CN111590085B - Au-Ag nano-chain composite SERS substrate and preparation method and application thereof - Google Patents
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Abstract
The invention provides an Au-Ag nano-chain composite SERS substrate and a preparation method and application thereof, and relates to the field of pesticide detection. The invention provides a preparation method of an Au-Ag nanochain composite SERS substrate, the Au-Ag nanochain composite SERS substrate prepared by the preparation method, and a method for detecting glyphosate by using the SERS substrate. The detection method is based on the principle of inhibiting a nanoenzyme inhibitor, cysteine can inhibit the activity of Au-Pt nanoenzyme, the inhibition effect of the cysteine is weakened by complexing bivalent copper ions with glyphosate and complexing the cysteine, TMB is developed through catalysis of the nanoenzyme, signals of an oxidation product OxTMB are measured by SERS, so that the content of the glyphosate is indirectly quantified, the detection linear range is 1000 ppm-10ppb, and the LOD value is 5ppb.
Description
Technical Field
The invention belongs to the technical field of pesticide detection, and particularly relates to an Au-Ag nano-chain composite SERS substrate, and a preparation method and application thereof.
Background
Glyphosate is a non-selective and residue-free biocidal herbicide, is very effective on perennial rooting weeds, and is widely used in rubber, mulberry, tea, orchards and sugarcane fields. Mainly inhibits enol pyruvyl shikimic acid phosphate synthetase in plants, thereby inhibiting the conversion of shikimic acid to phenylalanine, tyrosine and tryptophan, interfering protein synthesis and leading to plant death.
Glyphosate is an effective active ingredient in various herbicides widely used at present, is supervised and used in the European Union, and is listed as a 2A class carcinogen by the international cancer research organization of the world health organization. At present, the glyphosate detection methods mainly comprise HPLC, GC, LC-MS/MS, electrochemical detection methods and the like. However, the methods all have the defects of high detection limit and low sensitivity, while the SERS detection method has the advantages of high sensitivity, simple method and low cost, and how to detect the content of glyphosate by using SERS becomes a new research topic.
Disclosure of Invention
In view of the above, the invention aims to provide an Au-Ag nanochain composite SERS substrate, a preparation method and an application thereof, which can establish a glyphosate indirect SERS detection method for inhibiting a nanoenzyme inhibitor, have the advantages of low cost, wide detection range, low detection limit and the like, and are expected to realize sensitive detection of glyphosate molecules.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an Au-Ag nano-chain composite SERS substrate, which comprises the following steps: (1) Mixing a silver nitrate aqueous solution, a trisodium citrate aqueous solution, a sodium borohydride aqueous solution and water, and stirring to obtain an Ag nuclear solution; the molar ratio of silver nitrate to trisodium citrate to sodium borohydride in the aqueous solution of silver nitrate, aqueous solution of trisodium citrate and aqueous solution of sodium borohydride during mixing is 1;
(2) Mixing the Ag nuclear solution with HAuCl 4 And (3) mixing the aqueous solution while stirring, heating to boil, adding the ascorbic acid aqueous solution, continuously boiling for 10min, and cooling to obtain the Au-Ag nano-chain composite SERS substrate.
Preferably, the volume ratio of the total volume of the silver nitrate aqueous solution, the trisodium citrate aqueous solution and the sodium borohydride aqueous solution to the water in the step (1) is 6.5.
Preferably, the volume ratio of the silver nitrate aqueous solution to the trisodium citrate aqueous solution to the sodium borohydride aqueous solution is 1; the concentration of silver nitrate in the silver nitrate aqueous solution is 0.1M, the concentration of trisodium citrate in the trisodium citrate aqueous solution is 0.1M, and the concentration of sodium borohydride in the sodium borohydride aqueous solution is 25mM.
Preferably, the Ag core solution, HAuCl, in step (2) 4 The volume ratio of the aqueous solution to the ascorbic acid aqueous solution is 25:24: (2-10); the HAuCl 4 HAuCl in aqueous solution 4 Has a concentration of 0.465mM, and the concentration of the ascorbic acid in the ascorbic acid aqueous solution is 0.1M.
Preferably, the Ag core solution, HAuCl 4 The volume ratio of the aqueous solution to the ascorbic acid aqueous solution is 25:24:6.
the invention also provides the Au-Ag nanochain composite SERS substrate prepared by the preparation method, the Au-Ag nanochain composite SERS substrate has a nano chain structure, and only has SERS signals to the oxidation product OxTMB and no SERS signals to the TMB in a target reaction system.
