min;
  • the volume ratio of the agent may preferably be 400:200:10:10;
  • the eluent may be a water-miscible organic solvent aqueous solution, and the water-miscible organic solvent may be selected from the group consisting of acetonitrile, ethanol, methanol, acetone, and One of methyl sulfoxide and the like;
  • the mass ratio of the water-miscible organic solvent may be 10% to 30%, preferably 20%; and the time of the third oscillation may be 5 to 30 s, preferably 10 s.
  • the metal sol may be selected from 55 nm Au, 55nm Ag, 55nm with pinhole SHINERS, 120nm Au, 120 nm has one of pinhole SHINERS, etc.;
  • the inorganic salt flocculant may have a molar ratio of 0.01 to 5 M, preferably 0.08 M;
  • the inorganic salt flocculating agent may be selected from the group consisting of barium chloride, potassium iodide, sodium iodide, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride, potassium sulfate, sodium sulfate, magnesium sulfate, potassium phosphate, sodium phosphate, One of potassium carbonate, sodium carbonate, etc.;
  • the Raman spectrometer can have a power of 280 mW, a laser wavelength of 785 nm, and a scanning range of 200 to 2000 nm.
  • the Raman spectrometer has a power of 280 mW, a laser wavelength of 785 nm, and an integration time of 5 s.
  • Example 2 Similar to Example 1, the difference is in the source of the fruit and vegetable sample: a commercially available Chinese cabbage spiked with a sample of trisulfide.
  • the trithiophos test curve of the pakchoi of Example 2 is shown in Fig. 2.
  • the Raman spectrometer has a power of 280 mW, a laser wavelength of 785 nm, and an integration time of 5 s.
  • Example 2 Similar to Example 1, the difference is in the source of the fruit and vegetable sample: a commercially available orange peel plus a sample of trisulfide.
  • the test curve of the trithiophos in the orange of Example 3 is shown in Fig. 3.
  • the Raman spectrometer has a power of 180 mW, a laser wavelength of 785 nm, and an integration time of 5 s.
  • Example 2 Similar to Example 1, the difference is in the source of the fruit and vegetable samples: a commercially available apple spiked trisulfide sample.
  • the Raman spectrometer has a power of 280 mW, a laser wavelength of 785 nm, and an integration time of 5 s.
  • the reinforcing agent used in the present invention comprises bare gold, silver, copper nanoparticles (having a particle size of 30 to 200 nm), and pinhole-containing SHINERS particles and pinhole-free SHINERS particles having a core particle diameter of 30 to 200 nm, and a shell
  • the layer thickness is 1 to 10 nm.
  • the pretreatment method is to extract the test substance in the sample from the fruits and vegetables by using acetonitrile (which may contain 0.1% to 1% acetic acid), and remove a small amount of water contained in the sample by using anhydrous magnesium sulfate, and use the bonded silica PSA. And graphitized carbon GCB to remove the organic acid and other substrates in the extract, and extract the test substance by petroleum ether (low-polar organic solvent such as n-hexane, cyclohexane or heptane) for further purification and purification.
  • acetonitrile which may contain 0.1% to 1% acetic acid
  • graphitized carbon GCB to remove the organic acid and other substrates in the extract
  • petroleum ether low-polar organic solvent such as n-hexane, cyclohexane or heptane
  • surface-enhanced Raman spectroscopy as a detection technique, rapid detection of the substance to be tested can be achieved. Therefore, the previous treatment
  • the adsorbent used includes a bonded silica PSA and a graphitized carbon GCB, wherein the bonded silica PSA is used in an amount of 0.02 to 0.2 g, preferably 0.1 g, and graphitized carbon is 5 to 50 mg, preferably 20 mg.

