CN1793884A - Chiral identification senser and its preparation method - Google Patents
Chiral identification senser and its preparation method Download PDFInfo
- Publication number
- CN1793884A CN1793884A CN 200510111257 CN200510111257A CN1793884A CN 1793884 A CN1793884 A CN 1793884A CN 200510111257 CN200510111257 CN 200510111257 CN 200510111257 A CN200510111257 A CN 200510111257A CN 1793884 A CN1793884 A CN 1793884A
- Authority
- CN
- China
- Prior art keywords
- electrode
- sensor
- polyaniline
- response
- phenylalanine
- 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.)
- Pending
Links
Images
Abstract
A method for preparing identification transducer of hand character applies electrochemical and chemical process to synthesize optical active polyaniline then dresses it on electrode to be formed as transducer. The prepared transducer can be used to carry out detection and separation of amino acid and its hand character under multiple environments.
Description
Technical field
The present invention relates to galvanochemistry and biological technical field, specifically, the invention provides a kind of chiral identification senser and preparation method thereof.
Background technology
Discerning an amino acid whose important link is exactly at first to set up the surface of a chirality, could create the effective recognition site for enantiomter like this.Optically active polyaniline containing by Wallace group first in 1994 in the solution of (+) or (-) camphorsulfonic acid (Camphorsulfonic acid (CSA)) synthetic by electropolymerization.Recently Li and Wang have reported a kind of method of new synthesized polyaniline, and this polyaniline with height chirality is by synthetic in containing the CSA solution of aniline oligomer and high concentration.Chiral polyaniline is used aspect molecular recognition to some extent.People such as Kaner find that the attitude of mixing of going of the chiral polyaniline of being induced by (-) CSA can have very strong interaction with the L-phenylalanine, and and the effect of D-phenylalanine very weak, they have confirmed this point with circular dichroism spectra.But detect time polyaniline need be soaked for three weeks in amino acid whose solution and just obtain enough signals of sensitivity with circular dichroism spectra.This group is also studied this system with QCM (Quartz Crystal Microbalance), finds that equally chiral polyaniline has recognition reaction to the phenylalanine of isomorphism type not.Sheridan and Breslin have reported that the L-phenylalanine can be adsorbed on the chiral polyaniline that (-) CSA induces, and have detected the desorption current peak of L-phenylalanine with the differentiated pulse voltammetry.
In the former report, most document concentrates on the preparation and the sign of chiral polyaniline, have only seldom document chiral polyaniline to be used for the identification of chiral molecules, and up to now, utilize chiral polyaniline identification film that the electric potential type sensor of chiral amino acid enantiomorph mixed system original position analysis is not appeared in the newspapers as yet.
Summary of the invention
An object of the present invention is to provide a kind of chiral identification senser.
Another object of the present invention provides the preparation method of above-mentioned chiral identification senser.
The invention provides a kind of chiral identification senser, electrode surface covers the chiral polyaniline film in this sensor, and the thickness of film is 0.5～50 μ m.
Electrode can be indium oxide and tin oxide compound film material (ITO) electrode in the sensor, glass-carbon electrode or platinum electrode etc.
The sensor electrode surface polyaniline can be the chiral polyaniline that d-camphorsulfonic acid or l-camphor sulfonic acid are induced.After the chiral polyaniline of being induced by (-) CSA went to mix, we were called (-) polyaniline ((-) PA) with it; After the chiral polyaniline of being induced by (+) CSA went to mix, we were called (+) polyaniline ((+) PA) with it.
In the sensor, electrode surface has chiral polyaniline 5.3 * 10 for every square centimeter
-6～5.3 * 10
-5Mole.
On the other hand, the present invention also provides the preparation method of above-mentioned chiral immunosensor.This method may further comprise the steps successively:
(1) induces the preparation chiral polyaniline with d-camphorsulfonic acid or l-camphor sulfonic acid;
(2) cleaning and activated electrode;
(3) chiral polyaniline that (1) is obtained covers on the electrode that (2) obtain, and the thickness of chiral polyaniline film is 0.5～50 μ m;
(4) behind the pole drying that (3) are obtained, immersed in the water removed oxygen 5～12 hours, treat that open circuit potential is stable, promptly make sensor.
The electrode of (2) cleaning and activation can be the ITO electrode in the said method, glass-carbon electrode, perhaps platinum electrode.
In the said method, sensor electrode surface chiral polyaniline film covers electrode surface by the galvanochemistry synthetic method.Also can cover electrode surface by dripping method.
