CN104914096A - Clenbuterol detection operating fluid and detection method thereof - Google Patents
Clenbuterol detection operating fluid and detection method thereof Download PDFInfo
- Publication number
- CN104914096A CN104914096A CN201510230199.1A CN201510230199A CN104914096A CN 104914096 A CN104914096 A CN 104914096A CN 201510230199 A CN201510230199 A CN 201510230199A CN 104914096 A CN104914096 A CN 104914096A
- Authority
- CN
- China
- Prior art keywords
- clenbuterol
- solution
- μms
- melamine
- testing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a clenbuterol detection operating fluid and a method thereof. The operating fluid is a colloidal solution obtained through mixing nano-gold colloid with a melamine solution, wherein the colloid particle size of the nano-gold colloid is smaller than 8nm; and the concentration of the melamine solution is 5[mu]M. The operating fluid combining the clenbuterol and melamine synergistically induced nano-gold aggregation effect and the catalytic activity of nano-gold mimic enzyme, and can be used to detect clenbuterol in a sample. A mimic enzyme chromogenic substrate involved in the invention is TMB, and the involved sample contains urine and pork. The clenbuterol visualization detection method has the advantages of high sensitivity, low cost and very good application prospect, and provides necessary support for future researches, production and supervision.
Description
Technical field
The invention belongs to technical field of analytical chemistry, relate to a kind of Clenbuterol testing liquid and detection method.
Background technology
Clenbuterol is the one of beta-receptor activator, is used for the treatment of the diseases such as bronchial astehma, chronic bronchitis and pulmonary emphysema.Heavy dose is used in feed and can promotes that lipolysis suppresses fat deposition, can significantly improve the lean meat percentage of trunk, improves meat and improve food conversion ratio, therefore cry again " clenbuterol hydrochloride ".
But, can be formed residual after Clenbuterol uses in RP-HPLC, especially residual higher at the internal organs such as liver of pig, enter human body after edible and can cause cardiovascular and toxic and side effect that is central nervous system, directly be detrimental to health, therefore, as far back as dispatch in 1997, the Ministry of Agriculture forbade that clenbuterol hydrochloride uses in feed and husbandry sector.Dec 27 calendar year 2001, on February 9th, 2002, April 9, the Ministry of Agriculture issues the documents respectively and forbids that food animal prohibits the use beta-agonists class medicine as feed addictive (No. 176, the Ministry of Agriculture, No. 193 bulletins, No. 1519 regulations).
Because " clenbuterol hydrochloride " can bring more economic worths, be widely used in husbandry sector as the illegal medicine that adds for a long time.The clenbuterol hydrochloride poisoning that China reports the earliest causes for port live hog for 1998, after this this kind of event often occurs, on April 27th, 2009, the United Daily News is reported: in domestic beef items (beef oil, steamed beef soup) found hydrochloric Clenbuterol by Korea S again.Henan Shuan Hui " 3.15 " " clenbuterol hydrochloride " event in the shock whole nation in 2011, has pushed to the teeth of the storm residual to " clenbuterol hydrochloride " especially." clenbuterol hydrochloride " residual event has become the malignant tumor in China's aquaculture and meat food safety field, and the development and the foodstuff security system that seriously hinder China's animal husbandry are set up.
The method of current detection Clenbuterol is mainly divided into two large classes: instrument analytical method and immune analysis method.Instrument analytical method mainly comprises combined gas chromatography mass spectrometry (GC-MS, GC-MS/MS), high performance liquid chromatography (HPLC), high performance liquid chromatography MS (HPLC-MS, HPLC-MS/MS), capillary electrophoresis (CE) etc.Immune analysis method mainly comprises euzymelinked immunosorbent assay (ELISA) (ELISA), radio immunoassay (IA) colloid gold immune affinity chromatography (GICA) etc.But due to the complicacy of food samples and sample size huge, existing analytical approach can not meet the needs of beta-receptor activator fast high-flux examination.Therefore need to set up a kind of method that is quick, simple, sensitive, low cost and detect Clenbuterol in food; In No. 235, Ministry of Agriculture bulletin regulation to the requirement of Clenbuterol for must not detect in all Edible tissues of all food animals.
Summary of the invention
The present invention is directed to defect of the prior art and deficiency, provide the new approaches that a kind of Clenbuterol detects, solve existing detection means can not fast, multiple types detection sample and the problem that wastes time and energy of testing process.
