CN116574414A - Graphite powder/starch chiral selector, glassy carbon electrode, preparation method and application - Google Patents
Graphite powder/starch chiral selector, glassy carbon electrode, preparation method and application Download PDFInfo
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- 229920002472 Starch Polymers 0.000 title claims abstract description 118
- 239000008107 starch Substances 0.000 title claims abstract description 118
- 235000019698 starch Nutrition 0.000 title claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021397 glassy carbon Inorganic materials 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims abstract description 87
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005557 chiral recognition Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002484 cyclic voltammetry Methods 0.000 claims description 8
- 238000012512 characterization method Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims 1
- QIVBCDIJIAJPQS-SECBINFHSA-N D-tryptophane Chemical compound C1=CC=C2C(C[C@@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-SECBINFHSA-N 0.000 abstract description 45
- 230000000694 effects Effects 0.000 abstract description 21
- 230000035945 sensitivity Effects 0.000 abstract description 7
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- 238000001514 detection method Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
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- 230000035484 reaction time Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000003674 animal food additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
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- 229920001661 Chitosan Polymers 0.000 description 1
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- 235000013615 non-nutritive sweetener Nutrition 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 230000002335 preservative effect Effects 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 125000000430 tryptophan group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C2=C([H])C([H])=C([H])C([H])=C12 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
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Abstract
The invention discloses a graphite powder/starch chiral selector and a preparation method and application thereof, wherein the graphite powder/starch chiral selector is prepared by taking graphite powder as a carrier and adsorbing soluble starch to form a surface structure with a chiral group identification, and the preparation method comprises the steps of dissolving the soluble starch and nano graphite powder in ethanol solution, and performing ultrasonic treatment to obtain the graphite powder/starch chiral selector; the graphite powder/starch chiral selector is modified on the glassy carbon electrode and can be applied to chiral recognition of tryptophan, the recognition capability of the modified glassy carbon electrode to D-Trp is higher than that of the modified glassy carbon electrode to L-Trp, and the sensitivity and recognition effect of the sensor are further improved through optimization of recognition conditions. The invention solves the problem that the tryptophan chiral selector cannot be made due to poor conductivity of starch, and simultaneously provides the tryptophan chiral recognition method with short analysis time and higher sensitivity.
Description
Technical Field
The invention relates to the field of chiral recognition, in particular to a graphite powder/starch chiral selector, a glassy carbon electrode, a preparation method and application.
Background
Amino acid is taken as a basic unit for constructing a life system, other tryptophan is chiral micromolecules except glycine, and is one of the most common chiral substances in life, and chiral molecules are divided into D type and L type, so that the chiral molecules have different or even opposite effects. D-Trp in tryptophan (D/L-Trpptophan, D/L-Trp) has certain value in food, feed industry and agriculture, and can be used as a non-nutritive sweetener, a feed additive and a plant growth agent, and particularly in the pharmaceutical industry, D-Trp is an important synthetic precursor of anticancer agents and immunosuppressants. L-Trp is a tryptophan that is necessary for the human and animal body and is not synthesized by itself, and is required to be taken in from food, and is called second essential tryptophan. The method is widely applied to industries such as medicines, foods, feed additives, agricultural environment detection and the like.
Inspection and separation of a pair of enantiomers can be achieved by chiral recognition techniques to obtain a single enantiomer of a particular monomer that is beneficial to the human body and environment. Common detection and identification methods are spectroscopy, chromatography and sensor methods. The detection method has the problems of low detection speed, low sensitivity and the like. Meanwhile, chiral selection agents in chiral recognition technology are key factors for realizing chiral recognition. Polysaccharides are common chiral selectors, and polysaccharide substances used for chiral recognition mainly comprise starch, cellulose, chitosan and the like. Starch is mainly composed of amylose and amylopectin, and has a complex double helix structure, which plays an important role in chiral separation of tryptophan enantiomers. However, since starch has poor conductivity, it cannot be directly used as a tryptophan chiral selector, and little research is currently conducted on the use of starch as a tryptophan chiral selector. It is therefore desirable to provide a chiral selector capable of improving the conductivity problem of starch and a tryptophan chiral recognition method capable of improving the detection speed and sensitivity.
