CN113075275A - Gold @ silver core-shell nanoparticle and method for electrochemical alternating-current impedance ultrasensitive chiral recognition by using same - Google Patents
Gold @ silver core-shell nanoparticle and method for electrochemical alternating-current impedance ultrasensitive chiral recognition by using same Download PDFInfo
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- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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Abstract
The invention belongs to the technical field of nano material preparation and molecular recognition, and relates to gold @ silver core-shell nano particles and a method for electrochemical alternating-current impedance ultrasensitive chiral recognition by using the same. The method comprises the following steps: preparing gold nanoparticles, preparing gold @ silver core-shell nanoparticles/tryptophan compound, preparing a gold @ silver core-shell nanoparticle/tryptophan compound modified electrode, and carrying out electrochemical alternating-current impedance ultrasensitive chiral recognition on tryptophan enantiomer. The invention has the beneficial effects that: the prepared gold @ silver core-shell nanoparticle/tryptophan compound can be used for ultra-sensitive chiral recognition of tryptophan enantiomers, and effective electrochemical impedance recognition can be realized on tryptophan enantiomers with the concentration as low as 0.1 nmol/L.
Description
Technical Field
The invention belongs to the technical field of nano material preparation and molecular recognition, and particularly relates to gold @ silver core-shell nano particles and a method for electrochemical alternating-current impedance ultrasensitive chiral recognition by using the same.
Background
Chiral and chiral analysis are of great interest in modern chemistry and chemical technology, and therefore the development of simple and intelligent enantiomer recognition devices has become a research hotspot in life sciences and many other related fields. Amino acids are important enantiomeric compounds, the different configurations of which play different and even opposite roles in life sciences. Therefore, chiral recognition of the enantiomers of amino acids is of great significance in life sciences. At present, the most common methods for enantioselective identification are mainly chromatograms and spectroscopy, however these two methods are costly and time consuming. Therefore, it is necessary to develop a low-cost, fast and sensitive chiral recognition method.
The electrochemistry has received wide attention of people due to the advantages of low cost, high speed, high sensitivity and the like. During the past decades, most researchers have focused on the selection of chiral modifiers to construct electrochemical chiral sensors, including chitosan, beta-cyclodextrin, and bovine serum albumin, among others. However, non-electroactive chiral modifiers can block electron transport at the electrode/solution interface, thereby severely affecting the sensitivity of electrochemical chiral recognition. Therefore, it is important to develop new electroactive chiral modifiers for ultrasensitive chiral recognition.
In recent years, colorimetric chiral recognition based on the intrinsic chirality of monometallic nanoparticles such as gold and silver nanoparticles has received considerable attention. However, there are relatively few reports of electrochemical chiral recognition using core-shell structured nanoparticles. Colorimetric chiral recognition is the use of a target to selectively induce aggregation of nanoparticles, resulting in a change in the color and surface plasmon resonance of the nanoparticle solution. However, the main disadvantage of chiral identification by colorimetric methods is their poor sensitivity and the inability to efficiently identify enantiomers at low concentrations. In order to overcome the defect, gold @ silver core-shell nanoparticles are prepared and used for electrochemical alternating current impedance ultrasensitive chiral identification of enantiomers.
Disclosure of Invention
The invention aims to provide a preparation method of a gold @ silver core-shell nanoparticle/tryptophan compound for electrochemical alternating-current impedance ultrasensitive chiral recognition, which realizes ultrasensitive chiral recognition of tryptophan enantiomer with the concentration as low as 0.1 nmol/L.
The technical scheme provided by the invention is as follows:
the preparation method of the gold @ silver core-shell nanoparticle comprises the following steps:
preparing gold nanoparticles by adopting tetrachloroauric acid trihydrate and sodium citrate; and heating the gold nanoparticles to boiling, and adding a sodium citrate solution and a silver nitrate solution to obtain the gold @ silver core-shell nanoparticles.
Further, the preparation of gold nanoparticles comprises the following steps:
adding water into the tetrachloroauric acid trihydrate solution, stirring, heating the solution to boiling, adding the sodium citrate solution, changing the solution from light yellow to dark red, and continuously stirring at high temperature to obtain the gold nanoparticles.