In the said method, electrode can pass through the air-dry method drying in (4).
Among the present invention, there is chiral polyaniline film 5.3 * 10 on the sensor electrode surface that makes for every square centimeter
-6～5.3 * 10
-5Mole, promptly the coverage of chiral polyaniline film is 5.3 * 10
-6Molcm
-2～5.3 * 10
-5Molcm
-2
Sensor according to preparation can be found the response test of phenylalanine, (+) polyaniline electrode is similar to the response of (-) polyaniline electrode to the L-phenylalanine to the response of D-phenylalanine, and (+) polyaniline electrode is similar to the response of D-phenylalanine to response and (-) polyaniline electrode of L-phenylalanine.So, below other parameter of sensor is optimized or is that example is studied with (-) polyaniline sensor all to the character examination of sensor.
Sensor of the present invention has certain selectivity to the phenylalanine of isomorphism type not, i.e. enantioselectivity.Therefore we measure the potpourri of two kinds of configurations of phenylalanine.When [L-Phe]/[D-Phe] greater than 10 the time, the response slope of (-) PA electrode pair phenylalanine is about about 59mV/dec, along with the increase of [D-Phe]/[L-Phe] ratio, the linear response slope reduces gradually.When [D-Phe]/when [L-Phe] was 1: 2, the linear response slope was 49mV/dec; When [D-Phe]/when [L-Phe] was 1: 1, the linear response slope was 45mV/dec; When measuring pure D-phenylalanine, then to drop to minimum value be 35mV/dec to the linear response slope.Specifically see Figure 12.
Find that in the present invention the response time of sensor is relevant with the coverage of polyaniline with response slope.The response time of L-phenylalanine on (-) PA electrode is greater than the response time of D-phenylalanine on this electrode.Response time is defined as from adding analytic sample to the time that obtains stable potential value.Response slope increases along with the increase of the coverage of polyaniline, if the configuration of polyaniline and amino acid whose configuration coupling, final response can reach and can this spy respond; If configuration does not match under the situation of same coverage, response slope is 35mV/dec.The coverage of polyaniline (θ) is represented with the quantity of monomer aniline.It is to calculate according to following formula:
M is the amount of substance of the aniline monomer that drops into when synthesized polyaniline; V represents the cumulative volume of the polyaniline solutions that obtains after the polymerization; On behalf of us, v be modified at the volume of the polyaniline on the glass-carbon electrode; A is the area of glass-carbon electrode.The 95%th, the productive rate of polyaniline.As can be seen from Table 1, optimized coverage is 4.24 * 10
-5Molcm
-2Aniline monomer.With the expression normalization of coverage, that is, optimum coverage is 1 in table 1.
The pH value of solution is to contain 1.0 * 10 to the influence of sensor of the present invention
-2Carry out in the solution of M phenylalanine.The result shows that when the pH value changed, the open circuit potential of electrode did not have too big variation between 6-10.This may be that therefore, the open circuit potential of electrode does not have big variation because in the neutral pH interval, the redox state of polyaniline is not changed.
Studies show that do not have damping fluid to make this sensor of supporting electrolyte and still can carry out chiral Recognition, because amino acid itself just has amino and carboxyl, itself just can be used as supporting electrolyte.Therefore, when measuring, need not to add in addition other electrolyte.Specifically see Figure 13.
Stability to sensor of the present invention is studied, and finds that the response slope of electrode does not have too big variation in error range in one month.The life-span of this this sensor of description of test is quite long.
The present invention has synthesized optically active polyaniline by galvanochemistry and two kinds of synthetic methods of chemistry and with transmission electron microscope and circular dichroism spectra it has been characterized.Use the synthetic optically active polyaniline of chemical synthesis to be modified at and make sensor on the electrode.This sensor is easy to use, and is highly sensitive, and good stability not only can be used for measuring pure enantiomter, can also be used to measure the potpourri of enantiomter, the detection that is applicable to amino acid under the multiple environment and chirality thereof with separate.
Description of drawings
Fig. 1 is sensor detector figure.1 is RE (contrast electrode), and 2 is CE (to electrode), and 3 is WE (working electrode), and 4 is CHI 660 (Shanghai occasion China instrument company), and 5 is computer equipment.
Fig. 2 is the power on circular dichroism spectrogram of chiral polyaniline of chemosynthesis of ITO electrode.Wherein solid line is represented the circular dichroism spectrogram of the chiral polyaniline of being induced by (-) CSA, and dotted line is represented the circular dichroism spectrogram of the chiral polyaniline of being induced by (+) CSA.