Disclosure of Invention
In order to solve the problems that the starch in the prior art is poor in conductivity and cannot be used as a chiral selector to identify tryptophan chiral molecules, and the existing identification method is long in analysis time and low in sensitivity, the graphite powder/starch chiral selector, the preparation method and the application thereof in tryptophan chiral identification are provided.
In order to achieve the above object, the technical scheme of the present invention is as follows.
The graphite powder/starch chiral selector is prepared by taking graphite powder as a carrier and adsorbing soluble starch to form a surface structure with a chiral recognition group;
the mass ratio of the soluble starch to the nano graphite powder is 1:2-5.
Further, the graphite powder/starch chiral selector is prepared by dispersing soluble starch and nano graphite powder in ethanol.
The invention also provides a preparation method of the graphite powder/starch chiral selector, which comprises the following steps:
adding the soluble starch and the nano graphite powder into ethanol for ultrasonic dispersion to obtain graphite powder-starch chiral selector dispersion liquid.
Further, the ultrasonic time is 1.5-2.5h.
The invention also provides a glassy carbon electrode modified by the graphite powder/starch chiral selector, which is prepared by forming a film on the surface of the glassy carbon electrode by the graphite powder/starch chiral selector.
The invention also provides a preparation method of the glassy carbon electrode modified by the graphite powder/starch chiral selector, which comprises the following steps:
and forming a film on the surface of the pretreated glassy carbon electrode by the graphite powder/starch chiral selector to obtain the glassy carbon electrode modified by the graphite powder/starch chiral selector.
Further, the pretreatment of the glassy carbon electrode is to polish the surface of the glassy carbon electrode.
Further, the pretreatment of the glassy carbon electrode is to pretreat 0.1 μm and 0.05 μm Al 2 O 3 Diluting the polishing powder with ultrapure water to paste, sequentially adding 0.1 μm of glassy carbon electrode into paste Al 2 O 3 Polishing powder and 0.05 mu m of pasty Al 2 O 3 Polishing the polishing powder to form mirror surfaces, washing the mirror surfaces with ultrapure water, and naturally airing the mirror surfaces at room temperature.
The invention also provides an application of the glassy carbon electrode modified by the graphite powder/starch chiral selector in tryptophan chiral recognition.
The invention also provides a tryptophan chiral recognition method, which comprises the following steps:
immersing the glassy carbon electrode modified by the graphite powder/starch chiral selector into a solution containing tryptophan, and carrying out chiral recognition on the tryptophan through cyclic voltammetry characterization;
further, the tryptophan solution has a pH of 3-9; the concentration of tryptophan in the tryptophan solution is 2-8mmol/L.
Further, the time for immersing the glassy carbon electrode into the solution containing tryptophan is 5-60min, and the temperature is 5-40 ℃;
the tryptophan solution also comprises a test base solution, wherein the test base solution is KCl solution and K 3 [Fe(CN) 6 ]Solution and K 4 [Fe(CN) 6 ]A mixed solution of the solutions, the K 3 [Fe(CN) 6 ]Solution and the K 4 [Fe(CN) 6 ]The volume ratio of the solution is 1:1, the concentration of the KCl solution is 0.1mol/L, K 3 [Fe(CN) 6 ]Solution and K 4 [Fe(CN) 6 ]The concentration of the solutions was 5mmol/L.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention solves the problem of poor conductivity of the existing starch serving as a chiral selector by preparing the graphite powder/starch chiral selector. The graphite powder has high temperature resistance, electric conduction and thermal conduction, and can be well dispersed on the surface of the glassy carbon electrode to form a film, and the graphite powder has loose and porous structure, large specific surface area and good electric conduction performance. The chiral selector prepared from the graphite powder and the starch can well solve the problem of poor conductivity of the starch.
2. In the graphite powder/starch chiral selector prepared by the invention, graphite powder is used as a carrier, and soluble starch is adsorbed to form a modified electrode surface capable of selectively adsorbing chiral molecules, so that the modified electrode surface is used for identifying D-Trp and L-Trp. The chiral selector modified glassy carbon electrode has different degrees of D-Trp and L-Trp, i.e. different generated electrochemical signals, so that the purpose of chiral recognition can be achieved.
3. The prepared graphite powder/starch chiral selector is modified on the glassy carbon electrode for chiral identification of tryptophan, and has the advantages of high sensitivity, simplicity in operation and the like. The method for identifying the tryptophan chiral is optimized, and the identification effect on the D-Trp and the L-Trp is further improved.