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Abstract

一种果蔬中三硫磷残留快速检测方法，将果蔬样品放入容器中，加入提取剂、储水剂，超声提取，得提取液；将提取液放入带盖容器中，加入无水硫酸镁、石墨化碳和键合硅胶PSA，振荡后静置，将上清液放入另一带盖容器中，加入低极性有机溶剂，第二次振荡后第二次静置，取0.5～4ml放入试管中，氮气吹干，再加入洗脱剂，第三次振荡，取洗脱液于检测池中，然后加入金属溶胶和无机盐絮凝剂混匀，放入拉曼光谱仪检测室内进行检测。操作简便、无需专业人员即可实现检测；检测时间短、可实现大批量样品的快速筛选；准确度高，无假阳性现象发生；不需大量的有机溶剂及有毒试剂，对于检测人员的身体健康及环境都不会照成危害。

Description

一种果蔬中三硫磷残留快速检测方法
技术领域
本发明涉及果蔬农药残留检测，尤其是涉及一种果蔬中三硫磷残留快速检测方法。
背景技术
有机磷农药种类繁多，毒性较大，主要是通过皮肤接触、呼吸和直接食用等方式进入人体。目前在全球注册的有机磷农药达上百种，在我国大量使用 的有机磷农药也多达数十种。有机磷农药的结构通式为 X=PZ(R1)(R2), 其中 X 表示=O 或=S, Z表示卤基、烷氧基或其他取代基等, R1、R2 表示甲氧基(CH3O-) 或乙氧基(C2H5O-)。有机磷农药的分子结构分为两 类：一类是 P=O，如敌敌畏、氧化乐果等；另一类是P=S，如甲拌磷、甲基嘧啶磷等。有机磷农药在结构上含有 P=O、P=S、C-P、C-O-P、C-N-P、C-S-P 键, 除敌百虫和乐果外大多数不溶于水, 溶于有机溶剂, 在 碱性条件下易水解。有机磷农药可通过呼吸、接触等方式进入人体, 经血液和淋巴循环到全身各器官和组织。有机磷农药进入神经系统后与乙酰胆碱酯酶活性中心结合生成磷酸化胆碱酯酶,磷酸化胆碱酯酶较难水解, 破坏了胆碱酯酶的活性, 使得乙酰胆碱在神经突触上大积累, 干扰了神经冲动的正常传导, 最后导致动物体的死亡。有机磷农药具有广谱高效、易降解、价格低廉等优点, 是我国防治多种害虫害的首选农药品种。但是由于有机磷农药的大量使用使得农作物和果蔬表面存在有机磷农药残留,对人民群众的生活和生命安全造成严重的威胁。所以，长期食用利用SO2漂白的食品对人体有巨大的危害。由此，在国家标准GB 2763-2014《食品安全国家标准食品中农药最大残留限量》中没有对三硫磷进行规定，即三硫磷不能在食品中残留。
目前我国果蔬中有机磷残留量的检测主要标准有NYT 761-2008《蔬菜和水果中有机磷、有机氯、拟除虫菊酯和氨基甲酸酯类农药多残留的测定》、GBT 19648-2006《水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法》、SNT0148-2011《进出口水果蔬菜中有机磷农药残留量检测方法 气相色谱和气相色谱-质谱法》以及GBT 5009.218-2008《水果和蔬菜中多种农药残留量的测定》，这些标准都是采用有机溶剂进行匀浆提取，结合液液萃取或固相萃取进行除杂，最后用色谱进行检测。这些标准的方案都需要对样品进行复杂的前处理，测定时间均较长,需要专业技术人员在实验室完成。
另外，QuEChERS和色谱结合检测有机磷在实验室应用广泛，其采用醋酸酸化的乙腈提取，采用分散固相萃取的方式净化。与国内现有标准相比，虽然简化了前处理过程，不需要专业技术人员，但其仍采用色谱进行检测，终端测试还是需要专业人员，无法离开实验室。
目前，市面上也有有机磷农药快速检测卡，其是利用对有机磷高度敏感的胆碱酯酶和显色剂做成酶试纸，此方法虽然操作简便，但其易出现假阳性，并且只能测定对胆碱酯酶高度敏感的有机磷，无法鉴别具体是哪种有机磷。
发明内容
本发明的目的在于提供一种果蔬中三硫磷残留快速检测方法。
本发明包括以下步骤：
1）将果蔬样品放入容器中，加入提取剂、储水剂，超声提取，得提取液； 在步骤1）中，所述果蔬样品可采用2g；所述果蔬包括青菜、包菜、梨、苹果、橘子等；所述提取剂与储水剂的配比可为5～10ml∶0.5～2g，优选8ml∶1g，其中提取剂以体积计算，储水剂以质量计算；所述提取剂可采用乙腈或乙腈和乙酸，所述乙酸按体积百分比可为乙腈的0.1%～1%；所述储水剂可选自无水硫酸镁、无水硫酸钠等中的一种；所述超声提取的时间可为2～10min，优选5min。
