CN107422023B - 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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- CN107422023B CN107422023B CN201710152016.8A CN201710152016A CN107422023B CN 107422023 B CN107422023 B CN 107422023B CN 201710152016 A CN201710152016 A CN 201710152016A CN 107422023 B CN107422023 B CN 107422023B
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- 150000003349 semicarbazides Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000523 sample Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005259 measurement Methods 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000002203 pretreatment Methods 0.000 claims abstract description 7
- 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
- 239000007788 liquid 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
- 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
- 238000000691 measurement method Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 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
- 230000010355 oscillation Effects 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
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000001212 derivatisation Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 14
- 238000012360 testing method Methods 0.000 abstract description 8
- 239000012086 standard solution Substances 0.000 abstract description 4
- 239000012074 organic phase Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 10
- 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
- 238000005516 engineering process Methods 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
- 239000002778 food additive Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 230000008569 process Effects 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
- 230000009286 beneficial effect Effects 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
- 230000008859 change Effects 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
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000020477 pH reduction Effects 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
- 239000013558 reference substance 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
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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)
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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, disclose a kind of electrochemical fast detecting method of semicarbazides.The method are as follows: sample to be tested is added in hydrochloric acid solution, derivating agent progress semicarbazides derivative reaction is added, reaction solution is centrifuged, it takes supernatant liquor to adjust pH value to be extracted to after between 6~7 with organic solvent, take organic phase with being dried with nitrogen removing organic solvent, membrane filtration is used after gained extract is dissolved in bottom liquid, the sample to be tested after obtaining pre-treatment；The semicarbazides standard solution of various concentration is respectively configured, using the electrochemical signals in portable electrochemical work station measurement various concentration sample solution, draws standard curve；Then the electrochemical signals in sample to be tested are tested, the amino urea concentration in sample to be tested is calculated by standard curve.Detection method high sensitivity of the invention, testing cost is low, and field quick detection semicarbazides may be implemented.
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 technique
Semicarbazides is a kind of white crystal, soluble easily in water, chemical formula H2N-NH-CO-NH2.It is that Flour product additive is even
The metabolite of azodicarbonamide.Many countries in the world, as Canada, European Union and the U.S. etc., it is specified that azodicarbonamide dosage
45mg/kg should be lower than, " supervised about food additives are reinforced according to " People's Republic of China's the law of food safety ", hygiene department
Management work notice " (not supervising hair [2009] 89) and the Ministry of Public Health 2011 the 6th announce etc. and to provide, 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 will cause tremendous influence, continues dosage intake, will lead to rats death.
Semicarbazides has the combination of the detectors such as detection method such as high performance liquid chromatography and ultraviolet, fluorescence, liquid chromatogram matter
Compose joint technology etc., but these equipment testing costs are high, should not carry and this high performance technology in application by
Certain limitation.Electrochemical Detection is there is relatively high selectivity and sensitivity as a kind of small-sized technological merit, detects valence
Lattice are low and easy to operate, therefore are widely used in species analysis.Electrochemical detector has portable electrochemical work station and occurs,
It reduces that testing cost is low, realizes field quick detection, has certain development and application space really, there is potential practical application
Value, is beneficial to promote the use of.
Summary of the invention
In order to solve the disadvantage that the above prior art and shortcoming, the purpose of the present invention is 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) sample to be tested pre-treatment:
Sample to be tested is added in hydrochloric acid solution, it is derivative that derivating agent progress semicarbazides is added after oscillation, ultrasonic treatment
Change reaction, reaction solution be centrifuged, takes supernatant liquor to adjust pH value between 6~7, then carry out liquid-liquid extraction with organic solvent,
It takes organic phase with removing organic solvent is dried with nitrogen, membrane filtration is used after gained extract is dissolved in bottom liquid, after obtaining pre-treatment
Sample to be tested；
(2) Specification Curve of Increasing:
Ultrapure water and methanol mixed solvent configuration concentration with volume ratio for 1:1 be 0 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ
The semicarbazides sample solution of 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, using just
Take the electrochemical signals in formula electrochemical workstation measurement various concentration sample solution: electrode system uses three-electrode system, packet
Include working electrode, reference electrode, to electrode three parts, measurement method is differential pulse voltammetry；Then it is with amino urea concentration
Abscissa (X), differential pulse voltammetry signal value are ordinate (Y), draw standard curve；
(3) using the electrochemical signals in premenstrual treated the sample to be tested of portable electrochemical work station measurement, then
The amino urea concentration in sample to be tested is calculated by the standard curve of step (2).