4. The recognition capability of the chiral surface formed by the graphite powder/starch chiral selector on D-Trp is higher than that of L-Trp, so that tryptophan enantiomer can be accurately recognized, and separation of D-Trp and L-Trp is facilitated.
Drawings
FIG. 1 is a CV diagram of a glassy carbon electrode modified by a graphite powder/starch chiral selector and an unmodified glassy carbon electrode in example 6 of the present invention.
FIG. 2 is a CV diagram of tryptophan chiral recognition by a glassy carbon electrode modified by a graphite powder/starch chiral selector in example 6 of the present invention.
FIG. 3 is a CV diagram of D-Trp recognition at different sweep rates for a graphite powder/starch chiral selector modified glassy carbon electrode in example 6 of the present invention.
FIG. 4 is a graph showing the current change of the base fluid at different pH values for the graphite powder/starch chiral selector modified glassy carbon electrode of example 6 of the present invention.
FIG. 5 is a graph showing the effect of graphite powder/starch chiral selector modified glassy carbon electrode in example 6 of the present invention on L-Trp and D-Trp selectivity recognition under different pH test base fluids.
FIG. 6 is a graph showing the effect of reaction time with L-Trp solution and D-Trp solution at different immersion times of the graphite powder/starch chiral selector modified glassy carbon electrode in example 6 of the present invention.
FIG. 7 is a graph showing the effect of graphite powder/starch chiral selector modified glassy carbon electrode on ΔIt at different immersion times in example 6 of the present invention.
FIG. 8 is a graph showing the effect of graphite powder/starch chiral selector modified glassy carbon electrode in example 6 of the present invention on L-Trp and D-Trp recognition at different immersion temperatures.
FIG. 9 is a graph showing the effect of graphite powder/starch chiral selector modified glassy carbon electrode on ΔI at different immersion temperatures in example 6 of the present invention.
FIG. 10 is a graph showing the effect of chiral recognition in D-Trp and L-Trp solutions of different concentrations for a graphite powder/starch chiral selector modified glassy carbon electrode in example 6 of the present invention.
FIG. 11 is a graph showing the effect of graphite powder/starch chiral selector modified glassy carbon electrode on ΔI at different concentrations of D-Trp solution and L-Trp solution in example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
A preparation method of a graphite powder/starch chiral selector comprises the following steps:
s1, weighing soluble starch and nano graphite powder, putting the soluble starch and the nano graphite powder into a beaker, and dissolving the soluble starch and the nano graphite powder with absolute ethyl alcohol; wherein the mass ratio of the soluble starch to the nano graphite powder is 1:2;
s2, sealing the beaker by using a preservative film, placing the beaker into an ultrasonic cleaner for ultrasonic dispersion for 1.5 hours, and obtaining a graphite powder-starch chiral selector dispersion liquid with the ultrasonic frequency of 40KHz, and placing the graphite powder-starch chiral selector dispersion liquid into a refrigerator for standby.
Example 2
The procedure of example 1 was followed except that the mass ratio of the soluble starch to the nano-graphite powder in S1 was 1:3.
Example 3
The procedure of example 1 was followed except that the mass ratio of the soluble starch to the nano-graphite powder in S1 was 1:4.
Example 4
The procedure of example 1 was followed except that the mass ratio of the soluble starch to the nano-graphite powder in S1 was 1:5.
Example 5
A preparation method of a glassy carbon electrode modified by graphite powder/starch chiral selector comprises the following steps:
al of 0.1 μm or 0.05 μm 2 O 3 Diluting the polishing powder with ultrapure water to paste, sequentially adding 0.1 μm Al into the glassy carbon electrode 2 O 3 Polishing powder and 0.05 μm Al 2 O 3 Polishing the polishing powder to form mirror surfaces, washing the mirror surfaces with ultrapure water, and naturally airing the mirror surfaces at room temperature; and 5 mu L of the graphite powder/starch chiral selector in the embodiment 1 is dripped on the surface of the treated glassy carbon electrode by a microsyringe, and naturally dried to form a film at room temperature, so that the glassy carbon electrode modified by the graphite powder/starch chiral selector is obtained.