For solving the problem, the technical scheme that the present invention takes is:
A kind of Clenbuterol testing liquid, this working fluid is the colloidal solution obtained after nm of gold colloid and melamine solution mix, wherein: the colloidal particle size of described nm of gold colloid is less than 8nm; The concentration of described melamine solution is 4 ~ 6 μMs.
Concrete, described nm of gold colloid and the volume ratio of melamine solution are 7 ~ 11:1.
A kind of Determination of Clenbuterol, carries out chromogenic reaction by described Clenbuterol testing liquid and Clenbuterol standard solution, hydrogen peroxide and TMB and obtains standard color solution;
Testing sample solution and Clenbuterol testing liquid, hydrogen peroxide and TMB described in claim 1 or 2 carry out chromogenic reaction and obtain testing sample nitrite ion;
Testing sample nitrite ion and standard color solution are compared and obtains Cologne special sieve content detection value range.
Concrete, described Clenbuterol testing liquid and the volume ratio of Clenbuterol standard solution are 4.9 ~ 3.8:1, and the concentration of Clenbuterol standard solution is 0 μM, 5 μMs, 10 μMs, 20 μMs, 30 μMs and 50 μMs.
More specifically, described testing sample solution comprises urine sample dilution and bio-tissue sample extracting solution.
Further, this detection method also comprises and obtains the special sieve concentration standard curve in absorbance and Cologne by absorption photometry to the absorbance measurement that standard color solution carries out, then obtains the special sieve concentration value in Cologne by the absorbance measurement that absorption photometry carries out testing sample nitrite ion.
Beneficial effect of the present invention is:
(1) Clenbuterol combines with the congregation of melamine co-induction nm of gold and the catalytic activity of nm of gold analogue enztme by the present invention, can detect the Clenbuterol in sample, for later research, production and supervision etc. provide necessary support;
(2) after the present invention is simultaneously mixed with the Clenbuterol of variable concentrations as testing liquid after being mixed with melamine by the nm of gold colloid of a series of research discovery below 8nm, catalysis TMB and hydrogen peroxide colour developing obtain the solution showing different colours, the detection of Clenbuterol in urine sample can not only be carried out, the detection of Clenbuterol in animal tissue's sample can also be carried out, expand the kind of Clenbuterol energy sample product;
(3) in addition, testing liquid prepared by the present invention can be preserved 7 days at 4 DEG C, can with get with, mix with measuring samples and add again after TMB and hydrogen peroxide develop the color and can detect, with existing first melamine and the Clenbuterol of variable concentrations are mixed add nm of gold again after show different colors and compare the error decreasing and cause because drawing this operation of micro liquid, operating process is simultaneously more convenient, decreases the operation of an imbitition.
Accompanying drawing explanation
Fig. 1 is that the concentration (μM) of Clenbuterol is followed successively by 0,5,10,20,30 and 50 from left to right only containing the color camera of the Clenbuterol testing liquid of variable concentrations in embodiment 1;
Fig. 2 is the color camera of the Clenbuterol testing liquid containing variable concentrations after adding hydrogen peroxide and TMB in embodiment 1, and the concentration (μM) of Clenbuterol is followed successively by 0,5,10,20,30 and 50 from left to right;
Fig. 3 is the colorimetric card of the Clenbuterol detection system containing variable concentrations obtained in embodiment 1, and the concentration (μM) of Clenbuterol is 0,5,10,20,30 and 50 from left to right;
Fig. 4 is the nm of gold transmission electron microscope picture in embodiment 2 in testing liquid, A figure represents that, not containing the transmission electron microscope picture of nm of gold in the testing liquid of Clenbuterol, B figure represents the transmission electron microscope picture of nm of gold in the testing liquid containing Clenbuterol (30 μMs);
Fig. 5 is the spectrogram of three kinds of different system solutions of label in embodiment 3, and illustration is corresponding photo, and the label 1,2 and 3 in figure represents the sample solution of different system respectively;
Fig. 6 is the typical curve containing the Clenbuterol detection system of variable concentrations in embodiment 1;
Below in conjunction with specification drawings and specific embodiments, the present invention is illustrated.
Embodiment
TMB of the present invention and tetramethyl benzidine.
