CN104792762B - A kind of method that utilization CdTe quantum quantitatively detects salbutamol - Google Patents
A kind of method that utilization CdTe quantum quantitatively detects salbutamol Download PDFInfo
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Abstract
The present invention provides a kind of method that utilization CdTe quantum quantitatively detects salbutamol, by the CdTe quantum of the TGA by surface modification with test substance salbutamol after phosphate buffer is well mixed, the fluorescence intensity of system is detected using molecular fluorescence photometer, the trace detection to salbutamol can be achieved, this is due in weakly alkaline solution system, the surface modification CdTe quantum of electronegative carboxyl forms new compound system by electrostatic interaction with positively charged target molecule salbutamol, causes fluorescent quenching；Testing result shows, fluorescent quenching of the salbutamol to CdTe quantum has higher sensitivity and the wider range of linearity, so as to utilize the change of CdTe quantum fluorescence intensity, realize the quantitative detection to salbutamol, and the method that utilization CdTe quantum of the present invention quantitatively detects salbutamol, experimental implementation is very simple, and detection time is short, and analysis cost is low.
Description
Technical field
The present invention relates to a kind of method that utilization CdTe quantum quantitatively detects salbutamol, belong to the detection of salbutamol
Field.
Background technology
Salbutamol belongs to beta-receptor activator, and the nutritional ingredient in animal body can be made to be shifted from fat to muscle, performance
Go out repartitioning function effect, and then regulate and control the metabolism of animal body, strengthen lipolysis, promote protein synthesis, significantly carry
High carcass lean meat percentage and the price of deed.But, beta-receptor activator easily accumulates residual in animal tissue, particularly internal organ, its
The symptoms such as muscular tremor, arrhythmia cordis, headache can be triggered by being entered by food chain after human body, severe patient may threat to life.Mirror
In above reason, the beta-receptor activator such as salbutamol, Clenbuterol, Ractopamine was classified as by China in 1997 to be forbidden
The medicine used in feed and cultivation domestic animal drinking water.But, still there is culturist by its illegal use in animal husbandry at present,
Trigger medicament residue, so as to be caused serious harm to consumer health.
Chinese patent CN104251898 discloses a kind of film dialysis-Liquid Chromatography-Tandem Mass Spectrometry and determines a variety of in livestock products
The method of beta-receptor activator residual, is comprised the following steps that：(1) sample pre-treatments：The sample that 5g is crushed accurately is weighed, is added
20ml0.02mol/L ammonium acetate buffers (are tuned into pH4-5) with acetic acid, mix, ultrasound 20 minutes, and 8000 leave the heart 5 minutes, on
Clear liquid is moved into bag filter, and bag filter is immersed to the brown for filling 400-500ml0.02mol/L ammonium acetate buffers (pH4-5)
In beaker, rotor is put into, beaker is placed on magnetic stirring apparatus and dialysed, speed of agitator drives dialysis to be formed to be vortexed in cup
Bag is rotated, and bag filter does not sink to being defined, opaque sack on cup outer cover, and the time is 6h.Bag filter is taken out after the completion of dialysis, will be burnt
Dialyzate in cup is adjusted to pH to 9-10, in the pyriform shunting funnel for moving into 1L, adds 40ml solvent (hexamethylenes:Ethyl acetate
=4:1), extract 2 times, combining extraction liquid is rotated, with 0.1% aqueous formic acid (v/v) constant volume into 1.0ml, for HPLC-
MS/MS determines analysis；(2) HPLC-MS/MS is determined：Using the content of external standard method beta-receptor activator, liquid-phase chromatographic column is adopted
With Thermo Hypersil Gold (2.1mm × 100mm, 3 μm), filler is selected from Octadecylsilane bonded phase silica gel, and mobile phase is
0.1% aqueous formic acid A- acetonitrile B, flow velocity is 0.2ml/min, and condition of gradient elution is：T=0min, 96%A, 4%B；T=
2min, 96%A, 4%B；T=5min, 77%A, 23%B；T=12min, 5%A, 95%B；T=28min, 44%A, 56%B；
T=24min, 5%A, 95%B；T=24.1min, 96%A, 4%B；T=32min, 96%A, 4%B；Mass Spectrometry Conditions are：EFI
Mist ionization source cation scans ESI+, multiple-reaction monitoring pattern MRM；Electron spray voltage：5.5kV；Ion source temperature：550 DEG C, mist
Change atmospheric pressure GSI：40psi；Secondary air speed GS2：60psi, gas curtain atmospheric pressure CUR：40psi；Collision cell entrance potential EP：
10V；Collision cell exit potential CXP：13V, the ion pair of monitoring analyte carries out medicament residue confirmatory analysis.