The invention also provides application of the Au-Ag nano-chain composite SERS substrate in detection of glyphosate.
The invention also provides a method for detecting glyphosate based on the Au-Ag nano-chain composite SERS substrate, which comprises the following steps: (a) 1% of 0.5mL of HAuCl 4 Mixing with 49.5mL of water and heatingAdding 0.75mL of 1wt% sodium citrate aqueous solution until boiling, and boiling for 20min to obtain AuNPs solution; the heating process is accompanied by continuous stirring;
(b) Boiling the AuNPs solution with 1mL of 0.1M ascorbic acid aqueous solution and 1.25mL of 1wt% 2 PtCl 6 .6H 2 Mixing the O solution, boiling for 20min, and cooling to obtain an Au-Pt nano enzyme solution;
(c) Mixing the Au-Pt nanoenzyme solution with a sodium acetate buffer solution, a cysteine solution, a copper sulfate solution and a glyphosate solution, incubating for 1h, adding a TMB color developing agent, incubating and developing to obtain an inhibition system; the volume ratio of the Au-Pt nanoenzyme solution to the sodium acetate buffer solution, the cysteine solution, the copper sulfate solution and the glyphosate solution is 50; the concentration of the sodium acetate buffer solution is 50mM, the concentration of the cysteine solution is 5mM, and the concentration of the copper sulfate solution is 5mM;
(d) Mixing the inhibition system with the Au-Ag nano-chain composite SERS substrate solution, and then performing SERS test, wherein the intensity is 100%, and the integration time is 7500ms; taking the logarithm value of the glyphosate concentration as the abscissa and 1605cm -1 The peak value of the characteristic peak of the OxTMB is used as a vertical coordinate to draw a standard curve, and the glyphosate concentration is measured and calculated by utilizing the standard curve; the volume ratio of the inhibition system to the Au-Ag nano-chain composite SERS substrate solution is 1:4.
Preferably, the standard curve in step (d) is Y =5160.83X +43858.30 2 ＝0.995。
The invention provides a preparation method of an Au-Ag nano-chain composite SERS substrate, the Au-Ag nano-chain composite SERS substrate prepared by the preparation method can overcome the defect that Au and Ag nanoparticles are easy to agglomerate, the stability is stronger, the prepared Au-Ag composite nano material (with a nano chain structure) with a special appearance has a better enhancement effect than single Au and Ag nanoparticles, only an oxidation product OxTMB has an SERS signal in a target reaction system, no SERS signal is generated for TMB, and preference interference generated by TMB can be avoided.
The invention also provides application of the Au-Ag nanochain composite SERS substrate in detecting glyphosate and a specific detection method, wherein cysteine can inhibit the activity of Au-Pt nanoenzyme based on the principle of inhibiting the activity of a nanoenzyme inhibitor, the glyphosate is used for complexing bivalent copper ions and then complexing the cysteine, so that the inhibition effect of the cysteine is weakened, TMB is catalyzed by the nanoenzyme for developing color, and signals of an oxidation product OxTMB are detected by SERS, so that the content of the glyphosate is indirectly quantified. The detection method has the advantages of low cost, wide detection range, low detection limit and the like, has the detection linear range of 1000 ppm-10ppb and the LOD value of 5ppb, and is expected to realize sensitive detection of glyphosate molecules.
Drawings
FIG. 1 is a transmission electron microscope structure diagram of an Au-Ag nanochain composite SERS substrate, wherein the left side diagram is a chain structure under 50nm, and the right side diagram is a partial enlarged view under 20 nm;
FIG. 2 illustrates the effect of different components added to an inhibition system on SERS signals;
FIG. 3 is a standard curve of SERS measurement, wherein the upper graph shows the SERS spectra with different concentrations of glyphosate added; the lower graph is obtained by taking the logarithm of the abscissa concentration and then adding 1605cm -1 And (4) taking a standard curve drawn by SERS intensity.
