CN104535703B - A kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts - Google Patents
A kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts Download PDFInfo
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Abstract
The present invention relates to a kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts, by bean sprouts to be measured break process, fragmentation is placed on hydro-oxidation sodium water solution and methanol solution in vessel, after concussion shakes up, carry out light wave extraction 10s-3min, high speed centrifugation process, gets supernatant and obtains liquid to be measured through membrane filtration, liquid to be measured is entered Liquid Chromatography-Tandem Mass Spectrometry instrument and detects.The features such as the inventive method has fast, efficient, high sensitivity, for quality safety monitoring in bean sprouts, market provides new guarantee.
Description
Technical field
The present invention relates to the detection method of growth regulator in a kind of bean sprouts.
Background technology
China bean sprouts, based on workshop-based production, in order to pursue high profit, wantonly being added the phenomenon that plant growth regulator facilitates bean sprout growth and being happened occasionally in the production run of bean sprouts.Wherein 4-chlorophenoxyacetic acid (4-CPA), 6-benzyladenine (6-BA) is the principal ingredient of comparatively conventional " AB powder " in problem bean sprout cultivation process, " rootless bean sprouts element " etc.Absorption plant growth regulator in 4-CPA belongs to, the balance of energy regulating plant strain internal hormone, stimulates ovary increasing, supplements auxin in plant not enough, growth promoting effects.6-BA is similar to plant endogenous hormones structural property, can promote the formation of bud, suppresses the growth of root in bean sprout growth process.Human body takes in too much 6-BA Diazolidinyl Urea mucous membrane, occurs the phenomenons such as Nausea and vomiting.No. 159, State General Administration for Quality Supervision bulletin explicitly points out, 6-BA and 4-CPA must not as Additive Production and use." ordeal bean bud " event of illegally adding the plant growth regulator such as " AB powder ", " rootless bean sprouts element " in the process of production bean sprouts receives the concern of people gradually, becomes a significant problem of current field of food safety.
In current bean sprouts, to have pre-treating method loaded down with trivial details for the detection method of 6-BA and 4-CPA, poor sensitivity, the shortcomings such as one-component can only be detected, the standard " GB/T23381-2009 " issued as national standard body only detects to the 6-BA in bean sprouts, and method detects limit for height, be difficult to meet high-sensitive testing requirement.Each relevant departments of country are also in the detection method actively researching and developing polycomponent plant growth regulator, such as, Zhejiang Province's provincial standard " DB33/T625.3-2007 ", but, this standard pin employs different pretreatment technologies and instrument analytical method to 6-BA and 4-CPA, this certainly will will increase Detection task, consumes more resource.
Summary of the invention
The object of the invention is to overcome prior art deficiency, and a kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts is provided, the features such as the method has fast, efficient, high sensitivity, for quality safety monitoring in bean sprouts, market provides new guarantee.
The technical scheme that the present invention takes is:
Detect a method for 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts simultaneously, comprise step as follows:
(1) sample pre-treatments: by bean sprouts to be measured break process, fragmentation is placed on hydro-oxidation sodium water solution and methyl alcohol in vessel, and after concussion shakes up, carry out light wave extraction 10s-3min, high speed centrifugation process, gets supernatant and obtain liquid to be measured through membrane filtration;
(2) liquid to be measured is entered Liquid Chromatography-Tandem Mass Spectrometry instrument to detect
HPLC testing conditions:
Chromatographic column: EclipsePlusC18;
Mobile phase: A phase is the formic acid water of 0.1% (v/v), and B phase is acetonitrile;
Flow velocity: 0.2mL/min;
Column temperature: 30 DEG C;
Sample size: 10 μ L;
Gradient elution program: 0 ~ 4min, B phase rises to 65% from 25%, 4 ~ 5min, B phase rises to 100% from 65%, and 5 ~ 7.2min, B phase keeps 100% constant, and 7.2 ~ 7.3min, B phase is down to 25% from 100%, and 7.3 ~ 10min, B phase keeps 25% constant;
MS/MS condition:
Adopt multiple-reaction monitoring pattern;
Ion gun: electric spray ion source (+ESI);
6-benzyladenine adopts positive ion mode to detect, and 4-chlorophenoxyacetic acid sodium adopts negative ion mode to detect;
Dry gas: N
2, dry gas temperature: 300 DEG C, dry gas flow velocity: 10L/min;
Atomizing pressure: 30Psi;
Capillary voltage: 4000V;
6-benzyladenine and 4-chlorophenoxyacetic acid sodium parent ion and daughter ion parameter see the following form:
The concentration of the sodium hydrate aqueous solution in said method described in step (1) is 10mM, and addition is every gram of broken bean sprouts 0.5ml; Methyl alcohol addition is every gram of broken bean sprouts 0.5ml.