Concrete principle of the present invention is that the melamine of low concentration can be adsorbed on nm of gold surface ,-the NH of Clenbuterol
2,-NH ,-OH and-Cl and melamine alkyl-NH
2form hydrogen bond with fragrance-NH-group, such Clenbuterol is as a kind of " crosslinking chemical ", and collaborative melamine causes the gathering of nm of gold, and nm of gold is assembled rear catalytic activity and uprised, darkening after catalysis TMB and hydrogen peroxide develop the color;
By a series of research, the present invention simultaneously finds that the melamine of nm of gold colloid and low concentration that particle diameter is less than 8nm is as testing liquid, the concentration of optional melamine is 0.5uM, add again after mixing with the Clenbuterol of variable concentrations after TMB and hydrogen peroxide develop the color and detect, the detection of Clenbuterol in urine sample can not only be carried out, the detection of Clenbuterol in animal tissue's sample can also be carried out, expand the kind of Clenbuterol energy sample product;
Filter after urine sample solution of the present invention is diluted to finite concentration by pure water and obtain urine sample solution to be measured; Bio-tissue sample extracting solution of the present invention, for lean pork, loose meatball is stirred by the HCl dropwise ethanol of the lean pork after homogenate glass bar, on oscillator, jolting is extracted, pH>12 adjusted by centrifuging and taking supernatant, extracts with normal hexane, merges hexane extract rotary evaporator and is concentrated into dry, residue dissolved in purified water, obtains with 0.25 μm of membrane filtration.
Embodiment 1: the preparation of testing liquid and the detection limit of Clenbuterol
1, material/agent:
Gold chloride, sodium borohydride, sodium acetate and hydrogen peroxide and TMB are purchased from Chemical Reagent Co., Ltd., Sinopharm Group, melamine is purchased from Tianjin Kermel Chemical Reagent Co., Ltd., Clenbuterol is purchased from Chinese food medicine identification research institute, and experimental water is pure water;
2, method:
(1) nm of gold colloid is prepared: all glass apparatus all need to use chloroazotic acid soaked overnight, purified rinse water, dry for standby; The chlorauric acid solution 1mL of 25mM is added in 79mL water, the disposable sodium borohydride solution 2mL adding 1% of brand-new with vigorous stirring, continue lucifuge and stir 1 hour, with 0.25 μm of membrane filtration, 4 DEG C save backup, and the obtained colloidal particle size with the nm of gold colloid of Mimetic enzyme activity is 8nm;
(2) testing liquid: add nm of gold colloid 30mL and the 5 μM of melamine 3mL obtained in (1) in the beaker of 50mL, and stirring 3min is made it even, make testing liquid, working fluid can be preserved 7 days at 4 DEG C;
(3) vial getting 5 2mL adds the Clenbuterol 50 μ L of testing liquid 200 μ L prepared by step (2) and variable concentrations respectively successively, room temperature reaction 15min, add the hydrogen peroxide 200 μ L of 1.4M subsequently successively, the TMB200 μ L of 8.3mM, sodium acetate buffer solution (pH=4.5) the 200 μ L of 0.05M, room temperature reaction 30min, work in coordination with melamine induced nano gold due to Clenbuterol to assemble, the catalytic activity of nm of gold is improved different, being of different shades of final system;
(4) concentration of Clenbuterol used is followed successively by: 0 μM, 5 μMs, 10 μMs, 20 μMs, 30 μMs and 50 μMs, adds in testing liquid, the oxidation product color change of range estimation TMB, and measures the absorption spectrum of TMB oxidation product;
3, result:
Composition graphs 1,2 and 3, photo figure in Fig. 1 is the color diagram of the testing liquid of the Clenbuterol solution only containing variable concentrations, Fig. 2 is sodium acetate buffer solution (pH=4.5) the 200 μ L of TMB200 μ L and 0.05M of hydrogen peroxide 200 μ L, the 8.3mM adding 1.4M and the solution colour figure after room temperature reaction 30min, known by the contrast of two width pictures: Clenbuterol concentration is higher, the oxidation product blueness of TMB is darker, the blue depth can be obtained and detect colorimetric card, see Fig. 3; And simple Clenbuterol and nano Au colloid liquid solution mix develop the color (Fig. 1) mixes compared with develop the color (Fig. 2) in conjunction with Clenbuterol and nano Au colloid liquid solution with changing the color after the catalysis of hydrogen peroxide, color in obvious Fig. 2 more easily judges, is conducive to detecting fast;
Simultaneously Clenbuterol concentration is higher, and the absorption value at 652nm place is larger, according to the concentration Criterion curve of Δ A652 and Clenbuterol, sees Fig. 6; In the present embodiment, detecting of Clenbuterol is limited to 0.38 μM, and the range of linearity is 1 ~ 50 μM.