Example 6
The procedure of example 5 was repeated except that the graphite powder/starch chiral selector of example 2 was added dropwise to the treated glassy carbon electrode; the specific method comprises the following steps:
al of 0.1 μm or 0.05 μm 2 O 3 Diluting the polishing powder with ultrapure water to paste, sequentially adding glassy carbon electrode into 0.1 μm paste Al 2 O 3 Polishing powder and 0.05 mu m of pasty Al 2 O 3 Polishing the polishing powder to form mirror surfaces, washing the mirror surfaces with ultrapure water, and naturally airing the mirror surfaces at room temperature; mu.L of graphite powder/starch from example 2 was taken with a microsyringeAnd (3) dripping the chiral selector on the surface of the treated glassy carbon electrode, naturally airing the glassy carbon electrode at room temperature to form a film, and obtaining the glassy carbon electrode modified by the graphite powder/starch chiral selector.
Example 7
The procedure of example 5 was repeated except that the graphite powder/starch chiral selector of example 3 was added dropwise to the treated glassy carbon electrode; the specific method comprises the following steps:
al of 0.1 μm or 0.05 μm 2 O 3 Diluting the polishing powder with ultrapure water to paste, sequentially adding glassy carbon electrode into 0.1 μm paste Al 2 O 3 Polishing powder and 0.05 mu m of pasty Al 2 O 3 Polishing the polishing powder to form mirror surfaces, washing the mirror surfaces with ultrapure water, and naturally airing the mirror surfaces at room temperature; and 5 mu L of the graphite powder/starch chiral selector in the embodiment 3 is dripped on the surface of the treated glassy carbon electrode by a microsyringe, and naturally dried to form a film at room temperature, so that the glassy carbon electrode modified by the graphite powder/starch chiral selector is obtained.
Example 8
The procedure of example 5 was repeated except that the graphite powder/starch chiral selector of example 4 was added dropwise to the treated glassy carbon electrode; the specific method comprises the following steps:
al of 0.1 μm or 0.05 μm 2 O 3 Diluting the polishing powder with ultrapure water to paste, sequentially adding glassy carbon electrode into 0.1 μm paste Al 2 O 3 Polishing powder and 0.05 mu m of pasty Al 2 O 3 Polishing the polishing powder to form mirror surfaces, washing the mirror surfaces with ultrapure water, and naturally airing the mirror surfaces at room temperature; and 5 mu L of the graphite powder/starch chiral selector in the embodiment 4 is dripped on the surface of the treated glassy carbon electrode by a microsyringe, and naturally dried to form a film at room temperature, so that the glassy carbon electrode modified by the graphite powder/starch chiral selector is obtained.
The following experiments were performed to demonstrate the high conductivity and low resistance of the graphite powder/starch chiral selector modified glassy carbon electrode and the effect on tryptophan chiral recognition.
1. Influence of mass ratio of nano graphite powder to soluble starch on conductivity of glassy carbon electrode modified by graphite powder/starch chiral selector
And (3) immersing the graphite powder/starch chiral selector modified glassy carbon electrodes prepared in the above examples 5-8 into a test base solution with a pH value of 7 respectively for cyclic voltammetry test. Wherein the test base solution is KCl solution and K 3 [Fe(CN) 6 ]Solution and K 4 [Fe(CN) 6 ]A mixed solution of solutions; KCl solution concentration is 0.1mol/L, K 3 [Fe(CN) 6 ]The concentration of the solution is 5mmol/L, K 4 [Fe(CN) 6 ]The concentration of the solution is 5mmol/L, K 3 [Fe(CN) 6 ]Solution and K 4 [Fe(CN) 6 ]The volume ratio of the solutions was 1:1 (the above test base solution is a common test base solution, the test base solutions mentioned below are all the same as the above test base solution in proportion, and the proportion of the test base solution is not repeated here).
TABLE 1 oxidation peak current values at different ratios of nano graphite powder to soluble starch
Note that: the mass ratio is the mass ratio of the nano graphite powder to the soluble starch.