Further, the gold @ silver core-shell nanoparticle comprises the following steps: heating the gold nanoparticle solution to boiling, adding a sodium citrate solution and a silver nitrate solution, changing the solution from deep red to orange, and continuously stirring at high temperature to obtain the gold @ silver core-shell nanoparticles.
The invention also provides application of the gold @ silver core-shell nano particles in electrochemical alternating-current impedance ultrasensitive chiral recognition.
An electrochemical alternating-current impedance ultrasensitive chiral recognition method comprises the steps of adding tryptophan solution into the gold @ silver core-shell nano particles, standing for reaction to obtain gold @ silver core-shell nano particles/tryptophan complexes, dropwise coating the gold @ silver core-shell nano particles/tryptophan complexes on the surface of a glassy carbon electrode, and drying under an infrared lamp to obtain gold @ silver core-shell nano particles/tryptophan complex modified electrodes; the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode is statically placed in a potassium chloride solution containing potassium ferricyanide/potassium ferrocyanide, an electrochemical alternating-current impedance spectrogram of the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode is recorded, and the ultrasensitive chiral recognition of a tryptophan enantiomer is realized by comparing the electrochemical alternating-current impedance spectrogram.
Further, if the electrochemical alternating-current impedance spectrograms of the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode and the gold @ silver core-shell nanoparticle modified electrode are compared, if the charge transfer resistance of the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode is obviously increased and the difference value exceeds 50 omega, the tryptophan is D-tryptophan; if the difference is not more than 10 omega, the L-tryptophan is obtained.
Furthermore, the frequency range of the electrochemical alternating-current impedance is 0.01-106Hz, amplitude of 5 mV.
Further, the drying time under an infrared lamp is 10-20 min.
Further, the potassium chloride solution containing potassium ferricyanide/potassium ferrocyanide has a concentration of 5mmol/L potassium ferricyanide/potassium ferrocyanide in 0.1mol/L potassium chloride solution.
Further, the tryptophan concentration may be as low as 0.1 nmol/L.
The preparation method of the gold @ silver core-shell nanoparticle/tryptophan compound for electrochemical alternating-current impedance ultrasensitive chiral recognition comprises the following steps:
a. preparing gold nanoparticles: adding 1mL of tetrachloroauric acid trihydrate solution into 98mL of water, stirring, heating the solution to boiling, adding 1mL of sodium citrate solution, changing the solution from light yellow to deep red, and continuously stirring at high temperature for 10min to obtain gold nanoparticles;
b. preparing gold @ silver core-shell nanoparticles: b, putting 20mL of the gold nanoparticles prepared in the step a into a beaker, heating the solution to boiling, adding 1mL of sodium citrate solution and 20 mu L of silver nitrate solution, changing the solution from deep red to orange, and continuously stirring at high temperature for 10min to obtain gold @ silver core-shell nanoparticles;
c. preparing a gold @ silver core-shell nanoparticle/tryptophan complex: taking 2mL of the gold @ silver core-shell nanoparticles prepared in the step b, respectively adding 0.5mL of L-tryptophan and D-tryptophan solutions with certain concentrations, and standing at room temperature for reaction for 15min to obtain a gold @ silver core-shell nanoparticle/L-tryptophan compound and a gold @ silver core-shell nanoparticle/D-tryptophan compound;
d. preparing a gold @ silver core-shell nanoparticle/tryptophan compound modified electrode: c, respectively transferring the gold @ silver core-shell nanoparticle/L-tryptophan compound and the gold @ silver core-shell nanoparticle/D-tryptophan compound prepared in the step c to the surface of a glassy carbon electrode by using a liquid-transferring gun, and drying under an infrared lamp to obtain a gold @ silver core-shell nanoparticle/L-tryptophan compound modified electrode and a gold @ silver core-shell nanoparticle/D-tryptophan compound modified electrode;
e. electrochemical alternating-current impedance ultrasensitive chiral recognition of tryptophan enantiomer: d, standing the gold @ silver core-shell nanoparticle/L-tryptophan compound modified electrode and the gold @ silver core-shell nanoparticle/D-tryptophan compound modified electrode prepared in the step D in 20-30 mL of 0.1mol/L potassium chloride solution containing 5mmol/L potassium ferricyanide/potassium ferrocyanide in a frequency range of 0.01-106And respectively recording electrochemical alternating-current impedance spectrograms of two gold @ silver core-shell nanoparticle/tryptophan compound modified electrodes in an electrochemical window with the amplitude of 5mV at Hz. By comparing the difference of the charge transfer resistances of two gold @ silver core-shell nanoparticle/tryptophan compound modified electrodes on an electrochemical alternating-current impedance spectrogram, the ultrasensitive chiral recognition of a tryptophan enantiomer is realized.