Embodiment 2: transmission electron microscopy
Extraction embodiment one prepare testing liquid 200 μ L, the Clenbuterol 50 μ L of 30 μMs in the vial of 2mL, in contrast; Testing liquid 250 μ L prepared by embodiment one is only added in another vial; Two kinds of samples are dripped respectively on the copper mesh that two have plating carbon supporting film, not higher than 60 DEG C of dry for standby;
Under the accelerating potential of 200kV, the transmission electron microscope of above-mentioned sample is scanned with HT7700 transmission electron microscope.
To containing the testing liquid of Clenbuterol (30 μMs) and not carried out transmission electron microscopy containing the nm of gold in the testing liquid of Clenbuterol, obtain the transmission electron microscope picture in Fig. 4, A figure represents that, not containing the transmission electron microscope picture of nm of gold in the testing liquid of Clenbuterol, B figure represents the transmission electron microscope picture of nm of gold in the testing liquid containing Clenbuterol (30 μMs); Schemed, with the contrast of B figure, after the melamine by means of only low concentration mixes with nm of gold colloid, not occur clustering phenomena (scheming A) from A; After add Clenbuterol in testing liquid, there is obvious clustering phenomena (figure B); Analysis principle may be that melamine can be adsorbed on nm of gold surface ,-the NH of Clenbuterol
2, the alkyl-NH of-NH ,-OH and-Cl and melamine
2hydrogen bond is formed with fragrance-NH-group, such Clenbuterol is as a kind of " crosslinking chemical ", collaborative melamine causes the gathering of nm of gold, it can thus be appreciated that after the melamine adding low concentration and Clenbuterol, both create synergistic function to the gathering of nm of gold, improve the hydrogen peroxide catalyzed activity of simulation of nm of gold, can develop the color more fast, and the color of display obviously easily carries out naked eyes judgement.
Embodiment 3: visual comparison
No. 1 solution: nm of gold colloid 200 μ L, TMB solution (8.3mM) the 200 μ L of preparation in embodiment one and sodium acetate buffer solution (0.05M, pH=4.5) 200 μ L;
No. 2 solution: testing liquid 200 μ L, hydrogen peroxide (1.4M) 200 μ L, TMB (8.3mM) the 200 μ L of preparation in embodiment one and sodium acetate buffer solution (0.05M, pH=4.5) 200 μ L;
No. 3 solution: the testing liquid 200 μ L prepared in embodiment one, Clenbuterol titer (60uM) 50 μ L, hydrogen peroxide (1.4M) 200 μ L, TMB (8.3mM) 200 μ L and sodium acetate buffer solution (0.05M, pH=4.5) 200 μ L.
Above-mentioned three parts of solution are carried out to the absorbance measurement of 652nm, the vignette that the results are shown in Figure in 5, Fig. 5 is the color camera comparison diagram of above-mentioned three parts of solution; It can thus be appreciated that colloidal particle size is the nm of gold colloid of 8nm and the indifferent of testing liquid catalysis TMB, solution colour is very shallow; Add the obvious grow of catalytic capability after Clenbuterol, solution colour deepens.
Embodiment 4: to the detection of Clenbuterol in pig urcine
1, material/agent:
The testing liquid of preparation in embodiment one, the particle diameter of nm of gold is 8nm; Sodium acetate and hydrogen peroxide and TMB are purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and melamine is purchased from Tianjin Kermel Chemical Reagent Co., Ltd., and Clenbuterol is purchased from Chinese food medicine identification research institute; Urine capture is in testing station of Xibei Univ. of Agricultural & Forest Science & Technology;
2, method:
Get 10mL urine, dilute 50 times with pure water, with 0.25 μm of membrane filtration.Get in 10mL sample diluting liquid, add the Clenbuterol standard solution of different volumes 1mM, obtain a series of sample diluting liquid (see table 1) containing variable concentrations Clenbuterol.
