CN107422023A - A kind of electrochemical fast detecting method of semicarbazides - Google Patents
A kind of electrochemical fast detecting method of semicarbazides Download PDFInfo
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- CN107422023A CN107422023A CN201710152016.8A CN201710152016A CN107422023A CN 107422023 A CN107422023 A CN 107422023A CN 201710152016 A CN201710152016 A CN 201710152016A CN 107422023 A CN107422023 A CN 107422023A
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- 150000003349 semicarbazides Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000523 sample Substances 0.000 claims abstract description 23
- 238000012360 testing method Methods 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000012488 sample solution Substances 0.000 claims abstract description 8
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000006228 supernatant Substances 0.000 claims abstract description 4
- 238000005374 membrane filtration Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 2
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000001212 derivatisation Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 3
- 239000012074 organic phase Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 235000013312 flour Nutrition 0.000 description 9
- 238000011084 recovery Methods 0.000 description 5
- 241000700159 Rattus Species 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical class NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005180 public health Effects 0.000 description 2
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to technical field of analytical chemistry, discloses a kind of electrochemical fast detecting method of semicarbazides.Methods described is：Detected sample is added in hydrochloric acid solution and adds derivating agent progress semicarbazides derivative reaction, reaction solution is centrifuged, take supernatant liquor to adjust pH value to be extracted with organic solvent to after between 6~7, the drying of organic phase nitrogen is taken to remove organic solvent, membrane filtration is used after gained extract is dissolved in into bottom liquid, obtains the testing sample after pre-treatment；The semicarbazides standard liquid of various concentrations is respectively configured, the electrochemical signals in various concentrations sample solution are measured using portable electrochemical work station, draw standard curve；Then the electrochemical signals tested in testing sample, the amino urea concentration in testing sample is calculated by standard curve.The detection method high sensitivity of the present invention, testing cost are low, it is possible to achieve field quick detection semicarbazides.
Description
Technical field
The invention belongs to technical field of analytical chemistry, and in particular to a kind of electrochemical fast detecting method of semicarbazides.
Background technology
Semicarbazides, it is a kind of white crystal, soluble in water, chemical formula H2N-NH-CO-NH2.It is Flour product additive idol
The metabolite of azodicarbonamide.Many countries in the world, as Canada, European Union and the U.S. etc. are, it is specified that the dosage of azodicarbonamide
45mg/kg should be less than, according to《People's Republic of China's the law of food safety》, hygiene department《On strengthening food additives supervision
Management work notifies》The regulations such as No. 6 bulletin of (not supervising hair [2009] 89) and the Ministry of Public Health 2011 year, in food additive in 2011
The maximum usage amount for adding azodicarbonamide in agent product standard bulletin (Ministry of Public Health announce 2011 No. 8) wheat flour is
0.045g/kg(GB2760-2007).As for semicarbazides, 40mg/kg semicarbazides, the secretion of rat sex hormone are injected to infant rats
Horizontal and multiple reproductive organs can cause tremendous influence, continue dosage intake, can cause rats death.
The existing detector such as detection method such as high performance liquid chromatography and ultraviolet, the fluorescence combination of semicarbazides, liquid chromatogram matter
Compose GC-MS etc., but these equipment testing costs are high, should not carry and this high performance technology on applying by
Certain limitation.Electrochemical Detection is there is selectivity and sensitivity that comparison is high as a kind of small-sized technological merit, detects valency
Lattice are low and easy to operate, therefore are widely used in species analysis.The existing portable electrochemical work station of electrochemical detector occurs,
Reduce that testing cost is low, realizes field quick detection, have certain development and application space really, there is potential practical application
Value, is beneficial to promote the use of.
The content of the invention
In order to solve the shortcomings that above prior art and weak point, it is an object of the invention to provide a kind of semicarbazides
Electrochemical fast detecting method.