Further, the concentration of the tetrachloroauric acid trihydrate solution added in the step a is 0.01-0.04 mol/L, and the concentration of the sodium citrate solution is 0.01-0.13 mol/L.
Further, the concentration of the sodium citrate solution added in the step b is 0.01-0.13 mol/L, and the concentration of the silver nitrate solution is 10-90 mmol/L.
Furthermore, the concentration of the L-tryptophan and the concentration of the D-tryptophan added in the step c are both 0.1-0.19 nmol/L.
Furthermore, the volume of the gold @ silver core-shell nanoparticle/L-tryptophan compound and the volume of the gold @ silver core-shell nanoparticle/D-tryptophan compound which are transferred by the liquid-transferring gun in the step D are both 1-9 mu L, and the drying time under an infrared lamp is 10-20 min.
The invention has the beneficial effects that:
the invention adopts a simple one-pot method to synthesize gold @ silver core-shell nanoparticles which can be used as an electroactive chiral modifier, and further prepares a gold @ silver core-shell nanoparticle/tryptophan compound, wherein the prepared gold @ silver core-shell nanoparticle/tryptophan compound can be used for ultra-sensitive chiral recognition of tryptophan enantiomers, and effective electrochemical alternating current impedance recognition can be realized on tryptophan enantiomers with the concentration as low as 0.1nmol/L, which is mainly attributed to that the chiral molecular recognition behavior can be converted into easily observed and sensitive impedance signals by the electrochemical alternating current impedance method recognition. However, the colorimetric method which relies solely on direct visual observation cannot realize chiral recognition of 0.1nmol/L tryptophan enantiomer. Electrochemical ac impedance identification has a higher sensitivity.
Drawings
The experiment is further described below with reference to the accompanying drawings.
FIG. 1 is a transmission electron micrograph of gold nanoparticles of example one.
FIG. 2 is a transmission electron micrograph of the gold @ silver core-shell nanoparticles of example one.
FIG. 3 is the electrochemical AC impedance spectrum of the gold @ silver core-shell nanoparticle modified electrode, the gold @ silver core-shell nanoparticle/L-tryptophan complex modified electrode, and the gold @ silver core-shell nanoparticle/D-tryptophan complex modified electrode in 0.1mol/L potassium chloride solution containing 5mmol/L potassium ferricyanide/potassium ferrocyanide in example two.
FIG. 4 is a circular dichroism plot of gold @ silver core-shell nanoparticles, L-tryptophan, and D-tryptophan of example two.
FIG. 5 is a graph of the UV-VIS absorption spectra of gold @ silver core-shell nanoparticles, gold @ silver core-shell nanoparticles/L-tryptophan composites, and gold @ silver core-shell nanoparticles/D-tryptophan composites of comparative example I.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
The first embodiment is as follows:
the preparation method of the gold @ silver core-shell nano particles comprises the following steps:
(1) adding 1mL of 0.025mol/L tetrachloroauric acid trihydrate solution into 98mL of water, stirring, heating the solution to boiling, adding 1mL of 0.07mol/L sodium citrate solution, changing the solution from light yellow to dark red, and continuously stirring at high temperature for 10min to obtain the gold nanoparticles.