In the testing liquid that 200 μ L prepare, add the sample diluting liquid 50 μ L that with the addition of Clenbuterol, room temperature reaction 15min, add successively subsequently, the hydrogen peroxide 200 μ L of 1.4M, the TMB200 μ L of 8.3mM, sodium acetate buffer solution (pH=4.5) the 200 μ L of 0.05M, room temperature reaction 30min, the color after colour developing and colorimetric card contrast, and measure the absorption spectrum of TMB oxidation product.
3, result: reacted detection system and colorimetric card are contrasted, measures three times, and each measurement result, as seen can the content range of semiquantitative judgement Clenbuterol by colorimetric card visual colorimetric determination in table 1;
The absorbance of the 652nm typical curve substituted in embodiment one is calculated the concentration of Clenbuterol, and calculate the recovery, in the present embodiment, the recovery of Clenbuterol is 90.7 ~ 104.6% (see table 2).
Embodiment 5: the detection of Clenbuterol in pork
1, material/agent:
The testing liquid of preparation in embodiment one, the particle diameter of nm of gold is 8nm; Sodium acetate and hydrogen peroxide and TMB are purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and melamine is purchased from Tianjin Kermel Chemical Reagent Co., Ltd., and Clenbuterol is purchased from Chinese food medicine identification research institute; Pork is purchased from local market;
2, method:
Get the lean pork of 2.00g after homogenate in 10mL centrifuge tube, add 6mL acidic ethanol (the ethanol 100ml of 60%, add 0.5ml concentrated hydrochloric acid), and add the Clenbuterol standard solution of different volumes 1mM, loose meatball is stirred with glass bar, on oscillator, 15min is extracted in jolting, with the centrifugal 15min of 3000r/min, supernatant 2MNaOH liquid adjusts pH>12, extract with normal hexane (5mLx3), merging hexane extract rotary evaporator is concentrated into dry, residue dissolved in purified water is also settled to 2mL, with 0.25 μm of membrane filtration, obtain a series of sample extracting solution (see table 1) containing variable concentrations Clenbuterol,
In the testing liquid that 200 μ L prepare, add the sample extracting solution 50 μ L that with the addition of Clenbuterol, room temperature reaction 15min, add successively subsequently, the hydrogen peroxide 200 μ L of 1.4M, the TMB200 μ L of 8.3mM, sodium acetate buffer solution (pH=4.5) the 200 μ L of 0.05M, room temperature reaction 30min, the color after colour developing and colorimetric card contrast, and measure the absorption spectrum of TMB oxidation product;
3, result: reacted detection system and colorimetric card are contrasted, measures three times, and each measurement result, as seen can the content range of semiquantitative judgement Clenbuterol by colorimetric card visual colorimetric determination in table 1;
The absorbance of the 652nm typical curve substituted in embodiment one is calculated the concentration of Clenbuterol, and calculate the recovery, in the present embodiment, the recovery of Clenbuterol is 90.7 ~ 104.6% (see table 2).
Table 1 colorimetric card testing result
Table 2 recovery of standard addition
Embodiment 6: testing liquid prepared by the present invention can be preserved 7 days at 4 DEG C
1, testing liquid (melamine 0.5uM)
2, testing liquid (melamine 0.5uM) 200 μ L, Clenbuterol (10uM) 50 μ L, hydrogen peroxide (1.4M) 200 μ L, TMB (8.3mM) 200 μ L, sodium acetate buffer solution (0.05M, pH=4.5) 200 μ L.
3, testing liquid (melamine 0.5uM) 200 μ L, Clenbuterol (50uM) 50 μ L, hydrogen peroxide (1.4M) 200 μ L, TMB (8.3mM) 200 μ L, sodium acetate buffer solution (0.05M, pH=4.5) 200 μ L.
First and third, within five, seven days, carry out the absorbance measurement of 511nm respectively to 1, carry out the absorbance measurement of 652nm to 2,3, the results are shown in Table 3; It can thus be appreciated that testing liquid itself is very stable in 7 days, and also very stable to the testing result with Clenbuterol.
Table 3 absorbance changes
Claims (6)
1. a Clenbuterol testing liquid, is characterized in that, this working fluid is the mixed liquor obtained after nm of gold colloid and melamine solution mix, wherein:
The colloidal particle size of described nm of gold colloid is less than 8nm;
The concentration of described melamine solution is 4 ~ 6 μMs.
2. Clenbuterol testing liquid as claimed in claim 1, it is characterized in that, described nm of gold colloid and the volume ratio of melamine solution are 7 ~ 11:1.