Detailed Description
The invention provides a preparation method of an Au-Ag nano-chain composite SERS substrate, which comprises the following steps: (1) Mixing a silver nitrate aqueous solution, a trisodium citrate aqueous solution, a sodium borohydride aqueous solution and water, and stirring to obtain an Ag nuclear solution; the molar ratio of silver nitrate to trisodium citrate to sodium borohydride in the aqueous silver nitrate solution, aqueous trisodium citrate solution and aqueous sodium borohydride solution during mixing is 1;
(2) Mixing the Ag nuclear solution with HAuCl 4 And (3) mixing the aqueous solution while stirring, heating to boil, adding an ascorbic acid aqueous solution, continuously boiling for 10min, and cooling to obtain the Au-Ag nano-chain composite SERS substrate.
Mixing a silver nitrate aqueous solution, a trisodium citrate aqueous solution, a sodium borohydride aqueous solution and water, and stirring to obtain an Ag nuclear solution; during the mixing, silver nitrate aqueous solution, trisodium citrate aqueous solution and sodium borohydrideThe molar ratio of silver nitrate, trisodium citrate and sodium borohydride in the aqueous solution is 1. The volume ratio of the total volume of the silver nitrate aqueous solution, the trisodium citrate aqueous solution and the sodium borohydride aqueous solution to the water is preferably 6.5; the volume ratio of the silver nitrate aqueous solution to the trisodium citrate aqueous solution to the sodium borohydride aqueous solution is preferably 1. In the present invention, the molar concentration of silver nitrate in the aqueous silver nitrate solution is preferably 0.1M; the molar concentration of trisodium citrate in the aqueous trisodium citrate solution is preferably 0.1M; the molar concentration of sodium borohydride in the aqueous sodium borohydride solution is preferably 25mM. The aqueous sodium borohydride solution of the invention is preferably a freshly prepared aqueous solution, which is ready to use. In the present example, to illustrate the preparation of a solution of Ag nuclei, 250. Mu.L of 0.1MAGNO was added to 100mL of water 3 And 250. Mu.L of 0.1M trisodium citrate, and 6mL of 25mM freshly prepared sodium borohydride was rapidly added and stirred for 30min, but this cannot be considered as the scope of the present invention alone. The sources of the silver nitrate, trisodium citrate and sodium borohydride are not particularly limited in the present invention, and conventional commercially available reagents in the field may be used.
After obtaining the Ag nuclear solution, the invention combines the Ag nuclear solution with HAuCl 4 And (3) mixing the aqueous solution while stirring, heating to boil, adding the ascorbic acid aqueous solution, continuously boiling for 10min, and cooling to obtain the Au-Ag nano-chain composite SERS substrate. In the present invention, before the mixing while stirring, it is preferable to take out a part of the Ag core solution into a 250mL round-bottomed flask, stir it at 800rpm, and add HAuCl dropwise while stirring 4 Heating the water solution to boiling, and adding the ascorbic acid water solution continuously for boiling for 10min. The Ag nuclear solution and HAuCl of the invention 4 The volume ratio of the aqueous solution to the ascorbic acid aqueous solution is preferably 25: (2 to 10), more preferably 25: 6; the Ag nuclear solution and HAuCl 4 The volume ratio of the aqueous solution to the aqueous ascorbic acid solution is preferably 25: 6. HAuCl of the present invention 4 HAuCl in aqueous solution 4 Is preferably 0.465mM, and the molar concentration of the ascorbic acid in the aqueous ascorbic acid solution is preferably 0.1M. In the present example, to illustrate this procedure, 25mL of the above preparation was takenThe prepared Ag nuclear solution was placed in a 250mL round bottom flask, stirred at 800rpm, and 20mL of 0.465mM HAuCl was added dropwise 4 Heating to boil, adding 2-10 mL ascorbic acid (0.1M) solution, and boiling for 10min.
The invention also provides the Au-Ag nanochain composite SERS substrate prepared by the preparation method, the Au-Ag nanochain composite SERS substrate has a nano chain structure, and only has SERS signals to the oxidation product OxTMB and no SERS signals to the TMB in a target reaction system. The transmission electron microscope image of the Au-Ag nanochain in the Au-Ag nanochain composite SERS substrate is shown in figure 1, the shape and the structure of the synthesized SERS substrate are chain-shaped, an SERS signal is only generated on an oxidation product OxTMB in a target reaction system, and no SERS signal is generated on the TMB, so that the interference generated by the TMB can be avoided, and the Au-Ag nanochain composite SERS substrate can be used for detecting the content of glyphosate.
The invention also provides application of the Au-Ag nano-chain composite SERS substrate in detection of glyphosate.