Fig. 3 is the circular dichroism spectrogram of the synthetic chiral polyaniline of interfacial.
Fig. 4 is the open circuit potential survey sheet of phenylalanine on the ITO electrode.(■) represent and modified chiral polyaniline (●) on the ITO electrode and represent and do not modify polyaniline on the ITO electrode.
Fig. 5 is the response diagram of naked glass-carbon electrode to phenylalanine.
Fig. 6 is that (-) polyaniline modified electrode is measured the original response figure of (time-current potential) to the open circuit potential of L-phenylalanine.With the standard calomel electrode is contrast electrode.
Fig. 7 is the original response figure that (-) polyaniline modified electrode is measured the open circuit potential of D-phenylalanine.With the standard calomel electrode is contrast electrode.
Fig. 8 is naked glass-carbon electrode (●) and (-) polyaniline modified electrode (■) concentration-potential response figure to the L-phenylalanine.
Fig. 9 is naked glass-carbon electrode (●) and (-) polyaniline modified electrode (■) concentration-potential response figure to the D-phenylalanine.
Figure 10 is (-) polyaniline modified electrode to L-phenylalanine (■) with to the response diagram of D-phenylalanine (●).
Figure 11 is (+) polyaniline modified electrode to D-phenylalanine (■) with to the response diagram of L-phenylalanine (●).
Figure 12 is the linear response slope replot of potpourri of the enantiomter of different proportion.(■) represent the response slope of 100% L-phenylalanine; (●) representative [D-Phe]/[L-Phe] is 1: 10 response slope; () representative [D-Phe]/[L-Phe] is 1: 2 response slope; (△) representative [D-Phe]/[L-Phe] is 1: 1 response slope; (zero) represents the response slope of 100% D-phenylalanine.As seen, [D-Phe]/[L-Phe] be 1: 10 response slope and 100% L-phenylalanine response slope much at one.
Figure 13 is (-) PA sensor response comparison diagram to phenylalanine in water neutralising phosphoric acid damping fluid.(zero) representative in water to the response of L-phenylalanine; (●) representative in phosphate buffer to the response of L-phenylalanine; () representative in water to the response of D-phenylalanine; (■) representative in phosphate buffer to the response of D-phenylalanine.
Figure 14 is the original response figure of (-) PA sensor to the L-alanine.
Figure 15 is the original response figure of (-) PA sensor to the D-histidine.
Figure 16 is the original response figure of (-) PA sensor to the L-halfcystine.
Figure 17 is the original response figure of (-) PA sensor to D-tyrosine.
Figure 18 is the original response figure of (-) PA sensor to the D-proline.
Figure 19 is that (-) PA sensor is to some amino acid whose response diagram summations.
Embodiment
The all ingredients instrument that relates among the embodiment is equipped with according to following method:
Aniline: Shanghai chemical reagent work produces, and uses after the decompression distillation;
Sodium dihydrogen phosphate, sodium hydrogen phosphate: analyze purely, Tianjin chemical reagent work produces.
Ammonium peroxydisulfate, (1S)-(+)-and (1R)-(-)-10-camphorsulfonicacid D-/L-phenylalanine (D/L-Phe), D/L-histidine (D/L-His), D/L-alanine (D/L-Ala), D/L-halfcystine (D/L-Cys), D/L-tyrosine (D/L-Tyr) is purchased the company in Aldrich.
Transmission electron microscope (TEM): JEOL JEM-2011 (Japan)
Circular dichroism spectrometer (CD): Jasco 715 spectrometer
The D/L-Tyr of D/L-Phe, D/L-His, D/L-Ala, D/L-Cys and the 0.002M of configuration 0.1M.
All solution allocation all adopt the milli-Q water that comes from milli-Q synthesis A10 system.Open circuit potential is measured and is adopted the CHI660 electrochemical workstation.Measuring body is a three-electrode system, wherein contrast electrode and electrode used saturated calomel electrode and platinum electrode respectively.Glass-carbon electrode and ITO electrode are as working electrode.Glass-carbon electrode is at first used γ-Al of 1.0 μ m
2O
3Burnishing powder polishes, and then uses 0.3 and 0.05 μ m γ-Al respectively
2O
3Polish last drip washing electrode and ultrasonic cleaning.