Described light wave extracts preferred 2min.
Described high speed centrifugation is treated to the centrifugal 10min of first 8000rpm; Get the supernatant centrifugal 10min of 12000rpm again.
In order to compare light wave extraction method and the ultrasonic extraction extraction efficiency to 6-benzyladenine and 4-chlorophenoxyacetic acid sodium, the standard solution of 40 and 100ng/g is added in blank moyashi sample, 3min is got indescribably with ultrasonic wave added and light wave auxiliary separating, other experiment conditions are identical, the peak area of comparison object thing.Experimental result draws, the effect that light wave extracts, a little more than ultrasonic extraction, therefore uses the pre-treating method of light wave assisted extraction.
For studying the impact of different extraction times on the extraction efficiency of 6-benzyladenine and 4-chlorophenoxyacetic acid sodium, light wave extraction time is constantly increased to 2.5min by 10s, and comparison object thing peak area changes.Result shows, in 10s-2.0min, extraction time is directly proportional to peak area increases, and the light wave time, peak area was substantially constant more than after 2min.Therefore this experiment light wave extraction time is preferably 2min.
In order to reach the best chromatogram separating effect to 6-benzyladenine and 4-chlorophenoxyacetic acid sodium, conventional flow visualizing and chromatographic column are investigated.Experiment is to acetonitrile-water system and methanol-water system, and when experimental result shows to use acetonitrile-0.1% formic acid aqueous systems as mobile phase, chromatographic peak profile is symmetrical, highly sensitive.The chromatographic column of different model is investigated, finds use the good separating effect of EclipsePlusC18 chromatographic column and have good chromatographic peak profile.
The present invention is based on pre-treatment while that light wave assisted extraction and high performance liquid chromatography-tandem mass (HPLC-MS/MS) developing a kind of and detect the new method of 6-benzyladenine and 4-chlorophenoxyacetic acid sodium, achieve the multi-analyte immunoassay of plant growth regulator in bean sprouts.The features such as the method has fast, efficient, high sensitivity, for quality safety monitoring in bean sprouts, market provides new guarantee.
Accompanying drawing explanation
Fig. 1 is 6-benzyladenine and 4-chlorophenoxyacetic acid sodium MRM chromatogram;
Fig. 2 is that different extraction time is on the impact of extraction efficiency.
Embodiment
Further illustrate below in conjunction with specific embodiment.
The key instrument used in embodiment has: Agilent-1200 type quick separating high performance liquid chromatography (Agilent company), 6410 type triplex tandem level Four bars mass spectrum (Agilent company).Acetonitrile (chromatographically pure, Tedia company).All experiment reagents are all preserved at 4 DEG C.
Embodiment 1
(1) pretreatment process
Get bean sprouts to be measured sample to put into historrhexis's machine and carry out break process, get broken good sample 10g, be placed in 50mL tool screw top centrifuge pipe; Add 5mL10mM sodium hydrate aqueous solution and 5mL methanol solution, after concussion shakes up, carry out light wave extraction 2min (noting abundant illumination), the centrifugal 10min of rear 8000rpm; Get supernatant 1mL, be placed in 1.5mL centrifuge tube, the centrifugal 10min of 12000rpm, get supernatant 0.45 μm of membrane filtration, put into auto injection bottle to be measured.
(2) liquid to be measured is entered Liquid Chromatography-Tandem Mass Spectrometry instrument to detect
HPLC condition
Chromatographic column: EclipsePlusC18 (2.1mm × 150mm, 3.1 μm, Agilent company).Mobile phase: A phase is the formic acid water of 0.1%, and B phase is acetonitrile.Gradient elution program: 0 ~ 4min, B phase rises to 65% from 25%, 4 ~ 5min, B phase rises to 100% from 65%, and 5 ~ 7.2min, B phase keeps 100% constant, and 7.2 ~ 7.3min, B phase is down to 25% from 100%, and 7.3 ~ 10min, B phase keeps 25% constant.Flow velocity: 0.2mL/min.Column temperature: 30 DEG C, sample size: 10 μ L.
MS/MS condition
Ion gun: electric spray ion source (+ESI), 6-benzyladenine adopts positive ion mode to detect, and 4-chlorophenoxyacetic acid sodium adopts negative ion mode to detect.Dry gas: N
2, dry gas temperature: 300 DEG C, dry gas flow velocity: 10L/min, atomizing pressure: 30Psi, capillary voltage: 4000V.Adopt multiple-reaction monitoring pattern, 6-benzyladenine and 4-chlorophenoxyacetic acid sodium parent ion and daughter ion parameter are in table 1, and MRM spectrogram is shown in Fig. 1.