2）将步骤1）得到的提取液放入带盖容器中，加入无水硫酸镁、石墨化碳和键合硅胶PSA，振荡后静置，将上清液放入另一带盖容器中，加入低极性有机溶剂，第二次振荡后第二次静置，取0.5～4ml放入试管中，氮气吹干，再加入洗脱剂，第三次振荡，取洗脱液于检测池中，然后加入金属溶胶和无机盐絮凝剂混匀，放入拉曼光谱仪检测室内进行检测。
在步骤2）中，所述提取液、无水硫酸镁、石墨化碳、键合硅胶PSA和低极性有机溶剂的配比可为3～8ml∶0.05～0.2g∶5～50mg∶0.02～0.2g∶2～5ml，所述提取液、无水硫酸镁、石墨化碳、键合硅胶PSA和低极性有机溶剂的配比可优选为5ml∶0.1g∶20mg∶0.1g∶3ml，其中，提取液、低极性有机溶剂以体积计算，无水硫酸镁、石墨化碳和键合硅胶PSA以质量计算；所述振荡的时间可为5～30s，优选20s；所述静置的时间可为0.5～5min，优选1min；所述低极性有机溶剂可选自石油醚、正己烷、环己烷、庚烷等中的一种；所述第二次振荡的时间可为5～30s，优选10s；所述第二次静置的时间可为0.5～5min，优选1min； 所述洗脱剂、洗脱液、金属溶胶和无机盐絮凝剂的体积比可为200～1000∶200∶10～100∶10，所述洗脱剂、洗脱液、金属溶胶和无机盐絮凝剂的体积比可优选为400∶200∶10∶10；所述洗脱剂可采用与水互溶的有机溶剂水溶液，所述与水互溶的有机溶剂可选自乙腈、乙醇、甲醇、丙酮、二甲亚砜等中的一种；所述与水互溶的有机溶剂的质量百分浓度可为10%～30%，优选20%；所述第三次振荡的时间可为5～30s，优选10s；所述金属溶胶可选自55nm Au、55nm Ag、55nm有针孔SHINERS、120nm Au、120nm有针孔SHINERS等中的一种；所述无机盐絮凝剂的摩尔比可为0.01～5M，优选0.08 M；所述无机盐絮凝剂可选自氯化钡、碘化钾、碘化钠、氯化钾、氯化镁、氯化钙、氯化铝、硫酸钾、硫酸钠、硫酸镁、磷酸钾、磷酸钠、碳酸钾、碳酸钠等中的一种；所述拉曼光谱仪的功率可为280mW，激光波长可为785nm，扫描范围可为200～2000nm。
与现有的果蔬中三硫磷残留检测方法相比，本发明具有以下突出优点：
1）操作简便、无需专业人员即可实现检测；
2）检测时间短、可实现大批量样品的快速筛选；
3）准确度高，无假阳性现象发生；
4）采用简单的吸附剂和液液萃取对三硫磷进行提取和、提纯和富集，使用金属溶胶进行检测，不会用到大量的有机溶剂及有毒试剂，对于检测人员的身体健康及环境都不会照成危害，对环境友好。
附图说明
图1为实施例1的包菜中三硫磷测试曲线。样品来源：市售包菜加标三硫磷样品，拉曼光谱仪功率280mW，激光波长785nm，积分时间5s；
图2为实施例2的小白菜中三硫磷测试曲线。样品来源：市售小白菜加标三硫磷样品，拉曼光谱仪功率280mW，激光波长785nm，积分时间5s；
图3为实施例3的橘子中三硫磷测试曲线。样品来源：市售橘子皮加标三硫磷样品，拉曼光谱仪功率180mW，激光波长785nm，积分时间5s；
图4为实施例4的苹果中三硫磷测试曲线。样品来源：市售苹果加标三硫磷样品，拉曼光谱仪功率280mW，激光波长785nm，积分时间5s。
具体实施方式
以下实施例将结合附图对本发明作进一步的说明。
实施例1
本实施例包括以下步骤：
1）将包菜样品放入容器中，加入提取剂、储水剂，超声提取，得提取液；所述包菜样品采用2g；所述提取剂与储水剂的配比可为5～10ml∶0.5～2g，优选8ml∶1g，其中提取剂以体积计算，储水剂以质量计算；所述提取剂可采用乙腈或乙腈和乙酸，所述乙酸按体积百分比可为乙腈的0.1%～1%；所述储水剂可选自无水硫酸镁、无水硫酸钠等中的一种；所述超声提取的时间可为2～10min，优选5min。包菜样品来源：市售包菜加标三硫磷样品。