The ito glass electrode can adopt conventional method to make.For example, the area with well cutting is about 1cm
2Ito glass and copper conductor by conducting resinl bonding after, place about 4～5 hours of infrared case baking, (70～80 ℃) after cooling, electrode is taken out, and this moment, ito glass connected together with lead, coated epoxy resin (2: 1) then on the surface of conducting resinl, after placing 2～3 hours under the room temperature, place about 3 hours of infrared case baking again, take out the cooling back, places after 24 hours again and can use.Earlier electrode is placed the ultrasonic cleaning of milli-Q water before using, ultrasonic cleaning in ethanol is then cleaned the back and is coated polyaniline solutions uniformly on the ITO surface.
In the solution that contains 1M (+)/(-) CSA and 0.2M aniline, carry out three-dimensional voltolisation, use saturated calomel electrode and gauze platinum electrode as contrast electrode with to electrode respectively, the ITO electrode is a working electrode, uses the method for continuous current polymerization to carry out electropolymerization in above-mentioned solution.The present invention adopts the continuous current polymerization of three steps, and uses current density very little, and the current density of the first step is 0.002mA/cm
2, polymerization time is half an hour; The current density in second step is 0.001mA/cm
2, polymerization time is three hours; The current density in the 3rd step is 0.0005mA/cm
2, polymerization time is three hours.
The synthetic method concrete steps are as follows: A. difference weighing 3.5g (+) CSA and (-) CSA are in two measuring cups, and then weighing 0.49g (NH
4)
2S
2O
4Two parts in above-mentioned two measuring cups, add 1mL water and dissolve.B. getting new distilled aniline 0.195mL dissolves in 4mL benzene.After treating that solution dissolves fully among the A, B is poured among the A.
Because water and benzene are immiscible, so at the two alternate interfaces that produced.After two kinds of solution mixed about 3 ~ 5 minutes, cyan polyaniline began to form and be diffused into aqueous phase gradually, and after 24 hours, whole aqueous phase all is cyan polyaniline, and organic layer then presents brown, may be owing to formed the oligomer of aniline at organic layer.The secondary product on upper strata removed and collect all products of aqueous phase, owing to contain excessive CSA (camphorsulfonic acid) in the solution, so it is acid that polyaniline solutions is at this moment, with milli-Q water polyaniline is washed to neutral back (pH=7), ammoniacal liquor p-poly-phenyl amine with 0.1M went to mix 1 hour, and this moment, polyaniline was by the blackish green mazarine that become.And then the polyaniline washing that will go to mix with milli-Q water is stored in 4 ℃ of refrigerators stand-by to neutral.
The preparation of embodiment 3 sensors
The polyaniline of getting certain volume drops on the glass-carbon electrode of handling well, in air air-dry after, immerse and to remove in the water of oxygen, place a period of time and treat that open circuit potential can begin to carry out the mensuration of phenylalanine after stable.One straight-through N during placement
2, in order to avoid oxygen enters.
The sensor for preparing is placed electrochemical cell, the phenylalanine of isomorphism type is not tested, proving installation figure as shown in Figure 1.
The sign of the chiral polyaniline nano wire that embodiment 4 electrochemical processes are synthetic
With polymerization the ITO electrode of aniline carry out circular dichroism spectra and characterize, find on circular dichroism spectra, to have certain absorption (Fig. 2).On the circular dichroism spectra of the chiral polyaniline of inducing, can see the characteristic absorption peak of chiral polyaniline between 400-500nm by (+) CSA.When we characterize the polyaniline in the solution of collecting with circular dichroism spectra, in the characteristic absorption district of chiral polyaniline positive and negative absorption peak has appearred between the 400-500nm.By on the comparison electrode and the characteristic absorption peak of polyaniline in the solution, the characteristic absorption of finding the chiral polyaniline of being induced by (+) CSA on the ITO electrode shows on circular dichroism spectra and just absorbs.
The characterization result of the chiral polyaniline that embodiment 5 interfacial are synthetic
Synthetic polyaniline is characterized with TEM and CD respectively, and the diameter of the nanofiber of chiral polyaniline changes between the micron of length from 500nm to the hundreds of between 30-50nm in the transmission electron microscope picture of polyaniline.Further observe the situation of a nanofiber, visible polyaniline has certain helical structure.
With the circular dichroism spectrometer its chirality has been carried out detailed sign, its characterization result is seen Fig. 3.Characteristic absorption peak place (450-500nm) after as can be seen from Figure 3 the polyaniline of being induced by (-) CSA goes to mix in circular dichroism spectra shows as negative absorption, is labeled as (-) PA in the drawings; Correspondingly, the polyaniline of being induced by (+) CSA shows positive absorption herein after going to mix, be labeled as (+) PA in the drawings.Sweep velocity is 100nm/min in the mensuration process.