The object of the invention is achieved through the following technical solutions：
A kind of electrochemical fast detecting method of semicarbazides, including following detecting step：
(1) testing sample pre-treatment：
Detected sample is added in hydrochloric acid solution, vibration, derivating agent progress semicarbazides derivative is added after being ultrasonically treated
Change reaction, reaction solution centrifuged, take supernatant liquor to adjust pH value between 6~7, then carry out liquid-liquid extraction with organic solvent,
Take the drying of organic phase nitrogen to remove organic solvent, membrane filtration is used after gained extract is dissolved in into bottom liquid, after obtaining pre-treatment
Testing sample；
(2) Specification Curve of Increasing：
Using volume ratio as 1:1 ultra-pure water and methanol mixed solvent configuration concentration is 0 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ
G/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L and 100 μ g/L semicarbazides sample solution, using just
Take the electrochemical signals in formula electrochemical workstation measurement various concentrations sample solution：Electrode system uses three-electrode system, bag
Include working electrode, reference electrode, to electrode three parts, measuring method is differential pulse voltammetry；Then using amino urea concentration as
Abscissa (X), differential pulse voltammetry signal value are ordinate (Y), draw standard curve；
(3) electrochemical signals in the testing sample after pre-treatment are measured using portable electrochemical work station, then
The amino urea concentration in testing sample is calculated by the standard curve of step (2).
Preferably, the derivating agent described in step (1) refers to the o-nitrobenzaldehyde solution that concentration is 0.1mol/L.
Preferably, hydrochloric acid solution and 0.3mol/L phosphoric acid that pH value refers to use 0.2mol/L are adjusted described in step (1)
Potassium solution adjusts pH value.
Preferably, organic solvent refers to ethyl acetate solution described in step (1).
Preferably, the bottom liquid described in step (1) refers to that the concentration that pH is 4.5 is 1mol/L hac buffers.
Preferably, the filter membrane described in step (1) refers to the hydrophylic filter membranes that pore size filter is 0.45 μm.
Preferably, the working electrode described in step (2) refers to a diameter of 3mm glass-carbon electrode；Described reference electrode
To be dipped in the Ag/AgCl reference electrodes in saturation KCl；Described is platinum electrode to electrode.
Relative to prior art, detection method of the invention has the following advantages that and beneficial effect：
For the present invention using semicarbazides content in portable electrochemical work station detection sample, detection instrument is compact, conveniently takes
Band, method high sensitivity, testing cost are low, it is possible to achieve field quick detection semicarbazides, can standardize use.
Brief description of the drawings
Fig. 1 is that (abscissa is voltage for the differential pulse voltammetry characteristic spectrograms of semicarbazides sample of various concentrations in embodiment
It is worth (V), ordinate is current value (A))；
Fig. 2 is that according to the standard curve of differential pulse voltammetry characteristic spectrogram result drafting, (abscissa is amino in embodiment
Urea concentration, ordinate are signal value of the semicarbazides in differential pulse voltammetry).
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment
The present embodiment carries out the detection of semicarbazides content to different type Flour product product in the market 6：
(1) testing sample pre-treatment：
1.0000g (being accurate to 0.0001g) Flour product is weighed to be dissolved in 10mL 0.2mol/L hydrochloric acid solutions, it is mixed with being vortexed
Clutch is ultrasonically treated after mixing, and adding 0.1mol/L o-nitrobenzaldehydes 1mL, (o-nitrobenzaldehyde solution methanol is prepared simultaneously
Dark place is stored in below 4 DEG C, its shelf-life is one week), reaction 16 is small at 37 DEG C after then being mixed on turbine mixer
When.After reaction terminates, room temperature is cooled to, centrifuges, takes supernatant liquor, is adjusted with 0.2mol/L hydrochloric acid and 0.3mol/L potassium phosphate solutions
Its pH is saved between 6~7, is then extracted with 5mL ethyl acetate, takes organic phase nitrogen drying at normal temperatures to remove ethyl acetate,
Gained extract is dissolved in the acetate buffer solution for the 1mol/L that 5mL pH are 4.5 and crosses 0.45 μm of hydrophylic filter membranes, before obtaining
Testing sample after processing.