The invention also provides a method for detecting glyphosate based on the Au-Ag nano-chain composite SERS substrate, which comprises the following steps: (a) 1% of 0.5mL of HAuCl 4 Mixing with 49.5mL of water, heating to boiling, adding 0.75mL of 1wt% sodium citrate aqueous solution, and boiling for 20min to obtain AuNPs solution; the heating process is accompanied by continuous stirring;
(b) Boiling the AuNPs solution with 1mL of 0.1M aqueous ascorbic acid solution and 1.25mL1wt% 2 PtCl 6 .6H 2 Mixing the O solution, boiling for 20min, and cooling to obtain Au-Pt nano enzyme solution;
(c) Mixing the Au-Pt nanoenzyme solution with a sodium acetate buffer solution, a cysteine solution, a copper sulfate solution and a glyphosate solution, incubating for 1h, adding a TMB color developing agent, incubating and developing color to obtain an inhibition system; the volume ratio of the Au-Pt nanoenzyme solution to the sodium acetate buffer solution, the cysteine solution, the copper sulfate solution and the glyphosate solution is 50;
(d) Mixing the inhibition system with an Au-Ag nano-chain composite SERS substrate solution, and performing an SERS test with the intensity of 100% and the integration time of 7500ms; to be provided withThe logarithmic value of the glyphosate concentration is the abscissa with 1605cm -1 The peak value of the characteristic peak of the OxTMB is taken as a vertical coordinate to draw a standard curve, and the glyphosate concentration is measured and calculated by utilizing the standard curve; the volume ratio of the inhibition system to the Au-Ag nano-chain composite SERS substrate solution is 1:4.
The invention 1% of 0.5mL by 1wt HAuCl 4 Heating the solution in 49.5mL of water to boil, adding 0.75mL of 1wt% sodium citrate, and boiling for 20min to obtain AuNPs solution; the heating is accompanied by continuous stirring. The stirring speed in the present invention is preferably 700rpm. The method of boiling and the rate of temperature rise are not particularly limited in the present invention, and the boiling may be carried out by heating by a conventional heating method in the art.
After obtaining the AuNPs solution, the present invention combines the boiling AuNPs solution with 1mL of 0.1M ascorbic acid aqueous solution and 1.25mL of 1wt% 2 PtCl 6 .6H 2 And mixing the O solution, boiling for 20min, and cooling to obtain the Au-Pt nano enzyme solution. The boiling and cooling methods are not particularly limited in the present invention, and conventional heating and cooling methods in the art may be used.
After obtaining the Au-Pt nano enzyme solution, mixing the Au-Pt nano enzyme solution with a sodium acetate buffer solution, a cysteine solution, a copper sulfate solution and a glyphosate solution, incubating for 1h, adding a TMB color developing agent, incubating and developing to obtain an inhibition system; the volume ratio of the Au-Pt nanoenzyme solution to the sodium acetate buffer solution, the cysteine solution, the copper sulfate solution and the glyphosate solution is 50. The preparation method of the inhibition system preferably comprises the following steps: 1mL NaAc/HAc (50mM, pH = 5) was added to 50. Mu. LAu-Pt nanoenzyme solution, 10. Mu.L of 5mM cysteine solution (fresh), and 10. Mu.L of 5mM CuSO 4 The solution and 1mL of glyphosate aqueous solution; incubating for 1h at room temperature; adding 200 μ L of TMB color developing agent, and incubating for 10min for color development.
After an inhibition system is obtained, the inhibition system is mixed with an Au-Ag nano chain composite SERS substrate solution and then SERS test is carried out, the intensity is 100%, and the integration time is 7500ms; taking the logarithm value of the glyphosate concentration as the abscissa and 1605cm -1 The peak value of characteristic peak of OxTMB is taken asDrawing a standard curve for the ordinate, and measuring and calculating the glyphosate concentration by using the standard curve; the volume ratio of the inhibition system to the Au-Ag nano-chain composite SERS substrate solution is 1:4. The standard curve of the invention is Y =5160.83X +43858.30 2 And =0.995. By using the method of the invention, the linear range of the detection concentration of the glyphosate is 1000 ppm-10ppb, and the LOD value is 5ppb.