The above method first carries out sample pre-treatments using film dialysis, determines livestock products using Liquid Chromatography-Tandem Mass Spectrometry again afterwards
A variety of beta-receptor activators in product, however, above-mentioned detection method is present, sample pre-treatments are complicated, detection process is cumbersome, be parsed into
This height, detection cycle length, expensive equipment, be difficult to operation the problems such as, it is difficult to carry out execute-in-place, limited in actual applications
System.
The content of the invention
The technical problems to be solved by the invention are to detect livestock products using Liquid Chromatography-Tandem Mass Spectrometry in the prior art
During middle beta-receptor activator, there is sample pre-treatments complexity, detection process is cumbersome, analysis cost is high, detection cycle length, instrument are held high
It is expensive, the problems such as be difficult to operation, so as to propose that a kind of simple to operate, cost is low and the quick CdTe for determining salbutamol can be realized
Fluorescent optical sensor and its preparation method and application.
In order to solve the above technical problems, technical scheme is as follows：
A kind of preparation method of the CdTe quantum detected for salbutamol, comprises the following steps：
(1) 0.12g-0.13g telluriums powder and 0.07g-0.09g sodium borohydrides are weighed respectively, and add 1-2ml high purity waters,
Reaction is stirred under the conditions of ice-water bath, transparent NaHTe solution is produced；
(2) 0.1-0.2gCdCl is weighed2·2.5H2O is dissolved in 200ml high purity waters, adds 100 μ L TGAs, is formed
The suspended liquid system of milky；
(3) 0.1molL is first used-1NaOH solution adjusts the pH of the suspended liquid system for 10-12, pre- inflated with nitrogen 30min,
Add the NaHTe solution described in step (1) under nitrogen protection again, control Cd2+、HTe-, TGA mol ratio be 0.8-
1.0:0.4-0.5:1.5-2.5, produces the CdTe quantum presoma of brown；
(4) described CdTe quantum presoma is transferred in reactor, 5-60min is heated at 140-160 DEG C, through cold
But, wash, centrifuge the CdTe quantum described in producing.
A kind of method for quantitatively detecting salbutamol using described CdTe quantum, it comprises the following steps：
(a) equation of linear regression of Stern-Volmer curves is made：
A series of salbutamol standard working solution of various concentrations is prepared, and it is moved in 5ml colorimetric cylinder respectively,
It is 1.45 × 10 that 1.5ml concentration is added into each colorimetric cylinder-3Mol/L CdTe solution, with pH=7.4 phosphate
Cushioning liquid constant volume, detects the fluorescence intensity F of each above-mentioned system with molecular fluorescence photometer after shaking up；Meanwhile, take 1.5ml dense
Spend for 1.45 × 10-3Mol/L CdTe solution is added in 5ml colorimetric cylinder, is determined with pH=7.4 phosphate buffer solution
Hold, the fluorescence intensity F of molecular fluorescence photometer detection architecture is used after shaking up0；
Using salbutamol concentration as abscissa, with F0/ F is ordinate, produces salbutamol and CdTe quantum fluorescence is quenched
The equation of linear regression of the Stern-Volmer curves gone out；
(b) the CdTe solution described in 1.5ml and the sample liquid containing salbutamol is taken to be added in 5ml colorimetric cylinder respectively,
With pH=7.4 phosphate buffer solution constant volume, shaking up makes it obtain system with the detection of molecular fluorescence photometer after fully reacting
Fluorescence intensity, compareed with the equation of linear regression of Stern-Volmer curves, produce containing for salbutamol in the sample liquid
Amount.
In step (a) and step (b), the testing conditions of the fluorescence intensity are：Excitation wavelength is 365nm, excite and
Transmite slit width is 5nm.