(2) Specification Curve of Increasing：
It is 1 with ultra-pure water and methanol volume ratio:The solution of 1 mixing prepares 100 μ g/L semicarbazide hydrochloride storing solution, and
Save it in dark place to store below 4 DEG C, for configuring semicarbazides standard liquid.Then concentration is respectively configured as 0 μ g/L, 10
μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L semicarbazides
Sample solution.Electrochemical signals in various concentrations sample solution are measured using portable electrochemical work station：Electrode system is adopted
(Ag/ in saturation KCl is dipped in three-electrode system, including working electrode (a diameter of 3mm glass-carbon electrode), reference electrode
AgCl reference electrodes), to electrode (platinum electrode) three parts, measuring method is differential pulse voltammetry；Gained differential pulse lies prostrate
It is as shown in Figure 1 to pacify characteristic spectrogram.Then using amino urea concentration as abscissa (X), differential pulse voltammetry signal value is ordinate
(Y) standard curve, is drawn, gained standard curve is as shown in Figure 2.Detection takes signal to noise ratio as 3 meters close to blank sample normal concentration
Calculate minimum detectability.The functional relation for obtaining standard curve is：Y=0.388+0.0158X (R2=0.999), minimum detection limit
For 0.003mg/kg.
(3) differential pulse in the testing sample after step (1) pre-treatment is measured using portable electrochemical work station
Voltammetric signal value, each type Flour product take 5 samples to be tested, and are then calculated by the standard curve of step (2)
Amino urea concentration in testing sample.
The result that semicarbazides content in different type Flour product in the market 6 is determined by above method is as shown in table 1：
The commercially available Flour product semicarbazides assay result of table 1
(NF：Do not detect).
The standard deviation and the rate of recovery of detection method are verified：
(1) accurately weighing 3 parts of blank flour 1.0000g (being accurate to 0.0001g) is used as matrix.Add different reference materials
Semicarbazides content, sample and test are handled according to the pretreatment process and detection method of above-described embodiment.Make 5 groups under each concentration
Parallel laboratory test.As a result it is as shown in table 2.
The mark-on flour semicarbazides rate of recovery of table 2 and precision testing result
As seen from the results in Table 2, when the semicarbazides standard for being separately added into 5 μ g/L, 20 μ g/L and 50 μ g/L concentration, the rate of recovery are
Between 92% to 99%, relative standard deviation is below 4.3%, illustrates that the detection method reliability of the present invention is high.
(2) water quality that the aquatic products shrimp containing semicarbazides lives is filtered, takes 3mL sample solutions to be separately added into semicarbazides
Standard liquid, the content for adding semicarbazides standard liquid is 5 μ g/L, 10 μ g/L and 20 μ g/L, is first filtered with double-layer filter paper, acid adding
Acidifying, mix, after centrifugation, then with water film filtering, pretreatment process and detection method processing sample according still further to above-described embodiment
And test, as a result as shown in table 3.