(2) And (2) putting 20mL of the gold nanoparticles prepared in the step (1) into a beaker, heating the solution to boiling, adding 1mL of 0.07mol/L sodium citrate solution and 20 mu L of 50mmol/L silver nitrate solution, changing the solution from deep red to orange, and continuously stirring at high temperature for 10min to obtain the gold @ silver core-shell nanoparticles.
FIG. 1 is a transmission electron microscope image of gold nanoparticles, from which it can be seen that the gold nanoparticles are well dispersed and uniformly distributed in size, and the average particle size of the gold nanoparticles is about 10 nm. FIG. 2 is a transmission electron microscope image of gold @ silver core-shell nanoparticles, from which it can be seen that the gold @ silver core-shell nanoparticles are well dispersed, and the average particle size of the gold @ silver core-shell nanoparticles is about 22 nm. The thickness of the silver shell layer formed on the surface of the gold nano-particles is about 6nm by calculation.
Example two:
the preparation method of the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode comprises the following steps:
(1) and taking 2mL of the gold @ silver core-shell nanoparticles prepared in the first embodiment, respectively adding 0.5mL of 0.1 nmol/L-tryptophan and D-tryptophan solutions, and standing at room temperature for reaction for 15min to obtain a gold @ silver core-shell nanoparticle/L-tryptophan compound and a gold @ silver core-shell nanoparticle/D-tryptophan compound.
(2) And (2) respectively transferring 5 mu L of the gold @ silver core-shell nanoparticle/L-tryptophan compound and the gold @ silver core-shell nanoparticle/D-tryptophan compound prepared in the step (1) by using a liquid-transferring gun to drip and coat the compound on the surface of a glassy carbon electrode, and drying for 15min under an infrared lamp to obtain the gold @ silver core-shell nanoparticle/L-tryptophan compound modified electrode and the gold @ silver core-shell nanoparticle/D-tryptophan compound modified electrode.
Standing two gold @ silver core-shell nanoparticle/tryptophan compound modified electrodes prepared in the step (2) in 25mL of 0.1mol/L potassium chloride solution containing 5mmol/L potassium ferricyanide/potassium ferrocyanide in a frequency range of0.01～106And respectively recording electrochemical alternating-current impedance spectrograms of the two gold @ silver core-shell nanoparticle/tryptophan compound modified electrodes in an electrochemical window with the amplitude of 5mV at Hz. As can be seen from fig. 3, the charge transfer resistance of the gold @ silver core-shell nanoparticle modified electrode is only 350 Ω, which is mainly because the gold @ silver core-shell nanoparticle has good charge transport capability. Compared with the gold @ silver core-shell nanoparticle modified electrode, the charge transfer resistance of the gold @ silver core-shell nanoparticle/L-tryptophan composite modified electrode is basically kept unchanged, and the charge transfer resistance of the gold @ silver core-shell nanoparticle/D-tryptophan composite modified electrode is obviously increased. This is mainly because the optical rotation of gold @ silver core-shell nanoparticles is the same as that of D-tryptophan, but opposite to that of L-tryptophan (fig. 4), and according to previous reports, two interacting chiral molecules are more likely to react if the optical rotation directions of the two molecules are the same. Thus, at the same concentration, D-tryptophan binds to the gold @ silver core-shell nanoparticles more readily than L-tryptophan. It is known that tryptophan has far weaker charge transport capability than gold @ silver core-shell nanoparticles, and therefore charge transfer of a ferricyanate ion/ferricyanate ion electric pair is significantly inhibited on the surface of a gold @ silver core-shell nanoparticle/D-tryptophan composite modified electrode, resulting in significantly increased charge transfer resistance.
Comparative example one:
the chiral recognition of low concentrations of tryptophan enantiomer (0.1nmol/L) was performed using colorimetric methods. 2mL of the gold @ silver core-shell nanoparticles prepared in the first example were added into a centrifuge tube, 0.5mL of 0.1 nmol/L-tryptophan and D-tryptophan solutions were added, and the mixture was allowed to stand at room temperature for 15min to react, and the UV-visible absorption spectra of the three solutions were measured, respectively, and the results are shown in FIG. 5. Compared with gold @ silver core-shell nanoparticles, the ultraviolet-visible absorption spectra of the gold @ silver core-shell nanoparticles/L-tryptophan complex and the gold @ silver core-shell nanoparticles/D-tryptophan complex are not obviously changed, plasma resonance absorption peaks only appear at 395nm and 495nm, and the colors of the three solutions are still orange. This shows that the colorimetric method can not realize chiral recognition of tryptophan enantiomer with low concentration (0.1nmol/L), while the electrochemical AC impedance method provided by the invention can realize chiral recognition of tryptophan enantiomer with low concentration, thereby having higher sensitivity.