The concentration of the standard working solution of the salbutamol is respectively 0.042 × 10-6、0.084×10-6、0.126×
10-6、0.168×10-6、0.210×10-6、0.252×10-6、0.420×10-6、0.630×10-6、0.84×10-6、1.26×
10-6、1.68×10-6、2.10×10-6mol/L。
The equation of linear regression of the Stern-Volmer curves is divided into two parts, and the concentration range of the salbutamol is
0.042×10-6-0.420×10-6When, the equation of linear regression of described Stern-Volmer curves is 0.8428 × 106C+
1.0434, linearly dependent coefficient is 0.976；
The concentration range of the salbutamol is 0.420 × 10-6-2.10×10-6During mol/L, Stern-Volmer curves
Equation of linear regression be F0/ F=0.1491 × 106C+1.3078, linearly dependent coefficient is 0.999.
The sample liquid containing salbutamol is urinated for pig.
The pig urine is by following pretreatment：
Pig urine samples liquid is taken, is 7.0 with NaOH solution regulation pH, filters and filtrate will be collected, produce analyte sample fluid.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：
(1) method that utilization CdTe quantum of the present invention quantitatively detects salbutamol, by by surface modification mercapto
The CdTe quantum of guanidine-acetic acid is well mixed with test substance salbutamol in phosphate buffer, glimmering using molecule afterwards
Light photometer is detected to the fluorescence intensity of system, you can realize the trace detection to salbutamol, this is due to weakly alkaline
In solution system, the surface modification CdTe quantum of electronegative carboxyl passes through with positively charged target molecule salbutamol
Electrostatic interaction forms new compound system, causes fluorescent quenching, so that using the change of CdTe quantum fluorescence intensity, it is real
Now to the quantitative detection of salbutamol, as a result show, salbutamol is 0.042 × 10-6-0.420×10-6In the range of mol/L
With 0.420 × 10-6-2.09×10-6In the range of mol/L, concentration and the relative intensity of fluorescence F of salbutamol0/ F presents good
Good linear relationship, linearly dependent coefficient is up to 0.976 and 0.999 respectively, so as to illustrate salbutamol to CdTe quantum
Fluorescent quenching has higher sensitivity and the wider range of linearity, and utilization CdTe quantum of the present invention quantitatively detects sand
The method of butylamine alcohol, experimental implementation is very simple, and detection time is short, and analysis cost is low, and relatively low detection limit is 2 × 10-8Mol/L,
The more a height of 86.6%-95.8% of recovery of standard addition, can be prevented effectively from and be detected in the prior art using Liquid Chromatography-Tandem Mass Spectrometry
In livestock products during beta-receptor activator, there is that sample pre-treatments are complicated, detection process is cumbersome, analysis cost is high, detection cycle length,
Expensive equipment, be difficult to operation the problems such as.
(2) CdTe quantum of the present invention quantitatively detect pig urine in salbutamol method, also the pig is urinated into
Row pretreatment, effectively to remove the interference of metal ion in pig urine samples.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, specific embodiment and combination below according to the present invention
Accompanying drawing, the present invention is further detailed explanation, wherein
Fig. 1 is the TEM figures of CdTe quantum of the present invention；
Fig. 2 is the XRD of CdTe quantum of the present invention；
Fig. 3 is the fluorescence spectra of CdTe quantum of the present invention；
Fig. 4 is that spectrum change figure is quenched to various concentrations salbutamol in CdTe quantum of the present invention；
Fig. 5 is Stern-Volmer curve of the salbutamol to CdTe quantum fluorescent quenching.
Embodiment
The technical characterstic of the present invention is expanded on further with reference to specific embodiment.
1st, instrument and reagent
Molecular fluorescence photometer (model：F7000, is provided by Hitachi, Ltd)；
Salbutamol standard items are purchased from sigma.