2）将步骤1）得到的提取液放入带盖容器中，加入无水硫酸镁、石墨化碳和键合硅胶PSA，振荡后静置，将上清液放入另一带盖容器中，加入低极性有机溶剂，第二次振荡后第二次静置，取0.5～4ml放入试管中，氮气吹干，再加入洗脱剂，第三次振荡，取洗脱液于检测池中，然后加入金属溶胶和无机盐絮凝剂混匀，放入拉曼光谱仪检测室内进行检测。所述提取液、无水硫酸镁、石墨化碳、键合硅胶PSA和低极性有机溶剂的配比可为3～8ml∶0.05～0.2g∶5～50mg∶0.02～0.2g∶2～5ml，所述提取液、无水硫酸镁、石墨化碳、键合硅胶PSA和低极性有机溶剂的配比可优选为5ml∶0.1g∶20mg∶0.1g∶3ml，其中，提取液、低极性有机溶剂以体积计算，无水硫酸镁、石墨化碳和键合硅胶PSA以质量计算；所述振荡的时间可为5～30s，优选20s；所述静置的时间可为0.5～5min，优选1min；所述低极性有机溶剂可选自石油醚、正己烷、环己烷、庚烷等中的一种；所述第二次振荡的时间可为5～30s，优选10s；所述第二次静置的时间可为0.5～5min，优选1min； 所述洗脱剂、洗脱液、金属溶胶和无机盐絮凝剂的体积比可为200～1000∶200∶10～100∶10，所述洗脱剂、洗脱液、金属溶胶和无机盐絮凝剂的体积比可优选为400∶200∶10∶10；所述洗脱剂可采用与水互溶的有机溶剂水溶液，所述与水互溶的有机溶剂可选自乙腈、乙醇、甲醇、丙酮、二甲亚砜等中的一种；所述与水互溶的有机溶剂的质量百分浓度可为10%～30%，优选20%；所述第三次振荡的时间可为5～30s，优选10s；所述金属溶胶可选自55nm Au、55nm Ag、55nm有针孔SHINERS、120nm Au、120nm有针孔SHINERS等中的一种；所述无机盐絮凝剂的摩尔比可为0.01～5M，优选0.08 M；所述无机盐絮凝剂可选自氯化钡、碘化钾、碘化钠、氯化钾、氯化镁、氯化钙、氯化铝、硫酸钾、硫酸钠、硫酸镁、磷酸钾、磷酸钠、碳酸钾、碳酸钠等中的一种；所述拉曼光谱仪的功率可为280mW，激光波长可为785nm，扫描范围可为200～2000nm。
实施例1的包菜中三硫磷测试曲线参见图1。拉曼光谱仪功率280mW，激光波长785nm，积分时间5s。
实施例2
与实施例1类似，其区别在于果蔬样品来源：市售小白菜加标三硫磷样品。
实施例2的小白菜中三硫磷测试曲线参见图2，拉曼光谱仪功率280mW，激光波长785nm，积分时间5s。
实施例3
与实施例1类似，其区别在于果蔬样品来源：市售橘子皮加标三硫磷样品。
实施例3的橘子中三硫磷测试曲线参见图3，拉曼光谱仪功率180mW，激光波长785nm，积分时间5s。
实施例4
与实施例1类似，其区别在于果蔬样品来源：市售苹果加标三硫磷样品。
实施例4的苹果中三硫磷测试曲线参见图4。拉曼光谱仪功率280mW，激光波长785nm，积分时间5s。
本发明中采用的增强试剂，包括裸露的金、银、铜纳米粒子（粒径为30～200nm）及有针孔的SHINERS粒子和无针孔的SHINERS粒子的内核粒径为30～200nm，壳层厚度为1～10nm。
采用的前处理方式是利用乙腈（可以包含0.1%～1%乙酸）将样品中的待测物质从果蔬中提取出来，利用无水硫酸镁除去样品中的含有的少量水，采用键合硅胶PSA和石墨化碳GCB去除提取液中有机酸等基质，并通过石油醚（正己烷、环己烷、庚烷等低极性有机溶剂也可）萃取对待测物质进行再一次的提纯和净化，同时利用表面增强拉曼光谱技术作为检测技术，可实现对待测物质的快速检测，所以此前处理方式结合表面增强拉曼光谱技术可简化前处理流程，实现对待测物质的快速检测，适用于大批量样品的快速筛选
采用的吸附剂包括键合硅胶PSA和石墨化碳GCB，其中键合硅胶PSA用量为0.02～0.2g，优选为0.1g，石墨化碳为5～50mg，优选为20mg。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的试验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。

Claims (10)

  1. 一种果蔬中三硫磷残留快速检测方法，其特征在于包括以下步骤： 1）将果蔬样品放入容器中，加入提取剂、储水剂，超声提取，得提取液； 2）将步骤1）得到的提取液放入带盖容器中，加入无水硫酸镁、石墨化碳和键合硅胶PSA，振荡后静置，将上清液放入另一带盖容器中，加入低极性有机溶剂，第二次振荡后第二次静置，取0.5～4ml放入试管中，氮气吹干，再加入洗脱剂，第三次振荡，取洗脱液于检测池中，然后加入金属溶胶和无机盐絮凝剂混匀，放入拉曼光谱仪检测室内进行检测。
  2. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤1）中，所述果蔬样品采用2g；所述果蔬包括青菜、包菜、梨、苹果、橘子。