3. a Determination of Clenbuterol, is characterized in that, is mixed by the Clenbuterol testing liquid described in claim 1 or 2 to carry out chromogenic reaction and obtain standard color solution with Clenbuterol standard solution, hydrogen peroxide and TMB;
Testing sample solution mixes with Clenbuterol testing liquid, hydrogen peroxide and the TMB described in claim 1 or 2 and carries out chromogenic reaction and obtain testing sample nitrite ion;
Testing sample nitrite ion and standard color solution are compared and obtains Cologne special sieve content detection value range.
4. Determination of Clenbuterol as claimed in claim 3, it is characterized in that, described Clenbuterol testing liquid and the volume ratio of Clenbuterol standard solution are 4.9 ~ 3.8:1, and the concentration of Clenbuterol standard solution is 0 μM, 5 μMs, 10 μMs, 20 μMs, 30 μMs and 50 μMs.
5. the Determination of Clenbuterol as described in claim 3 or 4, is characterized in that, described testing sample solution comprises urine sample dilution and bio-tissue sample extracting solution.
6. the Determination of Clenbuterol as described in claim 3 or 4, it is characterized in that, this detection method also comprises carries out standard color solution absorbance measurement by absorption photometry and obtains the special sieve concentration standard curve in absorbance and Cologne, then obtains the special sieve concentration value in Cologne by the absorbance measurement that absorption photometry carries out testing sample nitrite ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510230199.1A CN104914096B (en) | 2015-05-07 | 2015-05-07 | A kind of Clenbuterol detection working solution and detection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510230199.1A CN104914096B (en) | 2015-05-07 | 2015-05-07 | A kind of Clenbuterol detection working solution and detection method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104914096A true CN104914096A (en) | 2015-09-16 |
| CN104914096B CN104914096B (en) | 2018-02-16 |
Family
ID=54083348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510230199.1A Expired - Fee Related CN104914096B (en) | 2015-05-07 | 2015-05-07 | A kind of Clenbuterol detection working solution and detection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104914096B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106124716A (en) * | 2016-07-21 | 2016-11-16 | 武汉市农业科学技术研究院农业环境安全检测研究所 | A kind of Clenbuterol method for quick |
| CN107999128A (en) * | 2017-12-06 | 2018-05-08 | 广东轻工职业技术学院 | A kind of basophilla analogue enztme and preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080299186A1 (en) * | 2007-06-01 | 2008-12-04 | Schering-Plough Healthcare Products, Inc. | Coatings for applying substances onto substrate carrier |
| CN103091313A (en) * | 2013-01-16 | 2013-05-08 | 中国科学院大学 | Method for visual rapid detection of clenbuterol by adopting nanogold probe |
| CN103833915A (en) * | 2012-11-20 | 2014-06-04 | 南开大学 | Molecular imprinting polymer nanoparticles for pure biological sample, and preparation method thereof |
| CN104020202A (en) * | 2014-06-27 | 2014-09-03 | 中国科学院苏州生物医学工程技术研究所 | Method for detecting content of clenbuterol in solution to be detected |
| US20140287527A1 (en) * | 2013-03-19 | 2014-09-25 | Land And Long International Trading Co. Limited | Method and apparatus for time-resolved fluorescence immunoassay testing |
-
2015
- 2015-05-07 CN CN201510230199.1A patent/CN104914096B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080299186A1 (en) * | 2007-06-01 | 2008-12-04 | Schering-Plough Healthcare Products, Inc. | Coatings for applying substances onto substrate carrier |
| CN103833915A (en) * | 2012-11-20 | 2014-06-04 | 南开大学 | Molecular imprinting polymer nanoparticles for pure biological sample, and preparation method thereof |
| CN103091313A (en) * | 2013-01-16 | 2013-05-08 | 中国科学院大学 | Method for visual rapid detection of clenbuterol by adopting nanogold probe |
| US20140287527A1 (en) * | 2013-03-19 | 2014-09-25 | Land And Long International Trading Co. Limited | Method and apparatus for time-resolved fluorescence immunoassay testing |
| CN104020202A (en) * | 2014-06-27 | 2014-09-03 | 中国科学院苏州生物医学工程技术研究所 | Method for detecting content of clenbuterol in solution to be detected |
Non-Patent Citations (4)
| Title |
|---|