The measurement of embodiment 6 ITO electrode open circuit potentials
Not modified ITO electrode is placed the electrolytic cell that contains 10mL water, in electrolytic cell, place contrast electrode afterwards again and to electrode, three electrodes are joined with CHI 660 electrochemical workstation corresponding electrode folder respectively, the open-circuit potential program of operation CHI 660 begins to show current potential-time diagram this moment on computer screen.After treating that current potential is stable, each L-phenylalanine solution that adds 100 μ L 0.1M in electrolytic cell treats that current potential adds for the second time after stable again, for the third time ... just stop adding much at one the time until the potential value that records for the n time and the n-1 time.We are converted into current potential-concentration logarithmic diagram with the current potential-time diagram of synchronous recording then.To modify (-) PA electrode and also measure with the method, then the result that will record compared with the control, the result is as shown in Figure 4.As can be seen from the figure, the phenylalanine of the ITO electrode pair high concentration of modified polyaniline does not have certain response, but ITO itself also can detect occurrence of amino acid.And the response of the ITO electrode pair phenylalanine behind the modification polyaniline will increase many.The linear fit that the linear response of Fig. 4 is partly carried out as can be seen, the linear response range of phenylalanine between-1gC=2.3～1.6, relative narrower.The straight slope of match is 22.86 ± 0.36mV/dec, and standard deviation is 0.25, and linearly dependent coefficient R is 0.998.
The measurement of embodiment 7 glass-carbon electrode open circuit potentials
ITO electrode among the embodiment 6 is substituted with glass-carbon electrode.In order to compare with the electrode of modifying behind the polyaniline, at first we have measured the response of naked glass-carbon electrode to phenylalanine, and its result as shown in Figure 5.As can be seen from the figure, naked glass-carbon electrode does not respond phenylalanine in the experimental error scope.
(-) polyaniline is modified on the glass-carbon electrode, and the response of detection to phenylalanine uses the same method.Fig. 6 is the current potential-time original response figure of L-phenylalanine on (-) PA modified electrode; Fig. 7 is the current potential-time original response figure of D-phenylalanine on (-) PA modified electrode.As can be seen from Figure 6, along with the growth of time, the concentration of phenylalanine is more and more higher in the electrolytic cell, and the response time is more and more longer, but after reaching-Ding concentration, the response time almost no longer changes.And in Fig. 7, the response time is subjected to the influence of amino acid concentration hardly, and from start to finish the response time does not all have too big variation.Careful contrast two figure can observe (-) polyaniline electrode and will grow the response time of the response time comparison D-phenylalanine of L-phenylalanine.
The linear fit that the linear response of Fig. 4 is partly carried out, and compare with current potential-concentration logarithmic diagram that Fig. 5 is converted to and to obtain Fig. 7; Compare with current potential-concentration logarithmic diagram that Fig. 6 is converted to and to obtain Fig. 8.Comparison diagram 7 and Fig. 8 are as can be known, in identical concentration range, (-) polyaniline electrode is about about 100mV the response of L-phenylalanine, and be about 60mV to the response of D-phenylalanine, illustrate that (-) polyaniline electrode can be in conjunction with more L-phenylalanine, and that the result of Fig. 6 showed the response time of L-phenylalanine is long.
Can clearerly see that from Fig. 8 and Fig. 9 naked glass carbon is measured not contribution of phenylalanine for polyaniline, therefore need not deduct the background of electrode itself.And the changing value of current potential increased than on ITO a lot, thereby improved detection sensitivity and reduced the influence of experimental error relatively.
(-) PA is modified on the electrode, measures its response, as shown in figure 10 two kinds of enantiomters of phenylalanine.As can be seen from the figure, wanting greatly of the response potential changing value comparison D-phenylalanine of the electrode pair L-phenylalanine that (-) PA modifies, and (-) PA is linear at the logarithm of certain concentration range and concentration to the response potential changing value of these two kinds of enantiomters.In this concentration range it is carried out linear fit, as can be seen, the electrode that (-) PA modifies is about 59mV/dec to the response slope of L-phenylalanine in the range of linearity, and the response slope of D-phenylalanine is about 35mV/dec.
More than be the response results of the electrode pair phenylalanine of (-) polyaniline modification, we also examine or check the electrode that (+) polyaniline is modified.Figure 11 is the response results of (+) polyaniline to phenylalanine.