  3. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤1）中，所述提取剂与储水剂的配比为5～10ml∶0.5～2g，优选8ml∶1g，其中提取剂以体积计算，储水剂以质量计算。
  4. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤1）中，所述提取剂采用乙腈或乙腈和乙酸，所述乙酸按体积百分比可为乙腈的0.1%～1%；所述储水剂可选自无水硫酸镁、无水硫酸钠中的一种；所述超声提取的时间可为2～10min，优选5min。
  5. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤2）中，所述提取液、无水硫酸镁、石墨化碳、键合硅胶PSA和低极性有机溶剂的配比为3～8ml∶0.05～0.2g∶5～50mg∶0.02～0.2g∶2～5ml，所述提取液、无水硫酸镁、石墨化碳、键合硅胶PSA和低极性有机溶剂的配比可优选为5ml∶0.1g∶20mg∶0.1g∶3ml，其中，提取液、低极性有机溶剂以体积计算，无水硫酸镁、石墨化碳和键合硅胶PSA以质量计算。
  6. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤2）中，所述振荡的时间为5～30s，优选20s；所述静置的时间可为0.5～5min，优选1min。
  7. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤2）中，所述低极性有机溶剂选自石油醚、正己烷、环己烷、庚烷中的一种；所述第二次振荡的时间可为5～30s，优选10s；所述第二次静置的时间可为0.5～5min，优选1min。
  8. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤2）中，所述洗脱剂、洗脱液、金属溶胶和无机盐絮凝剂的体积比为200～1000∶200∶10～100∶10，所述洗脱剂、洗脱液、金属溶胶和无机盐絮凝剂的体积比可优选为400∶200∶10∶10。
  9. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤2）中，所述洗脱剂采用与水互溶的有机溶剂水溶液，所述与水互溶的有机溶剂可选自乙腈、乙醇、甲醇、丙酮、二甲亚砜中的一种；所述与水互溶的有机溶剂的质量百分浓度可为10%～30%，优选20%；所述第三次振荡的时间可为5～30s，优选10s。
  10. 如权利要求1所述一种果蔬中三硫磷残留快速检测方法，其特征在于在步骤2）中，所述金属溶胶选自55nm Au、55nm Ag、55nm有针孔SHINERS、120nm Au、120nm有针孔SHINERS中的一种；所述无机盐絮凝剂的摩尔比可为0.01～5M，优选0.08 M；所述无机盐絮凝剂可选自氯化钡、碘化钾、碘化钠、氯化钾、氯化镁、氯化钙、氯化铝、硫酸钾、硫酸钠、硫酸镁、磷酸钾、磷酸钠、碳酸钾、碳酸钠中的一种；所述拉曼光谱仪的功率可为280mW，激光波长可为785nm，扫描范围可为200～2000nm。
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110672580A (zh) * 2019-09-28 2020-01-10 上海如海光电科技有限公司 一种食品饮料和植物油中四氢大麻酚的拉曼快速检测方法
CN111579319A (zh) * 2019-02-15 2020-08-25 中国水产科学研究院 一种基于磁分离的全自动样品前处理一体化装置
CN112557478A (zh) * 2020-10-10 2021-03-26 安徽大学 一种区分磷的不同价态含氧酸盐亚磷酸钠及次磷酸钠的方法
CN112630151A (zh) * 2020-12-18 2021-04-09 成都子之源绿能科技有限公司 Sers衬底及制备方法和采用sers测量农残的方法
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CN115569642A (zh) * 2022-09-09 2023-01-06 北京联合大学 氨基甲酸酯类农药的固相微萃取吸附剂