2nd, Stern-Volmer curves and detection limit
(1) standard liquid of salbutamol is taken, using pH=7.4 phosphate buffer solution as solvent, dilution step by step is obtained
The concentration of salbutamol is respectively 0.042 × 10 in a series of standard working solution of salbutamols, the standard working solution-6、0.084×10-6、0.126×10-6、0.168×10-6、0.210×10-6、0.252×10-6、0.420×10-6、0.630×
10-6、0.84×10-6、1.26×10-6、1.68×10-6、2.10×10-6mol/L；
(2) the salbutamol standard working solution of above-mentioned series concentration is moved in 5ml colorimetric cylinder respectively, to each institute
It is 1.45 × 10 to state and 1.5ml concentration is added in colorimetric cylinder-3Mol/L CdTe solution, with pH=7.4 phosphate buffer solution
Constant volume, detected after shaking up with molecular fluorescence photometer the fluorescence intensity of above-mentioned each system be respectively F1=1040, F2=1015,
F3=995.1, F4=963.3, F5=931.3, F6=846.7, F7=813.2, F8=764.8, F9=735.5, F10=
695th, F11=619.4, F12=569.3；Testing conditions are：Excitation wavelength is 365nm, excites and is with transmite slit width
5nm；
It is 1.45 × 10 to take 5ml colorimetric cylinder in addition and add 1.5ml concentration-3Mol/L CdTe solution, uses pH=
7.4 phosphate buffer solution constant volume, detects above-mentioned blank sample system (without husky butylamine after shaking up with molecular fluorescence photometer
Alcohol) fluorescence intensity F0For 1141, testing conditions are：Excitation wavelength is 365nm, and it is 5nm to excite with transmite slit width；
For the salbutamol standard working solution of above-mentioned series concentration, detect that obtained relative intensity of fluorescence is respectively
F0- F1=99, F0- F2=126, F0- F3=146, F0- F4=177.7, F0- F5=209.7, F0- F6=293.4, F0- F7=
327.8、F0- F8=376.2, F0- F9=405.5, F0- F10=445.5, F0- F11=521.6, F0- F12=571.7；
(c) using salbutamol concentration as abscissa, relative intensity of fluorescence is ordinate, produces the salbutamol to CdTe
The Stern-Volmer curves that quantum dot fluorescence is quenched, as shown in Figure 5；
The equation of linear regression of the Stern-Volmer curves is divided into two parts, and the concentration range of the salbutamol is
0.042×10-6-0.420×10-6During mol/L, the equation of linear regression of described Stern-Volmer curves is F0/ F=
0.8428×106C+1.0434, linearly dependent coefficient is 0.976；The concentration range of the salbutamol is 0.420 × 10-6-
2.10×10-6During mol/L, the equation of linear regression of described Stern-Volmer curves is F0/ F=0.1491 × 106C+
1.3078, linearly dependent coefficient is 0.999, so as to illustrate that fluorescent quenching of the salbutamol to CdTe quantum has higher spirit
Sensitivity and the wider range of linearity；
By the Parallel testing of the continuous 11 progress fluorescence intensity of blank sample system, as a result show, the standard deviation of measurement
For 0.0021, and the detection for going out this method detection salbutamol according to 3 times of standard deviation calculations is limited to 2 × 10-8mol/L。
3rd, the measure of sample
Embodiment 1
The present embodiment provides a kind of method that utilization CdTe quantum quantitatively detects salbutamol in pig urine samples liquid, described
Pig urine samples liquid is negative sample, it is known that salbutamol is free of in the negative pig urine samples liquid, is used to examine as blind sample
Survey, detection method comprises the following steps：
(a) preparation of the CdTe quantum, specific as follows：
(1) 0.1276g telluriums powder and 0.0800g sodium borohydrides are weighed respectively, and adds 1ml high purity waters, and sealed membrane is used rapidly
Sealing is sealed, is communicated while inserting injection needle with the external world, reaction 4h is carried out under the conditions of ice-water bath and strong magnetic agitation, stood
10min, produces the transparent NaHTe solution of pinkish；
Reaction equation is as follows：
4NaBH4+2Te+7H2O=2NaHTe+Na2B4O7+14H2↑
(2) 0.12gCdCl is weighed2·2.5H2O is dissolved in 200ml high purity waters, adds 100 μ L TGAs, forms breast
The suspended liquid system of white；
(3) 0.1molL is first used-1The pH that NaOH solution adjusts the suspended liquid system is 12, leads to high pure nitrogen 30min,
Then Cd in the NaHTe solution that 210 μ L steps (1) are prepared, control solution is added under nitrogen protection2+、HTe-, mercapto
The mol ratio of guanidine-acetic acid is 1.0:0.42:2.0, produce the CdTe quantum presoma of brown；
(4) described CdTe quantum presoma is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoroethyllining lining, put
50min is heated in 160 DEG C of baking ovens, described CdTe quantum is produced through cooling, washing, centrifugation；
(b) salbutamol is quantitatively detected using described CdTe quantum, it is specific as follows：
Pig urine samples liquid is taken, is 7.0 with NaOH solution regulation pH, filters and filtrate will be collected, produce analyte sample fluid；
Take CdTe solution and described analyte sample fluid described in 1.5ml to be added in 5ml colorimetric cylinder respectively, use pH=
7.4 phosphate buffer solution constant volume, shakes up the fluorescence for making it detect the system that obtains after fully reacting with molecular fluorescence photometer
Intensity F is 1141, and testing conditions are：Excitation wavelength is 365nm, and it is 5nm to excite with transmite slit width, and sweep speed is
1200nm/min；
Compareed with the equation of linear regression of Stern-Volmer curves, you can draw in the negative pig urine samples liquid and be free of
Salbutamol, the fact that testing result is with being free of salbutamol in the negative pig urine samples liquid is consistent.