As can be seen from Figure 11 (+) polyaniline electrode wants big to the response ratio of D-phenylalanine to the response of L-phenylalanine, and the spatial configuration of this explanation (+) polyaniline hole is more suitable for combining with the D-phenylalanine.The linear segment of Figure 11 is carried out match, (+) polyaniline electrode is 61mV/dec to the response slope of D-phenylalanine as can be seen, and be 31mV/dec to the response slope of L-phenylalanine, can conclude that according to these results (+) polyaniline electrode is similar to the response of (-) polyaniline electrode to the L-phenylalanine to the response of D-phenylalanine, and (+) polyaniline electrode is similar to the response of D-phenylalanine to response and (-) polyaniline electrode of L-phenylalanine.
The coverage of embodiment 8 polyanilines and response time are to the influence of sensor
The coverage of the response time of sensor and response slope and polyaniline has very big relation.Response time is defined as from adding analytic sample to the time that obtains stable potential value.The response time of L-phenylalanine on (-) PA electrode approximately is 450 seconds, and the response time of D-phenylalanine on this electrode approximately is 300 seconds.Response slope increases along with the increase of the coverage of polyaniline.As can be seen from Table 1, optimized coverage is 4.24 * 10
-5Molcm
-2Aniline monomer.With the expression normalization of coverage, that is, optimum coverage is 1 in table 1.
The relation of the coverage of table 1 polyaniline and the response time of electrode and response slope
| Coverage | Response time (s) | Response slope (mV/dec) | ||
| (-)PAn+L-Phe | (-)PAn+D-Phe | (-)PAn+L-Phe | (-)PAn+D-Phe | |
| 0.125 | 90±10 | 150±20 | 36.90±0.19 | 28.20±0.46 |
| 0.25 | 130±20 | 500±50 | 41.01±0.42 | 28.00±0.84 |
| 0.5 | 500±50 | 300±30 | 48.63±0.37 | 30.43±0.65 |
| 0.75 | 1000±100 | 250±30 | 55.42±0.98 | 33.50±0.51 |
| 1 | 450±50 | 300±20 | 59.04±0.16 | 34.71±0.40 |
| 1.25 | 600±50 | 200±20 | 58.15±0.13 | 33.80±0.36 |
The stability test of embodiment 9 sensors
Table 2 has shown the situation of change of electrode response slope in month, from the table data as can be seen, in one month, the response slope of electrode does not have too big variation in error range.The life-span of this this sensor of description of test is quite long.
The stability of table 2 sensor
| Time | ||||||
| Preparation just | Prepare after 10 days | Prepare after 30 days | ||||
| (-)PAn+L | (-)PAn+D | (-)PAn+L | (-)PAn+D | (-)PAn+L | (-)PAn+D | |
| Slope | 59.0±0.03 | 35.0±0.07 | 61.7±1.9 | 34.7±0.05 | 58.3±0.06 | 34.3±0.04 |
His-and-hers watches 2 data are carried out existing match.(-) PA sensor is 34.03 ± 0.24 to the mean value of D-phenylalanine response and the straight slope of standard deviation match, and standard deviation is 0.51, and the linear fit coefficients R is 0.9999.(-) PA sensor is 59.81 ± 0.18 to the mean value of L-phenylalanine measurement and the straight slope of standard deviation match, and standard deviation is 2.32, and the linear fit coefficients R is 0.9998.This point also is enough to illustrate having good stability of this sensor.
Embodiment 10 (-) PA sensor is to some amino acid whose responses
With the method detecting sensor of embodiment 7 to some amino acid whose corresponding.Figure 14 is the original response figure of L-alanine.Figure 15 is the original response figure of (-) PA sensor to the D-histidine, Figure 16 (-) PA sensor is to the original response figure of L-halfcystine, in this two width of cloth figure, measured response and other response are different, when measuring other amino acid, potential response changes to positive dirction, and the response current potential of this two seed amino acid is then changed to negative direction, may be because contain two N atoms in the histidine, and contain the cause of sulphur atom in the halfcystine.
Figure 17 and Figure 18 are respectively (-) PA sensors to D-tyrosine with to the response of D-proline, from these two figure as can be seen, polyaniline almost to this two seed amino acid without any response.It is because the solubleness of tyrosine in water is very little that this sensor does not have response to tyrosine, to proline do not have response may be because it to be a kind of cyclic amino acid and polyphenyl ammonia very big sterically hindered in conjunction with existing.
(-) PA sensor is listed in Figure 19 to all amino acid whose responses, though (-) PA is bigger to the response ratio of L-halfcystine and L-histidine, in the range of linearity that detects phenylalanine, the response of this two seed amino acid does not influence the mensuration of phenylalanine.