| HAO-HUA DENG.ET AL: "Colorimetric sensor based on dual-functional gold nanoparticles:Analyte-recognition and peroxidase-like activity", 《FOOD CHEMISTRY》 * |
| PINGLI HE.ET AL: "Direct Detection of β-Agonists by Use of Gold Nanoparticle-Based Colorimetric Assays", 《ANALYTICAL CHEMISTRY》 * |
| XIAOFANG ZHANG.ET AL: "Colorimetric sensing of clenbuterol using gold nanoparticles in the presence of melamine", 《BIOSENSORS AND BIOELECTRONICS》 * |
| 白文荟等: "纳米金比色法在食品安全检测中的应用研究进展", 《食品安全质量检测学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106124716A (en) * | 2016-07-21 | 2016-11-16 | 武汉市农业科学技术研究院农业环境安全检测研究所 | A kind of Clenbuterol method for quick |
| CN107999128A (en) * | 2017-12-06 | 2018-05-08 | 广东轻工职业技术学院 | A kind of basophilla analogue enztme and preparation method and application |
| CN107999128B (en) * | 2017-12-06 | 2020-11-13 | 广东轻工职业技术学院 | Alkalophilic mimic enzyme and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104914096B (en) | 2018-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Quantitative analysis of chloramphenicol, thiamphenicol, florfenicol and florfenicol amine in eggs via liquid chromatography-electrospray ionization tandem mass spectrometry | |
| Zhang et al. | Colorimetric sensing of clenbuterol using gold nanoparticles in the presence of melamine | |
| Wang et al. | Ionic liquid-based matrix solid-phase dispersion coupled with homogeneous liquid–liquid microextraction of synthetic dyes in condiments | |
| CN106883849A (en) | Graphene quantum dot that a kind of nitrogenous sulphur mixes and preparation method thereof and the application on lysine luciferase assay reagent is prepared | |
| CN106053674A (en) | Chromatographic detection method for simultaneously analyzing ammonium ions, amino acids and biogenic amine in tobacco leaves | |
| Zitka et al. | Microfluidic chip coupled with modified paramagnetic particles for sarcosine isolation in urine | |
| CN111220592B (en) | Rapid hydroxy sanshool detection method based on surface enhanced Raman spectrum | |
| CN107144558B (en) | Method for identifying illegal cooking oil by using Raman spectrum technology | |
| CN105445259B (en) | The method for quickly detecting clenbuterol hydrochloride based on functionalization gold nanoparticle | |
| Chen et al. | Integrated immunochromatographic assay for qualitative and quantitative detection of clenbuterol | |
| CN107024461A (en) | A kind of method of the double probe rapid detection of nitrite in food of fluorescence/colorimetric | |
| Khuhawar et al. | Liquid chromatographic determination of cis-platin as platinum (II) in pharmaceutical preparation, serum and urine samples of cancer patients | |
| CN104914096A (en) | Clenbuterol detection operating fluid and detection method thereof | |
| CN105403612A (en) | Method for rapidly detecting pesticide residue based on plant esterase | |
| CN107290452A (en) | A kind of method for detecting reference state heterocycle amine content | |
| CN104865232A (en) | Method for selectively detecting ascorbic acid by utilizing metal-organic framework material | |
| CN104101661B (en) | A kind of method for quick of Detection of Magdala in Food Through | |
| CN108459010A (en) | The detection method of Clenbuterol in a kind of animals urine based on liquid-liquid extraction-Surface enhanced Raman spectroscopy | |
| Si et al. | Novel methods for the rapid detection of trace tetracyclines based on the fluorescence behaviours of Maillard reaction fluorescent nanoparticles | |
| CN102384907A (en) | Method by utilize vanillin-sulfuric acid colorimetry to measure glabridin content | |
| CN108318594A (en) | A kind of method that liquid chromatography tandem mass spectrometry measures activity of adenosine deaminase and screens its inhibitor | |
| CN106198788A (en) | The HPLC detection method of albuterol in a kind of feedstuff or meat product | |
| Jing et al. | Rapid and sensitive determination of clenbuterol in porcine muscle and swine urine using a fluorescent probe | |
| CN106093264A (en) | A kind of assay method of Fructus Fragariae Ananssae Xanthophyll Cycle Components | |
| CN110609107A (en) | Method for detecting aflatoxins G2, G1, B2 and B1 in radix paeoniae alba decoction pieces by using ultra-high performance liquid chromatography-mass spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180216 Termination date: 20190507 |