Fig. 1 show the TEM figures of the CdTe quantum, it can be seen that the pattern of the CdTe quantum is
Spherical, good dispersion, particle diameter is 4.5nm and is distributed homogeneous.
Fig. 2 show the XRD of the CdTe quantum, it can be seen that diffraction peak is respectively：25.76、
42.16 and 48.36, corresponding to (111) of CdTe cubic systems, (220), and (311) three crystal faces, in order to be contrasted, XRD spectrums
Figure lower section has marked body schalenblende CdTe (solid line) and CdS (dotted line), finds these three values between CdTe and CdS, but
It is partial to CdTe crystal, so as to illustrate that the CdTe quantum belongs to zincblende cube crystalline phase.
Fig. 3 show the fluorescence spectra of CdTe quantum described in the present embodiment, it can be seen that the CdTe amounts
Preferably, when selection 365nm is excited, the maximum wavelength of its fluorescent emission is located at 550nm, and peak shape symmetry to the fluorescence property of son point
Good, its fluorescence intensity is up to 7624.
It is illustrated in figure 4 described CdTe quantum bent to being quenched in spectrum change figure, figure for various concentrations salbutamol
The concentration that line from top to bottom corresponds to salbutamol increases successively, i.e., the concentration of uppermost curve correspondence salbutamol is minimum in figure
For 0, the concentration of nethermost curve correspondence salbutamol is 2.10 × 10 to the maximum-6Mol/L, therefore, as seen from Figure 4, with
Salbutamol concentration increases to 2.10 × 10 from 0-6Mol/L, the fluorescence intensity of system gradually decreases to initial value
50.10%.
Embodiment 2
The present embodiment provides a kind of method that utilization CdTe quantum quantitatively detects salbutamol in pig urine samples liquid, detection
Method comprises the following steps：
(a) preparation of CdTe quantum, specific as follows：
(1) 0.12g telluriums powder and 0.0900g sodium borohydrides are weighed respectively, and adds 2ml high purity waters, are sealed with sealed membrane rapidly
Firmly seal, communicated while inserting injection needle with the external world, reaction 4h is carried out under the conditions of ice-water bath and strong magnetic agitation, stood
10min, produces the transparent NaHTe solution of pinkish；
(2) 0.1gCdCl is weighed2·2.5H2O is dissolved in 200ml high purity waters, adds 100 μ L TGAs, is formed milky white
The suspended liquid system of color；
(3) 0.1molL is first used-1The pH that NaOH solution adjusts the suspended liquid system is 10, leads to high pure nitrogen 30min,
Then Cd in the NaHTe solution that 210 μ L steps (1) are prepared, control solution is added under nitrogen protection2+、HTe-, mercapto
The mol ratio of guanidine-acetic acid is 0.8:0.4:1.5, produce the CdTe quantum presoma of brown；
(4) described CdTe quantum presoma is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoroethyllining lining, put
30min is heated in 140 DEG C of baking ovens, described CdTe quantum is produced through cooling, washing, centrifugation.