As can be seen from the results of the table, the oxidation peak current value is highest when the mass ratio of the starch to the nano graphite powder is 1:3. The oxidation peak current value of the starch and the nano graphite powder is minimum when the mass ratio is 1:2, the oxidation peak current value reaches the highest when the mass ratio is 1:3, and the oxidation peak current value is reduced along with the increase of the nano graphite powder but is not lower than the oxidation peak current value when the mass ratio is 1:2 when the mass ratio is 1:4 and 1:5. Therefore, when the mass ratio is 1:2, the graphite powder does not adsorb all the starch, so that the oxidation peak current value is the lowest, when the mass ratio is 1:3, the oxidation peak current value reaches the highest, which indicates that the graphite powder adsorbs all the starch, so that the oxidation peak current value is the highest, but when the mass ratio is 1:4 and 1:5, the graphite powder content is excessive, the electrode surface is blocked, and the oxidation peak current value is influenced.
2. Comparison of the conductivity of the graphite powder/starch chiral selector modified glassy carbon electrode and the unmodified glassy carbon electrode
The graphite powder/starch chiral selector modified glassy carbon electrode and the unmodified glassy carbon electrode in example 6 are respectively placed into a test base solution with a pH value of 7, cyclic voltammetry is adopted, CV scanning is carried out, and the scanning results are shown in figure 1.
As can be seen from fig. 1, the curve a is the CV curve of the unmodified glassy carbon electrode in the test base solution, and the curve b is the CV curve of the glassy carbon electrode modified by the graphite powder/starch chiral selector. Because the test base solution has a pair of redox couple Fe 3+ 、Fe 2+ Therefore, the glassy carbon electrode generates a pair of aligned reversible oxidation-reduction peaks in the test base solution, and the graphite powder has excellent conductivity and can promote the transfer of electrons on the surface of the glassy carbon electrode, so that the current value of the oxidation peak is increased compared with that of a curve a, which proves that the glassy carbon electrode modified by the graphite powder/starch chiral selector has better conductivity and low resistance.
3. Effect of glassy carbon electrode modified by graphite powder/starch chiral selector on tryptophan chiral recognition
Three glassy carbon electrodes in example 6 were respectively placed in a test base solution without tryptophan, a D-Trp solution containing 5mmol/L in the test base solution, and an L-Trp solution containing 5mmol/L in the test base solution, immersed for 15 minutes, and then CV scanning was performed, and the results are shown in FIG. 2. As can be seen from FIG. 2, curve a is the CV curve of the modified glassy carbon electrode immersed in the test base solution without tryptophan, curve b is the CV curve of the modified glassy carbon electrode immersed in the test base solution containing 5mmol/L of the L-Trp solution, and curve c is the CV curve of the modified glassy carbon electrode immersed in the test base solution containing 5mmol/L of the D-Trp solution. It can be seen from fig. 2 that the peak current values of the curve b and the curve c are reduced from those of the curve a. This is because L-Trp and D-Trp are protein molecules that inhibit electron transfer. Also, under the same conditions, the peak current value of curve c drops more, indicating that the amount of D-Trp adsorbed on the chiral surface is greater than the amount of L-Trp adsorbed, i.e., the chiral surface has a stronger effect on D-Trp.
Then, the glassy carbon electrode modified by the graphite powder/starch chiral selector in the embodiment 6 is placed in a D-Trp solution containing 5mmol/L in a test base solution, immersed for 15min, and placed at different sweeping speeds for CV characterization, wherein the sweeping speeds are respectively: 50mV/s, 80mV/s, 100mV/s, 150mV/s, 200mV/s, 300mV/s, 400mV/s, 500mV/s. As a result, as shown in fig. 3, a) in fig. 3 shows that as the sweep rate increases, the oxidation peak current value increases, and the reduction peak current value decreases, and B) shows that the oxidation-reduction peak current values have good linear relations with the sweep rate, respectively, and the linear relation of the oxidation peaks is: i=0.4445v+128.99, the linear relationship of the reduction peaks is: i= -0.4005v-130.41. It is explained that the oxidation-reduction reaction process of the electroactive substances on the glassy carbon electrode modified by the graphite powder/starch chiral selector is controlled by surface adsorption.
To further optimize the conditions for tryptophan chiral recognition for the graphite powder/starch chiral selector modified glassy carbon electrode, we performed the following experiments.