Table 16-benzyladenine and 4-chlorophenoxyacetic acid sodium
Embodiment 2
Testing procedure is with embodiment 1, and difference for a change light wave extraction time is constantly increased to 2.5min by 10s, and the change of object peak area is as Fig. 2.
Embodiment 3
Testing procedure is with embodiment 1, and difference is that cracked voltage changes at 10V ~ 150V, the mass-to-charge ratio of parent ion and different collision energy (0V ~ 40V),
Experimental technique is as follows: first, under the pattern of Select ion monitor, and input sample parent ion mass-to-charge ratio, optimize cracked voltage (10V ~ 120V), ensure the maximum transmitted efficiency of parent ion, namely as far as possible arrive collision pond more, specific experiment the results are shown in Figure 1, Fig. 2; Then, under daughter ion scan pattern, the input mass-to-charge ratio of parent ion and different collision energy (0V ~ 40V), investigate the impact of different collision energy on parent ion and daughter ion peak intensity, parent ion is selected almost to disappear, collision energy when daughter ion intensity is maximum.
Linear relationship and detection limit test
Get 6-benzyladenine and 4-chlorophenoxyacetic acid sodium standard reserving solution, the mixed standard solution of a series of different quality concentration of accurate formulation, under condition after optimizing, sample introduction measures respectively, repeat 6 times, with the mean value (Y) of each material quota ion peak area to the mass concentration (X of tested component, mg/mL) carry out linear regression, obtain regression equation, related coefficient and the range of linearity; With the concentration of signal to noise ratio (S/N ratio) (S/N) > 3 correspondence for detection limit, (S/N) concentration of > 10 correspondence is as quantitative limit, obtains detection limit and the quantitative limit of 6-benzyladenine and 4-chlorophenoxyacetic acid sodium.Result proves (table 2), and this method significantly lower than GB/T23381-2009, and is more starkly lower than DB33/T625.3-2007 to 4-chlorophenoxyacetic acid sodium to the detection limit of 6-benzyladenine.
The linear equation of table 2. object, the range of linearity, related coefficient, quantitative limit and detection limit
The mensuration high performance liquid chromatography of 6-benzyladenine in a.GB/T23381-2009 food
The nuisanceless bean sprouts of b.DB33/T625.3-2007 the 3rd part: the mensuration of 6-benzyladenine residual quantity and 4-chlorophenoxyacetic acid sodium residual quantity.
Recovery of standard addition:
Standard solution (3 Pitch-based sphere of 6-benzyladenine and 4-chlorophenoxyacetic acid sodium are added in mung bean sprouts and each a sample of moyashi, 20,100 and 500ng/g and 8,40 and 200ng/g), calculate its recovery and precision, replication 3 times, result is as shown in table 3.
The blank TIANZHU XINGNAO Capsul of table 3.6-benzyladenine and 4-chlorophenoxyacetic acid sodium and Precision test result (n=3)
A. the recovery is matrix relative recovery
The detection of actual sample
Utilize the bean sprouts (mung bean sprouts and moyashi each 2 kind) of this method to 4 different regions to detect, all do not detect 6-benzyladenine and 4-chlorophenoxyacetic acid sodium.
The present invention establishes the method for 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in high performance liquid chromatography-triplex tandem quadrupole rod Mass Spectrometer Method bean sprouts, the method pretreatment process is simple and quick, handling safety, and method is highly sensitive, reliable results meets testing requirement, can realize 6-benzyladenine in bean sprouts and 4-chlorophenoxyacetic acid sodium detects fast.