(b) salbutamol is quantitatively detected using described CdTe quantum, it is specific as follows：
Pig urine samples liquid is taken, is 7.0 with NaOH solution regulation pH, filters and filtrate will be collected, produce analyte sample fluid；
(2) the CdTe solution described in 1.5ml and the analyte sample fluid described in step (1) is taken to be added to 5ml colorimetric respectively
Guan Zhong, with pH=7.4 phosphate buffer solution constant volume, shaking up makes it be obtained after fully reacting with the detection of molecular fluorescence photometer
The fluorescence intensity F of system is 1140, and testing conditions are：Excitation wavelength is 365nm, and it is 5nm to excite with transmite slit width, is swept
Speed is retouched for 1200nm/min；
Compareed with the equation of linear regression of Stern-Volmer curves, you can draw salbutamol in the pig urine samples liquid
Content be ＜ 0.042 × 10-6mol/L。
Embodiment 3
The present embodiment provides a kind of method that utilization CdTe quantum quantitatively detects salbutamol in pig urine samples liquid, detection
Method comprises the following steps：
(a) preparation of CdTe quantum, specific as follows：
(1) 0.13g telluriums powder and 0.0700g sodium borohydrides are weighed respectively, and adds 1.5ml high purity waters, and sealed membrane is used rapidly
Sealing is sealed, is communicated while inserting injection needle with the external world, reaction 4h is carried out under the conditions of ice-water bath and strong magnetic agitation, stood
10min, produces the transparent NaHTe solution of pinkish；
(2) 0.2gCdCl is weighed2·2.5H2O is dissolved in 200ml high purity waters, adds 100 μ L TGAs, is formed milky white
The suspended liquid system of color；
(3) 0.1molL is first used-1The pH that NaOH solution adjusts the suspended liquid system is 11, leads to high pure nitrogen 30min,
Then Cd in the NaHTe solution that 210 μ L steps (1) are prepared, control solution is added under nitrogen protection2+、HTe-, mercapto
The mol ratio of guanidine-acetic acid is 1.0:0.5:2.5, produce the CdTe quantum presoma of brown；
(4) described CdTe quantum presoma is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoroethyllining lining, put
10min is heated in 150 DEG C of baking ovens, described CdTe quantum is produced through cooling, washing, centrifugation.
(b) salbutamol is quantitatively detected using described CdTe quantum, it is specific as follows：
Pig urine samples liquid is taken, is 7.0 with NaOH solution regulation pH, filters and filtrate will be collected, produce analyte sample fluid；
(2) the CdTe solution described in 1.5ml and the analyte sample fluid described in step (1) is taken to be added to 5ml colorimetric respectively
Guan Zhong, with pH=7.4 phosphate buffer solution constant volume, shaking up makes it be obtained after fully reacting with the detection of molecular fluorescence photometer
The fluorescence intensity F of system is 862.2, and testing conditions are：Excitation wavelength is 365nm, and it is 5nm to excite with transmite slit width,
Sweep speed is 1200nm/min；
Compareed with the equation of linear regression of Stern-Volmer curves, you can draw husky fourth in the positive pig urine samples liquid
The content of amine alcohol is 1.04 × 10-7mol/L。
In order to verify the accuracy and accuracy of detection method, using the efficient liquid of comparative maturity in the prior art
Phase chromatographic tandem mass-spectrometric technique determines the content of salbutamol in pig urine samples liquid, and testing result is 1.04 × 10-7Mol/L, from
And show to detect that the content of salbutamol is connected with using high performance liquid chromatography in pig urine samples liquid using the method for the invention
The result that mass-spectrometric technique is determined is consistent.
4th, recovery of standard addition
The standard liquid of salbutamol is added in blank pig urine samples liquid (i.e. the negative sample liquid of pig urine), control adds
It is respectively 0.75 × 10 to mark concentration-7、1.5×10-7、1.8×10-7Mol/L, according to the utilization CdTe described in the embodiment of the present invention
Quantum dot quantitatively detects that the method for salbutamol in pig urine samples liquid is tested, and 6 parallel surveys are carried out under each spiked levels
Amount, averages, according to actual plus scalar sum testing result, and the recovery of standard addition for calculating pig urine samples liquid is as shown in table 1, sample
The recovery of standard addition of liquid is 86.6%-95.8%.
The horizontal survey of table 1- mark-on sample liquids
| Mark-on amount (× 10-7mol/L) | 0.75 | 1.5 | 1.8 |
| Practical measurement average value | 0.65±0.08 | 1.34±0.18 | 1.72±0.22 |
| The rate of recovery (%) | 86.7±0.06 | 89.3±0.27 | 95.9±0.12 |
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.For
For those of ordinary skill in the art, other various forms of changes or change can be also made on the basis of the above description
It is dynamic.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change thus extended out
Among moving still in the protection domain of the invention.