1. Testing the influence of the pH value of the base solution on the chiral identification of tryptophan
The glassy carbon electrode modified by the graphite powder/starch chiral selector in example 6 is immersed in the test base solution with pH value of 3.0, 3.5, 4.0, 4.5, 5.5, 6.0, 6.5, 7.0, 8.0, 8.5 and 9.0 respectively, cyclic voltammetry characterization is carried out, and the test base solution with optimized pH value is obtained, and the result is shown in fig. 4.
5mmol/L of D-Trp and 5mmol/L of L-Trp solution are added into the test base solution after the pH value optimization, the two glassy carbon electrodes modified by the graphite powder/starch chiral selector in the example 6 are respectively immersed for 15min, CV scanning is carried out, and peak current values are measured, and the result is shown in FIG. 5.
As can be seen from fig. 4, as the pH of the test base solution increases, the peak current tends to decrease overall, and the decrease is more pronounced in the pH range of 4.5 to 6.5, and then starts to fluctuate and gradually decreases. From fig. 5, it can be seen that the effect of the glassy carbon electrode modified by the graphite powder/starch chiral selector on the selective recognition of D-Trp and L-Trp in the test base solutions with different pH values. And taking the pH value as an abscissa, and delta IpH as an ordinate, wherein delta IpH is the difference of the oxidation peak currents before and after the reaction of the modified glassy carbon electrode and the D-Trp minus the difference of the oxidation peak currents before and after the reaction of the modified glassy carbon electrode and the L-Trp. The Delta IpH value is greatest and the selectivity to D-Trp and L-Trp is best at pH 5.5. Considering together, the optimal choice of pH of the test base solution is 5.5.
2. Effect of immersion time on tryptophan chiral recognition
And respectively adding 5mmol/L of D-Trp solution and 5mmol/L of L-Trp solution into the test base solution with the pH value of 5.5, respectively immersing the two glassy carbon electrodes modified by the graphite powder/starch chiral selector in the embodiment 6, wherein the immersion time is respectively 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min and 60min, performing cyclic voltammetry scanning, and measuring peak current values, wherein the result is shown in figure 6.
As shown in fig. 6, the effect of the immersion time on the reaction degree is more remarkable, and the longer the immersion time is, the greater the reaction degree is, until the reaction is completed. The oxidation peak current values of the L-Trp and the D-Trp are obviously reduced along with the increase of the reaction time, but the broken lines of the L-Trp and the D-Trp show obviously different change trends when the reaction time is 45 min.
To further compare the effect of reaction time on the selective recognition of D-Trp and L-Trp, the following data processing was performed. As shown in fig. 7, the abscissa indicates the incubation time, and the ordinate indicates Δit (Δit is the difference between the oxidation peak currents before and after the reaction of the modified glassy carbon electrode with D-Trp minus the difference between the oxidation peak currents before and after the reaction of the modified glassy carbon electrode with L-Trp). It can be seen from fig. 7 that at 40 minutes, the value of Δit is the largest and the selectivity is the strongest, so the optimal immersion time is 40 minutes.
3. Influence of immersion temperature on tryptophan chiral recognition
And respectively adding 5mmol/L of D-Trp solution and 5mmol/L of L-Trp solution into the test base solution with the pH value of 5.5, respectively immersing the two glassy carbon electrodes modified by the graphite powder/starch chiral selector in the embodiment 6 for 40min, performing cyclic voltammetry scanning at the immersion temperature of 5-40 ℃, and measuring the peak current value, wherein the result is shown in figure 8.
As can be seen from fig. 8, as the temperature increases, the oxidation peak current values of both graphite powder/starch chiral selector modified glassy carbon electrodes decrease. This is because the temperature is raised in a certain range, and the reaction of the chiral selector with D-Trp and L-Trp can be promoted.
In order to further compare the effect of the invasion temperature on the selective recognition of D-Trp and L-Trp, data processing was performed such that, as shown in FIG. 9, the temperature is on the abscissa and the ordinate is DeltaI (DeltaI is the difference between the oxidation peak currents before and after the reaction of the modified glassy carbon electrode with D-Trp minus the difference between the oxidation peak currents before and after the reaction of the modified glassy carbon electrode with L-Trp), and as shown in FIG. 9, the amount of D-Trp and L-Trp adsorbed by the modified glassy carbon electrode is the largest when the invasion temperature is 25℃and the difference between the response current values is the largest, and therefore, the experimental optimum reaction temperature is 25 ℃.