Preferably, derivating agent described in step (1) refers to that concentration is the o-nitrobenzaldehyde solution of 0.1mol/L.
Preferably, adjusting pH value described in step (1) refers to hydrochloric acid solution and 0.3mol/L phosphoric acid using 0.2mol/L
Potassium solution adjusts pH value.
Preferably, organic solvent described in step (1) refers to ethyl acetate solution.
Preferably, bottom liquid described in step (1) refers to that the concentration that pH is 4.5 is 1mol/L hac buffer.
Preferably, filter membrane described in step (1) refers to that pore size filter is 0.45 μm of hydrophylic filter membranes.
Preferably, working electrode described in step (2) refers to that diameter is the glass-carbon electrode of 3mm；The reference electrode
For the Ag/AgCl reference electrode being dipped in saturation KCl；Described is platinum electrode to electrode.
Compared with the existing technology, detection method of the invention have the following advantages that and the utility model has the advantages that
For the present invention using semicarbazides content in portable electrochemical work station test sample, detection instrument is small and exquisite, conveniently takes
Band, method high sensitivity, testing cost is low, and field quick detection semicarbazides may be implemented, and can standardize use.
Detailed description of the invention
Fig. 1 is that (abscissa is voltage for the differential pulse voltammetry characteristic spectrogram of semicarbazides sample of various concentration 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).
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, 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) sample to be tested pre-treatment:
1.0000g (being accurate to 0.0001g) Flour product is weighed to be dissolved in 10mL 0.2mol/L hydrochloric acid solution, it is mixed with being vortexed
Clutch is ultrasonically treated after mixing, and adding 0.1mol/L o-nitrobenzaldehyde 1mL, (o-nitrobenzaldehyde solution methanol is prepared simultaneously
Dark place is stored at 4 DEG C or less, the shelf-life is one week), reaction 16 is small at 37 DEG C after then mixing on turbine mixer
When.After reaction, it is cooled to room temperature, is centrifuged, supernatant liquor is taken, with 0.2mol/L hydrochloric acid and 0.3mol/L potassium phosphate solution tune
Its pH is saved between 6~7, is then extracted with 5mL ethyl acetate, organic phase is taken to be dried with nitrogen removing ethyl acetate at normal temperature,
Gained extract is dissolved in the acetate buffer solution for the 1mol/L that 5mL pH is 4.5 and crosses 0.45 μm of hydrophylic filter membranes, before obtaining
Treated sample to be tested.
(2) Specification Curve of Increasing:
The semicarbazide hydrochloride stock solution of 100 μ g/L is prepared with the solution that ultrapure water and methanol volume ratio are 1:1 mixing, and
It saves it in dark place to store at 4 DEG C or less, for configuring semicarbazides standard solution.Then it is 0 μ g/L, 10 that concentration, which is respectively configured,
The semicarbazides of 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
Sample solution.Using the electrochemical signals in portable electrochemical work station measurement various concentration sample solution: electrode system is adopted
With three-electrode system, (Ag/ in saturation KCl is dipped in including working electrode (glass-carbon electrode that diameter is 3mm), reference electrode
AgCl reference electrode), to electrode (platinum electrode) three parts, measurement method is differential pulse voltammetry；Gained differential pulse volt
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.Close to blank sample normal concentration, taking signal-to-noise ratio is 3 meters for detection
Calculate minimum detectability.Obtain the functional relation of standard curve are as follows: Y=0.388+0.0158X (R2=0.999), minimum detection limit
For 0.003mg/kg.
(3) differential pulse in the sample to be tested using the measurement of portable electrochemical work station after step (1) pre-treatment
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 sample to be tested.
By semicarbazides content in different type Flour product in above method measurement in the market 6, the results are shown in Table 1:
The commercially available Flour product semicarbazides assay result of table 1
(NF: being not detected).