Claims (10)
1. a chiral identification senser is characterized in that, electrode surface covers the chiral polyaniline film in this sensor, and the thickness of film is 0.5～50 μ m.
2. sensor as claimed in claim 1 is characterized in that, electrode is ITO electrode, glass-carbon electrode or platinum electrode in this sensor.
3. sensor as claimed in claim 1 is characterized in that, this sensor electrode surface polyaniline is the chiral polyaniline that d-camphorsulfonic acid or l-camphor sulfonic acid are induced.
4. sensor as claimed in claim 1 is characterized in that, there is chiral polyaniline 5.3 * 10 on the sensor electrode surface for every square centimeter
-6～5.3 * 10
-5Mole.
5. the preparation method of sensor as claimed in claim 1 is characterized in that, this method may further comprise the steps successively:
(1) induces preparation chiral polyaniline film with d-camphorsulfonic acid or l-camphor sulfonic acid;
(2) cleaning and activated electrode;
(3) the chiral polyaniline film that (1) is obtained covers on the electrode that (2) obtain, and the thickness of chiral polyaniline film is 0.5～50 μ m;
(4) behind the pole drying that (3) are obtained, immersed in the water removed oxygen 5～12 hours, treat that open circuit potential is stable, promptly make sensor.
6. the preparation method of sensor as claimed in claim 5 is characterized in that, the electrode of (2) is ITO electrode, glass-carbon electrode or platinum electrode in this method.
7. the preparation method of sensor as claimed in claim 5 is characterized in that, the sensor electrode surface chiral polyaniline film that this method makes covers electrode surface by the galvanochemistry synthetic method.
8. the preparation method of sensor as claimed in claim 5 is characterized in that, the sensor electrode surface chiral polyaniline film that this method makes covers electrode surface by dripping method.
9. the preparation method of sensor as claimed in claim 5 is characterized in that, electrode is by the air-dry method drying in (4).
10. the preparation method of sensor as claimed in claim 5 is characterized in that, the coverage of the sensor electrode surface chiral polyaniline film that this method makes is 0.5～50 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510111257 CN1793884A (en) | 2005-12-08 | 2005-12-08 | Chiral identification senser and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510111257 CN1793884A (en) | 2005-12-08 | 2005-12-08 | Chiral identification senser and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1793884A true CN1793884A (en) | 2006-06-28 |
Family
ID=36805451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510111257 Pending CN1793884A (en) | 2005-12-08 | 2005-12-08 | Chiral identification senser and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1793884A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101963564A (en) * | 2010-08-20 | 2011-02-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Chiral sensor and preparation method thereof |
| CN104792844A (en) * | 2015-04-01 | 2015-07-22 | 常州大学 | Preparation of chitosan-carbon quantum dot composite film modified electrode and application of chitosan-carbon quantum dot composite film modified electrode to electrochemical identification of tryptophan enantiomer |
| CN106990154A (en) * | 2017-03-07 | 2017-07-28 | 常州大学 | A kind of method and its application by the camphorsulfonic acid radical ion synthesis of chiral conducting polymer that adulterates |
| CN107490611A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of polyaniline hybridized materials of chiral MOF and its preparation method and application |
| CN110483792A (en) * | 2019-08-09 | 2019-11-22 | 盐城工学院 | A kind of metal-organic framework materials and its application in quartz crystal microbalance method identification chiral molecules |
| CN114289070A (en) * | 2022-01-07 | 2022-04-08 | 扬州大学 | Supermolecule chiral nano catalyst and preparation method and application thereof |
-
2005
- 2005-12-08 CN CN 200510111257 patent/CN1793884A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101963564A (en) * | 2010-08-20 | 2011-02-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Chiral sensor and preparation method thereof |
| CN104792844A (en) * | 2015-04-01 | 2015-07-22 | 常州大学 | Preparation of chitosan-carbon quantum dot composite film modified electrode and application of chitosan-carbon quantum dot composite film modified electrode to electrochemical identification of tryptophan enantiomer |
| CN104792844B (en) * | 2015-04-01 | 2018-02-02 | 常州大学 | The preparation of a kind of complex film modified electrode of chitosan carbon quantum dot and its applied to electrochemical recognition Tryptophan enantiomer |
| CN106990154A (en) * | 2017-03-07 | 2017-07-28 | 常州大学 | A kind of method and its application by the camphorsulfonic acid radical ion synthesis of chiral conducting polymer that adulterates |