4. Effect of different concentrations of D-Trp solution and L-Trp solution on tryptophan chiral recognition
D-Trp solution and L-Trp solution with the concentrations of 2mmol/L, 3mmol/L, 4mmol/L, 5mmol/L, 6mmol/L, 7mmol/L and 8mmol/L are respectively added into test base solution with the pH value of 5.5, the graphite powder/starch chiral selector modified glassy carbon electrode in the example 6 is respectively immersed for 45min, the immersion temperature is 25 ℃, cyclic voltammetry scanning is carried out, and peak current values are measured, and the result is shown in figure 10.
FIG. 10 shows that the response current values of the oxidation peaks gradually decrease with increasing concentrations of the D-Trp solution and the L-Trp solution. In order to further compare the effect of the concentrations of the D-Trp solution and the L-Trp solution on the selective recognition of the D-Trp and the L-Trp, data processing was performed such that the concentrations were plotted on the abscissa and the Δi on the ordinate as shown in fig. 11 (where Δi is the difference between the oxidation peak currents before and after the reaction of the modified glassy carbon electrode with the D-Trp solution and the L-Trp solution of different concentrations, respectively), and the difference between the oxidation peak currents after the reaction of the glassy carbon electrode modified with the graphite powder/starch chiral selector and the enantiomer concentrations was gradually increased as the concentrations of the D-Trp solution and the L-Trp solution were continuously increased as shown in fig. 11.
From the above experiments, it can be seen that the chiral surface constituted by graphite powder/starch chiral selector shows good response to D-Trp and L-Trp, and the recognition capacity of the chiral surface to D-Trp is higher than that of L-Trp under the same conditions. By optimizing the tryptophan chiral recognition method, the detection effect and the detection sensitivity are improved, and experiments show that the chiral surface has a certain linear relation with the peak current values obtained after the D-Trp and L-Trp solutions with different concentrations act.
According to the invention, the graphite powder is used as a carrier, so that the problem that starch cannot be used as a chiral selector due to poor conductivity is solved, and meanwhile, the optimal identification condition is obtained by optimizing the tryptophan chiral identification condition, so that the identification efficiency is improved, and the method has important significance in the fields of medicine, pharmacy and biology.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The graphite powder/starch chiral selector is characterized in that the graphite powder/starch chiral selector is prepared by taking nano graphite powder as a carrier and adsorbing soluble starch to form a surface structure with a chiral recognition group;
the mass ratio of the soluble starch to the nano graphite powder is 1:2-5.
2. The graphite powder/starch chiral selector according to claim 1, wherein the graphite powder/starch chiral selector is prepared by dispersing soluble starch and nano-graphite powder in ethanol.
3. A method for preparing the graphite powder/starch chiral selector of claim 2, comprising the steps of:
adding the soluble starch and the nano graphite powder into ethanol for ultrasonic dispersion to obtain graphite powder/starch chiral selector dispersion liquid.
4. A method of preparing a graphite powder/starch chiral selector according to claim 3, wherein the ultrasound time is 1.5-2.5h.
5. The glassy carbon electrode modified by the graphite powder/starch chiral selector is characterized in that the glassy carbon electrode is prepared by forming a film on the surface of the glassy carbon electrode by the graphite powder/starch chiral selector in claim 1.
6. The preparation method of the glassy carbon electrode modified by the graphite powder/starch chiral selector is characterized by comprising the following steps of:
forming a film of the graphite powder/starch chiral selector on the surface of the pretreated glassy carbon electrode to obtain the glassy carbon electrode modified by the graphite powder/starch chiral selector.
7. Use of the glassy carbon electrode of claim 5 in tryptophan chiral recognition.
8. A method for chiral recognition of tryptophan, comprising the steps of:
after immersing the glassy carbon electrode modified by the graphite powder/starch chiral selector in the solution containing tryptophan, chiral identification of tryptophan is performed through cyclic voltammetry characterization.
9. The tryptophan chiral recognition method according to claim 8, wherein the tryptophan solution has a pH of 3 to 9; the concentration of tryptophan in the tryptophan solution is 2-8mmol/L.
10. The method for identifying tryptophan chirality according to claim 8, wherein the glassy carbon electrode is immersed in the solution containing tryptophan for 5 to 60 minutes at a temperature of 5 to 40 ℃.
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