The standard deviation and the rate of recovery of detection method are verified:
(1) 3 parts of blank flour 1.0000g (being accurate to 0.0001g) are accurately weighed as matrix.Different reference substances is added
Semicarbazides content handles sample and test according to the pretreatment process and detection method of above-described embodiment.Make 5 groups under each concentration
Parallel laboratory test.The results are shown in Table 2.
The 2 mark-on flour semicarbazides rate of recovery of table 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 is
Between 92% to 99%, relative standard deviation is below 4.3%, illustrates detection method high reliablity of the invention.
(2) water quality by the aquatic products shrimp life containing semicarbazides is filtered, and 3mL sample solution is taken to be separately added into semicarbazides
Standard solution, the content that semicarbazides standard solution is added is 5 μ g/L, 10 μ g/L and 20 μ g/L, is first filtered with double-layer filter paper, acid adding
Acidification mixes, after centrifugation, then with water film filtering, pretreatment process and detection method according still further to above-described embodiment handle sample
And test, the results are shown in Table 3.
The semicarbazides rate of recovery and precision mark-on measurement result in 3 aquatic products sample of table
As seen from the results in Table 3, the rate of recovery is between 93% to 102%, and relative standard deviation is below 2.3%, data knot
Fruit shows that detection method of the invention is reliable.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (5)
1. a kind of electrochemical fast detecting method of semicarbazides, it is characterised in that including following detecting step:
(1) sample to be tested pre-treatment:
Sample to be tested is added in hydrochloric acid solution, it is anti-that derivating agent progress semicarbazides derivatization is added after oscillation, ultrasonic treatment
It answers, reaction solution is centrifuged, take supernatant liquor to adjust pH value between 6~7, then carry out liquid-liquid extraction with organic solvent, taken
Gained extract is dissolved in after the liquid of bottom with membrane filtration by machine mutually with being dried with nitrogen removing organic solvent, after obtaining pre-treatment to
Sample；
(2) Specification Curve of Increasing:
Ultrapure water and methanol mixed solvent configuration concentration with volume ratio for 1:1 be 0 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L,
The semicarbazides sample solution of 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, use are portable
Electrochemical workstation measures the electrochemical signals in various concentration sample solution: electrode system uses three-electrode system, including work
Make electrode, reference electrode, to electrode three parts, measurement method is differential pulse voltammetry；Then with amino urea concentration for horizontal seat
Mark, differential pulse voltammetry signal value are ordinate, draw standard curve；
(3) using the electrochemical signals in premenstrual treated the sample to be tested of portable electrochemical work station measurement, then pass through
The amino urea concentration in sample to be tested is calculated in the standard curve of step (2)；
Derivating agent described in step (1) refers to that concentration is the o-nitrobenzaldehyde solution of 0.1mol/L；
Working electrode described in step (2) refers to that diameter is the glass-carbon electrode of 3mm；The reference electrode is to be dipped in saturation
Ag/AgCl reference electrode in KCl；Described is platinum electrode to electrode.
2. a kind of electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that: in step (1)
The adjusting pH value, which refers to, adjusts pH value using the hydrochloric acid solution and 0.3mol/L potassium phosphate solution of 0.2mol/L.
3. a kind of 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.
4. a kind of electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that: in step (1)
The bottom liquid refers to that the concentration that pH is 4.5 is 1mol/L hac buffer.
5. a kind of electrochemical fast detecting method of semicarbazides according to claim 1, it is characterised in that: in step (1)
The filter membrane refers to that pore size filter is 0.45 μm of hydrophylic filter membranes.
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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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| A novel label-free impedimetric immunosensor for detection of semicarbazide residue based on gold nanoparticles-functional chitosan composite membrane;Wen-Jie Jin 等;《Sensors and Actuators B》;20130720;第271-279页 * |
| 氨基脲分子印迹电化学传感器的制备及应用;利健文 等;《分析化学》;20160131;第44卷(第1期);第2.1-3.5节 * |
| 液相色谱-串联质谱法测定甲壳类水产品中氨基脲的含量;于慧娟 等;《分析化学》;20121031;第40卷(第10期);第2.4节 * |
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