The semicarbazides rate of recovery and precision mark-on measurement result in the aquatic products sample of table 3
As seen from the results in Table 3, between the rate of recovery is 93% to 102%, relative standard deviation is below 2.3%, data knot
Fruit shows that the detection method of the present invention is reliable.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of electrochemical fast detecting method of semicarbazides, it is characterised in that including following detecting step：
(1) testing sample pre-treatment：
Detected sample is added in hydrochloric acid solution, it is anti-that derivating agent progress semicarbazides derivatization is added after vibration, supersound process
Should, reaction solution is centrifuged, takes supernatant liquor to adjust pH value between 6~7, then carries out liquid-liquid extraction with organic solvent, taken
Machine is mutually dried up with nitrogen and removes organic solvent, is used membrane filtration after gained extract is dissolved in into bottom liquid, is obtained treating after pre-treatment
Test sample product；
(2) Specification Curve of Increasing：
Using volume ratio as 1:1 ultra-pure water and methanol mixed solvent configuration concentration be 0 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L,
40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L and 100 μ g/L semicarbazides sample solution, use are portable
Electrochemical signals in electrochemical workstation measurement various concentrations sample solution：Electrode system uses three-electrode system, including work
Make electrode, reference electrode, to electrode three parts, measuring method is differential pulse voltammetry；Then using amino urea concentration as horizontal seat
Mark, differential pulse voltammetry signal value is ordinate, draws standard curve；
(3) electrochemical signals in the testing sample after pre-treatment are measured using portable electrochemical work station, then passed through
The amino urea concentration in testing sample is calculated in the standard curve of step (2).
A kind of 2. electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that：In step (1)
Described derivating agent refers to the o-nitrobenzaldehyde solution that concentration is 0.1mol/L.
A kind of 3. electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that：In step (1)
The regulation pH value refers to hydrochloric acid solution and 0.3mol/L potassium phosphate solutions the regulation pH value using 0.2mol/L.
A kind of 4. electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that：In step (1)
The organic solvent refers to ethyl acetate solution.
A kind of 5. electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that：In step (1)
Described bottom liquid refers to that the concentration that pH is 4.5 is 1mol/L hac buffers.
A kind of 6. electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that：In step (1)
Described filter membrane refers to the hydrophylic filter membranes that pore size filter is 0.45 μm.
A kind of 7. electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that：The step
(2) working electrode described in refers to a diameter of 3mm glass-carbon electrode；Described reference electrode is the Ag/ being dipped in saturation KCl
AgCl reference electrodes；Described is platinum electrode to electrode.
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| CN201710152016.8A CN107422023B (en) | 2017-03-15 | 2017-03-15 | A kind of electrochemical fast detecting method of semicarbazides |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108181372A (en) * | 2017-12-20 | 2018-06-19 | 嘉兴学院 | The detection method of nitre sulphur ketone residual quantity in corn |
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| CN103487529A (en) * | 2013-10-15 | 2014-01-01 | 谱尼测试科技(天津)有限公司 | Method for detecting residual amount of semi carbazide in flour and flour products by high performance liquid chromatography |
| CN104569168A (en) * | 2013-10-17 | 2015-04-29 | 苏州市产品质量监督检验所 | Detection method for liquid chromatography tandem mass spectrometry of semi carbazide |
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2017
- 2017-03-15 CN CN201710152016.8A patent/CN107422023B/en not_active Expired - Fee Related
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| CN103487529A (en) * | 2013-10-15 | 2014-01-01 | 谱尼测试科技(天津)有限公司 | Method for detecting residual amount of semi carbazide in flour and flour products by high performance liquid chromatography |
| CN104569168A (en) * | 2013-10-17 | 2015-04-29 | 苏州市产品质量监督检验所 | Detection method for liquid chromatography tandem mass spectrometry of semi carbazide |
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| WEN-JIE JIN 等: "A novel label-free impedimetric immunosensor for detection of semicarbazide residue based on gold nanoparticles-functional chitosan composite membrane", 《SENSORS AND ACTUATORS B》 * |
| 于慧娟 等: "液相色谱-串联质谱法测定甲壳类水产品中氨基脲的含量", 《分析化学》 * |
| 利健文 等: "氨基脲分子印迹电化学传感器的制备及应用", 《分析化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108181372A (en) * | 2017-12-20 | 2018-06-19 | 嘉兴学院 | The detection method of nitre sulphur ketone residual quantity in corn |
| CN108181372B (en) * | 2017-12-20 | 2019-12-10 | 嘉兴学院 | Method for detecting residual quantity of mesotrione in corn |
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