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105572098A (zh) * 2016-01-12 2016-05-11 厦门大学 一种果蔬中三硫磷残留快速检测方法
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CN111948189A (zh) * 2019-05-15 2020-11-17 厦门市普识纳米科技有限公司 一种食品中投毒类物质的检测方法
CN110231329A (zh) * 2019-05-27 2019-09-13 河北伊诺光学科技股份有限公司 利用拉曼增强光谱检测食品中杀菌剂残留的方法
CN111735805A (zh) * 2020-06-19 2020-10-02 上海如海光电科技有限公司 一种食品水果中苯硫威的拉曼快速检测方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546988A (zh) * 2003-12-02 2004-11-17 厦门大学 蔬菜和水果中有机磷农药残留量的快速测定方法
US7119891B2 (en) * 2003-05-22 2006-10-10 White Brian N Detecting substances in drinking water reservoirs
CN103472051A (zh) * 2013-09-20 2013-12-25 华东交通大学 一种水果农药残留的表面增强拉曼光谱检测方法
CN104101591A (zh) * 2014-07-24 2014-10-15 江西农业大学 柑桔中痕量农药残留的表面增强拉曼光谱快速检测方法
CN105572098A (zh) * 2016-01-12 2016-05-11 厦门大学 一种果蔬中三硫磷残留快速检测方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104931483A (zh) * 2015-06-30 2015-09-23 北京工商大学 果蔬中农药残留的拉曼光谱检测方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7119891B2 (en) * 2003-05-22 2006-10-10 White Brian N Detecting substances in drinking water reservoirs
CN1546988A (zh) * 2003-12-02 2004-11-17 厦门大学 蔬菜和水果中有机磷农药残留量的快速测定方法
CN103472051A (zh) * 2013-09-20 2013-12-25 华东交通大学 一种水果农药残留的表面增强拉曼光谱检测方法
CN104101591A (zh) * 2014-07-24 2014-10-15 江西农业大学 柑桔中痕量农药残留的表面增强拉曼光谱快速检测方法
CN105572098A (zh) * 2016-01-12 2016-05-11 厦门大学 一种果蔬中三硫磷残留快速检测方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG, QIANLONG ET AL.: "Research on determination of 36 organphosphorus pesticide residues in fruits and vegetables by gas chromatography with gel permeation chromatography clean-up", CHINESE JOURNAL OF HEALTH LABORATORY TECHNOLOGY, vol. 22, no. 11, 30 November 2012 (2012-11-30) *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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