Claims (10)
1. The gold @ silver core-shell nanoparticle is characterized in that the preparation method of the gold @ silver core-shell nanoparticle comprises the following steps:
preparing gold nanoparticles by adopting tetrachloroauric acid trihydrate and sodium citrate; and heating the gold nanoparticles to boiling, and adding a sodium citrate solution and a silver nitrate solution to obtain the gold @ silver core-shell nanoparticles.
2. The gold @ silver core-shell nanoparticle of claim 1, wherein preparing gold nanoparticles comprises the steps of:
adding water into the tetrachloroauric acid trihydrate solution, stirring, heating the solution to boiling, adding the sodium citrate solution, changing the solution from light yellow to dark red, and continuously stirring at high temperature to obtain the gold nanoparticles.
3. The gold @ silver core-shell nanoparticle of claim 1, wherein the preparation of the gold @ silver core-shell nanoparticle comprises the steps of: heating the gold nanoparticle solution to boiling, adding a sodium citrate solution and a silver nitrate solution, changing the solution from deep red to orange, and continuously stirring at high temperature to obtain the gold @ silver core-shell nanoparticles.
4. The use of gold @ silver core-shell nanoparticles as claimed in any one of claims 1 to 3 for electrochemical ac impedance ultrasensitive chiral recognition.
5. An electrochemical alternating-current impedance ultrasensitive chiral recognition method, which is characterized in that the gold @ silver core-shell nanoparticles disclosed by claim 1 are added with a tryptophan solution and subjected to standing reaction to obtain a gold @ silver core-shell nanoparticle/tryptophan compound, the gold @ silver core-shell nanoparticle/tryptophan compound is dropwise coated on the surface of a glassy carbon electrode, and the glassy carbon electrode is dried under an infrared lamp to obtain a gold @ silver core-shell nanoparticle/tryptophan compound modified electrode; the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode is statically placed in a potassium chloride solution containing potassium ferricyanide/potassium ferrocyanide, an electrochemical alternating-current impedance spectrogram of the gold @ silver core-shell nanoparticle/tryptophan compound modified electrode is recorded, and the ultrasensitive chiral recognition of a tryptophan enantiomer is realized by comparing the electrochemical alternating-current impedance spectrogram.
6. The electrochemical alternating current impedance ultrasensitive chiral recognition method according to claim 5, wherein if the electrochemical alternating current impedance spectrogram of the gold @ silver core-shell nanoparticle/tryptophan complex modified electrode is compared with that of the gold @ silver core-shell nanoparticle modified electrode, if the difference of the charge transfer resistance of the gold @ silver core-shell nanoparticle/tryptophan complex modified electrode exceeds 50 Ω, the tryptophan is D-tryptophan; if the difference of the charge transfer resistance does not exceed 10 omega, the L-tryptophan is obtained.
7. The method for electrochemical AC impedance ultrasensitive chiral recognition according to claim 5, wherein the frequency range of the electrochemical AC impedance is 0.01-106Hz, amplitude of 5 mV.
8. The electrochemical alternating-current impedance ultrasensitive chiral recognition method according to claim 5, wherein the drying time under an infrared lamp is 10-20 min.
9. The electrochemical AC impedance ultrasensitive chiral recognition method according to claim 5, wherein the potassium chloride solution containing potassium ferricyanide/potassium ferrocyanide is a 0.1mol/L potassium chloride solution with a concentration of 5mmol/L potassium ferricyanide/potassium ferrocyanide.
10. The electrochemical AC impedance ultrasensitive chiral recognition method according to claim 5, wherein the tryptophan concentration is 0.1nmol/L or more.
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