| CN107490611A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of polyaniline hybridized materials of chiral MOF and its preparation method and application |
| CN107490611B (en) * | 2017-09-05 | 2019-09-27 | 济南大学 | Polyaniline hybridized material of a kind of chirality MOF- and its preparation method and application |
| CN110483792A (en) * | 2019-08-09 | 2019-11-22 | 盐城工学院 | A kind of metal-organic framework materials and its application in quartz crystal microbalance method identification chiral molecules |
| CN110483792B (en) * | 2019-08-09 | 2021-11-12 | 盐城工学院 | Metal-organic framework material and application thereof in identification of chiral molecules by quartz crystal microbalance method |
| CN114289070A (en) * | 2022-01-07 | 2022-04-08 | 扬州大学 | Supermolecule chiral nano catalyst and preparation method and application thereof |
| CN114289070B (en) * | 2022-01-07 | 2023-04-25 | 扬州大学 | Supermolecule chiral nano catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mazzotta et al. | Development of a sensor prepared by entrapment of MIP particles in electrosynthesised polymer films for electrochemical detection of ephedrine | |
| Ensafi et al. | An ionic liquid-type multiwall carbon nanotubes paste electrode for electrochemical investigation and determination of morphine | |
| CN101458223B (en) | Preparation of quantitative rapid detecting sensor of microcapsule algae toxin and applications | |
| CN1793884A (en) | Chiral identification senser and its preparation method | |
| Ensafi et al. | Simultaneous determination of ascorbic acid, epinephrine, and uric acid by differential pulse voltammetry using poly (3, 3′-bis [N, N-bis (carboxymethyl) aminomethyl]-o-cresolsulfonephthalein) modified glassy carbon electrode | |
| Yin et al. | Enantioselective sensing of chiral amino acids by potentiometric sensors based on optical active polyaniline films | |
| Babaei et al. | A sensor for simultaneous determination of dopamine and morphine in biological samples using a multi-walled carbon nanotube/chitosan composite modified glassy carbon electrode | |
| CN104807874A (en) | Preparation and application method of molecular imprinting electrochemical sensor | |
| Fu et al. | Electrochemiluminescence sensor for dopamine with a dual molecular recognition strategy based on graphite-like carbon nitride nanosheets/3, 4, 9, 10-perylenetetracarboxylic acid hybrids | |
| CN108546331A (en) | The preparation method of enzyme-metal organic frame composite membrane and the application of modified electrode bio-sensing | |
| CN103940867A (en) | Method for preparing photoelectric adapter sensor for detecting 17beta-estradiol | |
| CN104764775B (en) | Method for preparing triazole molecularly imprinted electrochemical sensor based on electropolymerized OPD/OAP composite membrane and application thereof | |
| Yan et al. | Selective recognition of ciprofloxacin hydrochloride based on molecular imprinted sensor via electrochemical copolymerization of pyrrole and o-phenylenediamine | |
| Sahraoui et al. | A Nitrite Electrochemical Sensor Based on Boron‐Doped Diamond Planar Electrochemical Microcells Modified with a Monolacunary Silicotungstate Polyoxoanion | |
| CN101059479A (en) | Electrochemical detection method for selectively determining plumbum ion density in water system | |
| CN105738441B (en) | A kind of modified glassy carbon electrode and its preparation method and application | |
| CN109001281B (en) | Molecular imprinting photoelectrochemical sensor based on organic-inorganic quantum dot P-N heterostructure and preparation method and application thereof | |
| CN102514261A (en) | Microbiological bio-imprinting membrane and preparation method thereof | |
| CN110044987A (en) | The method of the preparation method and its Electrochemical Detection troponin of the covalent organic frame modified electrode of ferrocenyl | |
| CN107121484B (en) | A kind of electrochemical method of Sensitive Detection glyphosate | |
| CN105223260B (en) | Electrochemical sensor of trace quick detection butyl p-hydroxybenzoate and preparation method thereof | |
| Liang et al. | Preparation of polynorepinephrine adhesive coating via one-step self-polymerization for enantioselective capillary electrochromatography coupled with electrogenerated chemiluminesense detection | |
| CN110261450A (en) | It is a kind of to detect dopamine and adrenaline modified glassy carbon electrode, preparation method and application simultaneously | |
| CN104020205B (en) | The imprinted polymer membrane electrode of parachloroanilinum, its preparation method and application process | |
| CN105866211A (en) | Preparation method and application for ampicillin molecular engram sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |