CN104931627A - Solid-phase extraction column and application thereof - Google Patents
Solid-phase extraction column and application thereof Download PDFInfo
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- CN104931627A CN104931627A CN201510253906.9A CN201510253906A CN104931627A CN 104931627 A CN104931627 A CN 104931627A CN 201510253906 A CN201510253906 A CN 201510253906A CN 104931627 A CN104931627 A CN 104931627A
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Abstract
The invention provides a solid-phase extraction column. A filler of the solid-phase extraction column is a multiwall carbon nano tube. The solid-phase extraction column provided by the invention can be used for carrying out enrichment and purification on four A-type trichothecene toxins in crops of maize, rice, wheat and the like at the same time. The solid-phase extraction column provided by the invention is simple to prepare, is easy to operate, and has good enrichment and purification effects on the four A-type trichothecene toxins in the crops.
Description
Technical field
The present invention relates to agricultural product security detection technique field, relate in particular to a kind of solid-phase extraction column and application thereof.
Background technology
A type Trichothecenes toxoid is the mycotoxin that a class is produced by sickle-like bacteria, mainly comprises T-2 toxin (T-2), HT2 toxin (HT2), neo-solaniol (NEO) and diacetyl scirpene alcohol (DAS) four kinds.These four kinds of toxin can extensively pollute the crops such as corn, wheat, rice, after people and animals eat such cereal with serious pollution by mistake, myocardial damage can be caused, gastrointestinal epithelial moves that film is hemorrhage, skin histology is downright bad, hematopoietic tissue destroys and immunosupress, nerve problems, cardiovascular system destruction etc., serious caused death.
Existingly be mainly Solid-Phase Extraction column purification about the anatoxic purification method of A type single-ended Bao Meixi race, business-like solid-phase extraction column is mainly HLB post, immune affinity column etc.But commercial immune affinity column price is very expensive, even if HLB post the most cheap, single price also wants about 20 yuan, and the immune affinity column that in GB GBT 23501-2009, pre-treatment adopts, single price even reaches 80-100 unit.And commercial solid-phase extraction column pillar, mostly for the purification of a certain toxin or a certain matrix, cannot realize the object that the multiple toxin of multiple matrix purifies simultaneously.At present, still lack a kind of cheap solid-phase extraction column, can effectively be used for four kinds of A type Trichothecenes toxoid Sync enrichment purifications in corn, wheat and rice.
Summary of the invention
First object of the present invention is to provide a kind of solid-phase extraction column, and its filler is multi-walled carbon nano-tubes;
Specifically, this solid-phase extraction column comprises upper sieve plate, multi-wall carbon nano-tube tube packing and lower sieve plate;
Multi-walled carbon nano-tubes wherein used can be Multiple Type, as 8nm i.d., 10-30 μm length, 500m
2/ g; Loading is 10-100mg; The packed column volume adopted is 0.1-1000mL, and internal diameter is 0.1-50cm; Respectively there is one piece of sieve plate at the upper and lower two ends of filler, and plate thickness is 1-5mm.
Present invention also offers the application of above-mentioned solid phase extraction column, it can be used for carrying out enrichment purification to four kinds of A type Trichothecenes toxoids in crops simultaneously.
Present invention also offers and a kind ofly apply above-mentioned solid phase extraction column carries out enrichment purification method to four kinds of A type Trichothecenes toxoids in crops, the method comprises the steps:
Carry out sample extracting solution loading;
The drip washing of first step leacheate;
The drip washing of second step leacheate;
Namely obtain containing four kinds of anatoxic sample solutions of A type Trichothecenes after elution.
Specifically,
(1) prepare sample extracting solution, i.e. sample solution: get corn, wheat, rice sample, with aqueous solutions of organic solvent ultrasonic extraction 1h, extract nitrogen dries up, add aqueous solutions of organic solvent again, vortex 30s, ultrasonic 1min, then adds water, vortex 30s, after ultrasonic 1min, obtains sample solution;
Wherein said aqueous solutions of organic solvent is the mixed liquor of methanol aqueous solution, acetonitrile solution or other organic solvent and water, and wherein the volume basis ratio of organic solvent is 0.001-20%, and loading volume is 1-100mL.
(2) first step leacheate is normal hexane or similar weakly polar organic solvent, and elution volume is 1-100mL.
(3) second step leacheate is methanol aqueous solution, acetonitrile solution or other organic solvent water mixed liquid, and wherein in leacheate, the volume basis ratio of organic solvent is 0.001-20%, and leacheate volume is 1-100mL.
(4) eluent is the methyl alcohol (v/v) containing (0.1-5%) formic acid or the acetonitrile (v/v) containing (0.1-5%) formic acid or containing other organic solvent (v/v) of (0.1-5%) formic acid, effluent volume is 1-100mL.In whole experimental implementation, flow rate of liquid (comprising sample solution, leacheate, eluent) is no more than 2mL/min.
Beneficial effect of the present invention is mainly reflected in:
(1) adopt the nano material with bigger serface as packing material first, for the purification to mycotoxin.Multi-walled carbon nano-tubes has good absorption property to object, can significantly remove interference impurity;
(2) follow general loading, drip washing, elution step, belong to conventional using method, general experimenter's simple training can use, and does not need special instruments and equipment, practical; Experiment flow is very fast, and whole process is no more than 1 hour;
(3) multi-walled carbon nano-tubes can obtain in commercialization, and price is 1g=20 unit, if with the loading of single solid-phase extraction column for 50mg, the price of that single solid-phase extraction column is no more than 5 yuan, compared with existing commercialization solid phase column, while guarantee clean-up effect, greatly provide cost savings;
(4) purification method of the present invention is stable, ripe, can be applicable to four kinds of A type Trichothecenes toxoid Sync enrichment purifications in the various types of grain such as corn, rice, wheat, applied widely, good purification.
Accompanying drawing explanation
Fig. 1 is the solid phase extraction column structural drawing based on multi-walled carbon nano-tubes packing material in invention example.
Wherein, 1, packed column; 2, upper sieve plate; 3, filler; 4, lower sieve plate
Fig. 2 is corn in invention example, wheat, rice by Solid-Phase Extraction column purification with do not purify comparing of appearance features.
Fig. 3 is the chromatogram of the matrix after purification.(A) rice (B) wheat (C) corn
Fig. 4 is the chromatogram (standard concentration 1ng/mL) of the matrix standard specimen after purification.(A) rice (B) wheat (C) corn
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but protection scope of the present invention is not limited in this:
Embodiment one prepares solid-phase extraction column
The structural representation of solid-phase extraction column is shown in Fig. 1, primarily of four part compositions: packed column (volume is 3mL), upper sieve plate (thickness 2mm), lower sieve plate (thickness 2mm) and filler (50mg, height is 5cm about);
Filler is that (Nanjing Xian Feng Nono-material Science & Technology Ltd., model is 8nm i.d., 10-30 μm length, 500m to multi-walled carbon nano-tubes
2/ g).
Embodiment two
The solid-phase extraction column of Application Example one carries out four kinds of anatoxic enrichment purifications of A type single-ended Bao Meixi race
The first step, prepares sample solution: take 2g corn, wheat, rice sample (the commercially available random sample in Shanghai) respectively, with 10mL acetonitrile/water solution (84/16, v/v) ultrasonic extraction 1h, get 5mL extract nitrogen to blow near dry, then add the acetonitrile/water solution (20/80, v/v) of 0.5mL, vortex 30s, ultrasonic 1min, then adds 4.5mL water, vortex 30s, after ultrasonic 1min, prepared column purification;
Second step, loading: said extracted liquid is added in decontaminating column, regulate vacuum tightness, make it cross column flow rate and be approximately 2mL/min, efflux discards;
3rd step, drip washing: first carry out first step drip washing with 5mL normal hexane, and then carry out second step drip washing by the methanol/water solution (5/95, v/v) of 5mL, the column flow rate of crossing of leacheate is approximately 2mL/min, and the efflux crossed after post discards;
4th step, wash-out: with the methanol solution wash-out of 5mL containing 1% (volume ratio) formic acid, negative pressure is drained, collect eluent, eluent nitrogen dries up, with the acetonitrile of 1mL/containing the aqueous solution (20/80 of 5mM ammonium acetate, v/v) constant volume, crosses the laggard LC-MS/MS of film and analyzes;
5th step, detects: adopt using high performance liquid chromatography tandem mass spectrum instrument (UHPLC-XEVO TQ-S, waters company, the U.S.) to detect sample.Liquid-phase condition is: mobile phase is (A) aqueous solution (m/v) containing 5% ammonium acetate; (B) methyl alcohol.Linear gradient elution: initial: 40%B, 0-4min 90%B, 4-4.5min 90%B, 4.5-4.8min40%B, balance 2.2min, total run time is 7min.Sampling volume is 5 μ L.Mass Spectrometry Conditions is: ion source temperature: 150 DEG C; Desolventizing temperature degree: 500 DEG C; Taper hole gas and desolventizing airshed are 30 and 1000L/h respectively.Adopt MRM method to detect, specifically the detected parameters of each toxin is in table 1.
arepresent quota ion.
Result:
(1) appearance features: as shown in Figure 2: from apparent, through multi-walled carbon nano-tubes fill after Solid-Phase Extraction column purification containing four kinds of anatoxic sample solutions of A type Trichothecenes (corn, wheat, rice) with do not purify compared with sample liquid, obvious clear, and the sample liquid through purifying, the great majority interference impurity such as pigment can be removed completely, the object of purification can be reached;
(2) matrix interference situation after sample purification: the sample as seen from Figure 3 after purification does not exist the interference impurity of any object substantially, the existence of noiseless chromatographic peak;
(3) the matrix mark-on situation after sample purification: the sample substrate after purification is added four kinds of standard items, be made into the matrix mark-on solution of 1ng/mL, as seen from Figure 4, good chromatographic peak can be gone out in the matrix mark liquid of 1ng/mL, not find matrix interference;
(4) recovery checking of method: adopt the recovery of matrix mark-on method to method to investigate, take 2g corn, wheat, rice sample respectively, add basic, normal, high three concentration levels (1 μ g/kg, 50 μ g/kg and 400 μ g/kg) four kinds of mycotoxin standard items, with former state originally for control group, each parallel three parts of experiments.Sample detects according to after above-mentioned steps purification, and recovery result is: corn sample: 73.4-91.4%; Wheat samples: 75.2-113.7%; Rice sample: 74.6-96.3%;
(5) the precision checking of method: within the same day, parallel 5 increment product are tested, and obtain withinday precision: 1.2-14.0% after purification assays; For three days on end, every day, parallel 5 increment product were tested, and obtained day to day precision: 3.2-17.1% after detection computations.
As fully visible, solid-phase extraction column of the present invention, can effectively to the A type single-ended Bao Meixi same clan toxin enrichment purification in the various types of grain such as corn, wheat, rice, have obvious clean-up effect, the preparation cost of single solid-phase extraction column is no more than 5 yuan, the various sample substrates after purification, sensitivity is all lower than 1ng/mL, apparently higher than existing analytical approach, and the recovery is high, and precision is good.Compared with existing commercialization solid-phase extraction column, under guarantee is even better than its accuracy and reproducible prerequisite, provides cost savings greatly, reduce matrix interference significantly, significantly improve method sensitivity.
Protection scope of the present invention is not limited to the description done in embodiment, and the amendment not departing from the present invention program center all belongs to protection scope of the present invention.
Claims (4)
1. a solid-phase extraction column, is characterized in that its filler is multi-walled carbon nano-tubes.
2. solid-phase extraction column according to claim 1, is characterized in that this solid-phase extraction column comprises upper sieve plate, multi-wall carbon nano-tube tube packing and lower sieve plate.
3. the application of solid-phase extraction column described in claim 1 or 2, it can be used for carrying out enrichment purification to four kinds of A type Trichothecenes toxoids in crops simultaneously.
4. application rights requires that solid-phase extraction column described in 1 or 2 carries out a method for enrichment purification to four kinds of A type Trichothecenes toxoids in crops, and the method comprises the steps:
Carry out sample extracting solution loading;
The drip washing of first step leacheate;
The drip washing of second step leacheate;
Namely obtain containing four kinds of anatoxic sample solutions of A type Trichothecenes after elution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770818A (en) * | 2016-12-03 | 2017-05-31 | 百奥森（江苏）食品安全科技有限公司 | A kind of drawing-in type impurity absorption pattern SPE column device |
| CN109350996A (en) * | 2018-12-15 | 2019-02-19 | 浙江省食品药品检验研究院 | A kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application |
| CN109541088A (en) * | 2018-11-28 | 2019-03-29 | 北京农业质量标准与检测技术研究中心 | A kind of purification method of patulin, solid-phase extraction column and its application |
| CN111617514A (en) * | 2019-02-27 | 2020-09-04 | 中国水产科学研究院 | Solid phase extraction column with adjustable sample loading volume |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003101580A1 (en) * | 2002-05-31 | 2003-12-11 | Austria Wirtschaftsservice Gesellschaft mit beschränkter Haftung | Solid mycoctoxin carriers |
| CN103344727A (en) * | 2013-07-29 | 2013-10-09 | 江西省农业科学院农产品质量安全与标准研究所 | Method for detecting microcystins in water body by using multi-walled carbon nanotubes |
| CN103389349A (en) * | 2013-08-01 | 2013-11-13 | 浙江省海洋水产研究所 | Method for detecting content of malachite green and metabolin thereof in aquiculture environment water body |
| CN103808838A (en) * | 2014-02-14 | 2014-05-21 | 甘肃农业大学 | Extraction purification and detection analysis method for trichothecenes in potato tuber suffering dry rot |
| WO2014183013A2 (en) * | 2013-05-10 | 2014-11-13 | Luminescent MD, LLC | Guanine chemiluminescence compound and applications |
-
2015
- 2015-05-18 CN CN201510253906.9A patent/CN104931627B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003101580A1 (en) * | 2002-05-31 | 2003-12-11 | Austria Wirtschaftsservice Gesellschaft mit beschränkter Haftung | Solid mycoctoxin carriers |
| WO2014183013A2 (en) * | 2013-05-10 | 2014-11-13 | Luminescent MD, LLC | Guanine chemiluminescence compound and applications |
| CN103344727A (en) * | 2013-07-29 | 2013-10-09 | 江西省农业科学院农产品质量安全与标准研究所 | Method for detecting microcystins in water body by using multi-walled carbon nanotubes |
| CN103389349A (en) * | 2013-08-01 | 2013-11-13 | 浙江省海洋水产研究所 | Method for detecting content of malachite green and metabolin thereof in aquiculture environment water body |
| CN103808838A (en) * | 2014-02-14 | 2014-05-21 | 甘肃农业大学 | Extraction purification and detection analysis method for trichothecenes in potato tuber suffering dry rot |
Non-Patent Citations (6)
| Title |
|---|
| BANSI D. MALHOTRA 等: "Nanomaterial-Based Biosensors for Food Toxin Detection", 《APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY》, vol. 174, no. 3, 31 October 2014 (2014-10-31), pages 880 - 896, XP 035399365, DOI: doi:10.1007/s12010-014-0993-0 * |
| WEN YINGYING 等: "Recent advances in solid-phase sorbents for sample preparation prior to chromatographic analysis", 《TRAC TRENDS IN ANALYTICAL CHEMISTRY》, vol. 59, 31 August 2014 (2014-08-31), pages 26 - 41 * |
| 张素玲 等: "碳纳米管在样品前处理中的应用", 《化学通报》, vol. 74, no. 3, 31 March 2011 (2011-03-31), pages 201 - 208 * |
| 曹慧 等: "多壁碳纳米管固相萃取技术同时测定蜂蜜中多类兽药残留", 《高等学校化学学报》, vol. 34, no. 12, 31 December 2013 (2013-12-31), pages 2710 - 2715 * |
| 李圣陶 等: "多壁碳纳米管固相萃取技术的应用", 《食品工业科技》, vol. 34, no. 13, 31 July 2013 (2013-07-31), pages 373 - 377 * |
| 王红斌等: "多壁碳纳米管固相萃取—高效液相色谱法测定水中７种三唑类农药残留", 《环境污染与防治》, vol. 37, no. 4, 30 April 2015 (2015-04-30) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770818A (en) * | 2016-12-03 | 2017-05-31 | 百奥森（江苏）食品安全科技有限公司 | A kind of drawing-in type impurity absorption pattern SPE column device |
| CN109541088A (en) * | 2018-11-28 | 2019-03-29 | 北京农业质量标准与检测技术研究中心 | A kind of purification method of patulin, solid-phase extraction column and its application |
| CN109350996A (en) * | 2018-12-15 | 2019-02-19 | 浙江省食品药品检验研究院 | A kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application |
| CN111617514A (en) * | 2019-02-27 | 2020-09-04 | 中国水产科学研究院 | Solid phase extraction column with adjustable sample loading volume |
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