Claims (4)
1. detect a method for 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts simultaneously, it is characterized in that, comprise step as follows:
(1) sample pre-treatments: by bean sprouts to be measured break process, fragmentation is placed on hydro-oxidation sodium water solution and methyl alcohol in vessel, and after concussion shakes up, carry out light wave extraction 10s-3min, high speed centrifugation process, gets supernatant and obtain liquid to be measured through membrane filtration;
(2) liquid to be measured is entered Liquid Chromatography-Tandem Mass Spectrometry instrument to detect
HPLC testing conditions:
Chromatographic column: EclipsePlusC18;
Mobile phase: A phase is the formic acid water of 0.1%, and B phase is acetonitrile;
Flow velocity: 0.2mL/min;
Column temperature: 30 DEG C;
Sample size: 10 μ L;
Gradient elution program: 0 ~ 4min, B phase rises to 65% from 25%, 4 ~ 5min, B phase rises to 100% from 65%, and 5 ~ 7.2min, B phase keeps 100% constant, and 7.2 ~ 7.3min, B phase is down to 25% from 100%, and 7.3 ~ 10min, B phase keeps 25% constant;
MS/MS condition:
Adopt multiple-reaction monitoring pattern;
Ion gun: electric spray ion source;
6-benzyladenine adopts positive ion mode to detect, and 4-chlorophenoxyacetic acid sodium adopts negative ion mode to detect;
Dry gas: N
2, dry gas temperature: 300 DEG C, dry gas flow velocity: 10L/min;
Atomizing pressure: 30Psi;
Capillary voltage: 4000V;
6-benzyladenine and 4-chlorophenoxyacetic acid sodium parent ion and daughter ion parameter see the following form:
2. a kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts according to claim 1, it is characterized in that, the concentration of the sodium hydrate aqueous solution described in step (1) is 10mM, and addition is every gram of broken bean sprouts 0.5ml; Methyl alcohol addition is every gram of broken bean sprouts 0.5ml.
3. a kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts according to claim 1, is characterized in that, described light wave extraction is 2min.
4. a kind of method simultaneously detecting 6-benzyladenine and 4-chlorophenoxyacetic acid sodium in bean sprouts according to claim 1, it is characterized in that, described high speed centrifugation is treated to the centrifugal 10min of first 8000rpm; Get the supernatant centrifugal 10min of 12000rpm again.
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| CN106404972B (en) * | 2016-03-14 | 2019-10-25 | 浙江省检验检疫科学技术研究院 | Gas-chromatography tandem mass spectrometry measures the remaining method of 6 plant growth regulators in bean sprouts simultaneously |
| CN107621498A (en) * | 2016-07-14 | 2018-01-23 | 罗牛山莱茵检测认证服务（海南）有限公司 | The detection method of one plant growth regulators residual |
| CN109212064A (en) * | 2018-09-19 | 2019-01-15 | 遵义市产品质量检验检测院 | The detection method of one plant growth regulators residual volume |
| CN109655555A (en) * | 2019-02-15 | 2019-04-19 | 中山出入境检验检疫局检验检疫技术中心 | A kind of method of 6-benzyladenine in measurement bean sprouts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05123174A (en) * | 1991-10-02 | 1993-05-21 | Ishikawajima Harima Heavy Ind Co Ltd | Production of fluorescent substance using cultured strawberry cell |
| CN102928530A (en) * | 2012-10-15 | 2013-02-13 | 谱尼测试科技股份有限公司 | Detection method for measuring residual quantity of urea in bean sprout by high performance liquid chromatography |
-
2015
- 2015-01-06 CN CN201510004968.6A patent/CN104535703B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05123174A (en) * | 1991-10-02 | 1993-05-21 | Ishikawajima Harima Heavy Ind Co Ltd | Production of fluorescent substance using cultured strawberry cell |
| CN102928530A (en) * | 2012-10-15 | 2013-02-13 | 谱尼测试科技股份有限公司 | Detection method for measuring residual quantity of urea in bean sprout by high performance liquid chromatography |
Non-Patent Citations (6)
| Title |
|---|
| Development of a novel amide-silica stationary phase for the reversed-phase HPLC separation of different classes of phytohormones;Hayriye Aral 等;《Talanta》;20130514;第116卷;第155–163页 * |
| Simultaneous Determination of 15 Plant Growth Regulators in Bean Sprout and Tomato with Liquid Chromatography–Triple Quadrupole Tandem Mass Spectrometry;Liyan Ma 等;《Food Anal. Methods》;20120921;第6卷;第941–951页 * |
| 四极杆飞行时间质谱法同时检测豆芽中的３种外源植物激素残留.《色谱》.2014,第32卷(第5期),第493～498页. * |
| 固相萃取-超高效液相色谱串联质谱法同时测定豆芽中6-苄基腺嘌呤、赤霉素和4-氯苯氧乙酸的残留量;张婧雯 等;《中国食品卫生杂志》;20140531;第26卷(第5期);第441-445页 * |
| 谢寒冰 等.高效液相色谱⁃ * |
| 超高效液相色谱-串联质谱法测定豆芽中7种药物残留;刘春生 等;《质谱学报》;20140731;第35卷(第4期);第302-310页 * |
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Application publication date: 20150422 Assignee: Shandong blue city analysis Co. Ltd. Assignor: Shandong Analysis Test Center Contract record no.: 2017370000043 Denomination of invention: Method for detecting 6-benzyladenine and 4-sodium chlophenoxycetate in bean sprouts at the same time Granted publication date: 20160210 License type: Common License Record date: 20170628 |
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