Claims (5)
1. a kind of method that utilization CdTe quantum quantitatively detects salbutamol, it comprises the following steps：
(a) Stern-Volmer curves are made：
A series of salbutamol standard working solution of various concentrations is prepared, and it is moved in 5ml colorimetric cylinder respectively, to every
It is 1.45 × 10 that 1.5ml concentration is added in the individual colorimetric cylinder-3Mol/L CdTe solution, with pH=7.4 phosphate-buffered
Solution constant volume, detects the fluorescence intensity F of each above-mentioned system with molecular fluorescence photometer after shaking up；Meanwhile, take the 1.5ml concentration to be
1.45×10-3Mol/L CdTe solution is added in 5ml colorimetric cylinder, with pH=7.4 phosphate buffer solution constant volume, is shaken
With the fluorescence intensity F of molecular fluorescence photometer detection architecture after even0；
Using salbutamol concentration as abscissa, with F0/ F is ordinate, produces salbutamol to CdTe quantum fluorescent quenching
The equation of linear regression of Stern-Volmer curves；
Wherein, the equation of linear regression of described Stern-Volmer curves is divided into two parts, the concentration model of the salbutamol
Enclose for 0.042 × 10-6-0.420×10-6During mol/L, the equation of linear regression of described Stern-Volmer curves is F0/ F=
0.8428×106C+1.0434, linearly dependent coefficient is 0.976；
The concentration range of the salbutamol is 0.420 × 10-6-2.10×10-6During mol/L, described Stern-Volmer is bent
The equation of linear regression of line is F0/ F=0.1491 × 106C+1.3078, linearly dependent coefficient is 0.999；
The preparation method of the CdTe quantum, comprises the following steps：
(1) 0.12g-0.13g telluriums powder and 0.07g-0.09g sodium borohydrides are weighed respectively, and adds 1-2ml high purity waters, in frozen water
Reaction is stirred under the conditions of bath, transparent NaHTe solution is produced；
(2) 0.1-0.2gCdCl is weighed2·2.5H2O is dissolved in 200ml high purity waters, adds 100 μ L TGAs, is formed milky white
The suspended liquid system of color；
(3) 0.1molL is first used-1NaOH solution adjusts the pH of the suspended liquid system for 10-12, pre- inflated with nitrogen 30min, then
The lower NaHTe solution added described in step (1) of nitrogen protection, controls Cd2+、HTe-, TGA mol ratio be 0.8-1.0:
0.4-0.5:1.5-2.5, produces the CdTe quantum presoma of brown；
(4) described CdTe quantum presoma is transferred in reactor, 5-60min is heated at 140-160 DEG C, through cooling down,
Washing, centrifugation produce described CdTe quantum；
(b) take the CdTe solution described in 1.5ml and the sample liquid containing salbutamol to be added in 5ml colorimetric cylinder respectively, use pH
=7.4 phosphate buffer solution constant volume, shaking up makes it obtain the glimmering of system with the detection of molecular fluorescence photometer after fully reacting
Luminous intensity, is compareed with the equation of linear regression of described Stern-Volmer curves, produces salbutamol in the sample liquid
Content.
2. the method that CdTe quantum according to claim 1 quantitatively detects salbutamol, it is characterised in that step (a)
In step (b), the testing conditions of the fluorescence intensity are：Excitation wavelength is 365nm, excites and is with transmite slit width
5nm。
3. the method that CdTe quantum according to claim 1 or 2 quantitatively detects salbutamol, it is characterised in that described
The concentration of the standard working solution of salbutamol is respectively 0.042 × 10-6、0.084×10-6、0.126×10-6、0.168×
10-6、0.210×10-6、0.252×10-6、0.420×10-6、0.630×10-6、0.84×10-6、1.26×10-6、1.68×
10-6、2.10×10-6mol/L。
4. the method that CdTe quantum according to claim 1 or 2 quantitatively detects salbutamol, it is characterised in that described
Sample liquid containing salbutamol is urinated for pig.
5. the method that CdTe quantum according to claim 4 quantitatively detects salbutamol, it is characterised in that the pig urine
By following pretreatment：
Pig urine samples liquid is taken, is 7.0 with NaOH solution regulation pH, filters and filtrate will be collected, produce analyte sample fluid.
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