The Au-Ag nanochain composite SERS substrate provided in the present invention, and the preparation method and application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1. Instruments and reagents used
RT2000 portable Raman spectrometer (same as Fang Wei Vision technology, inc.); a quartz tube heated automatic double pure water distiller (1810B, shanghai Asia Tech glass Co.) was used to distill the secondary distilled water; an electronic balance (beijing sidoris instruments ltd) for weighing the medicine; an ultrasonic cleaner (ultrasonic instruments ltd, kunshan); electrothermal cover heating jacket; chloroauric acid (sigma reagent); chloroplatinic acid (sigma reagent corporation); silver nitrate (sigma reagent corporation); cysteine (sigma reagent corporation); copper sulfate pentahydrate (alatin reagent corporation); glyphosate standard (dr. Ehrenstorfer gmbh); trisodium citrate (alatin reagent); sodium borohydride (alatin reagent company); ascorbic acid (sigma reagent corporation); TMB color developing agent.
2. Preparation of Au-Ag nano-chain composite SERS substrate
2.1 preparation of Ag core:
to 100mL of water was added 250. Mu.L of 0.1MAGNO 3 And 250 μ L of 0.1M trisodium citrate, 6mL of 25mM freshly prepared sodium borohydride was added rapidly and stirred for 30min.
2.2Au-Ag nanochains:
25mL of the Ag nuclear solution prepared above was placed in a 250mL round-bottom flask, stirred at 800rpm, and 20mL of 0.465mM HAuCl was added dropwise 4 Heated to boiling and 6mL ascorbic acid (0.1M) solution was added and boiling continued for 10min. And (6) cooling.
And 2.3, carrying out transmission electron microscope structure detection on the obtained Au-Ag nanochain composite SERS substrate, wherein the SERS substrate has a nano chain structure (figure 1), and only has an SERS signal to an oxidation product OxTMB in a target reaction system, and does not have an SERS signal to TMB, so that preference interference generated by TMB can be avoided.
Example 2
1. Preparing Au-Pt nanoenzyme:
0.5mL 1wt％HAuCl 4 the mixture was heated to boiling in 49.5mL of water, with constant stirring during heating (700 rpm), and 0.75mL of 1wt% sodium citrate was added and boiled for 20min. Adding 1mL of 0.1M ascorbic acid to the boiling AuNPs, adding 1.25mL of 1wt% 2 PtCl 6 .6H 2 And (O). Boiling for 20min, and cooling.
2. An inhibition system:
1mL of NaAc/HAc (50mM, pH = 5) was added with 50. Mu. LAu-Pt nanoenzyme, 10. Mu.L of 5mM cysteine solution (fresh), and 10. Mu.L of 5mM CuSO 4 Solution and 1mL of aqueous glyphosate solution. Incubate for 1h at room temperature. Adding 200 μ L of TMB color developing agent, and incubating for 10min for color development.
3. SERS test conditions:
SERS test is carried out on 400 microliter Au-Ag nano-chain substrate and 100 microliter solution of the inhibiting system, the strength is 100 percent, and the integration time is 7500ms.
When different components are added into an inhibition system, the influence on the SERS signal is shown in figure 2, when only Au-Pt nanoenzyme and glyphosate exist, glyphosate hardly has inhibition effect on the nanoenzyme, when the component cysteine is increased, the SERS signal is almost completely inhibited, when divalent copper ions are increased, the SERS signal is generated, but the signal is strong when only nanoenzyme and glyphosate or nanoenzyme, glyphosate and divalent copper ions do not exist, and the situation that the glyphosate and the divalent copper ions can complex cysteine to inhibit the inhibition effect of the cysteine on the nanoenzyme is shown.
Taking the logarithm value of the glyphosate concentration as the abscissa and taking the Raman shift value as 1605cm -1 The peak value of the characteristic peak of OxTMB at (2) is plotted as the ordinate on a standard curve (FIG. 3), the equation of which is: y =5160.83X+43858.30 2 Linear range of 10 =0.99500ppm to 10ppb, 1605cm - The characteristic peak at 1 has a minimum difference of 5ppb from the blank control.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. A method for detecting glyphosate based on an Au-Ag nano-chain composite SERS substrate is characterized by comprising the following steps: (a) 0.5mL 1wt% of HAuCl 4 Mixing with 49.5mL of water, heating to boiling, adding 0.75mL of 1wt% sodium citrate aqueous solution, and boiling for 20min to obtain AuNPs solution; the heating process is accompanied by continuous stirring;
(b) Boiling the AuNPs solution with 1mL of 0.1M ascorbic acid aqueous solution and 1.25mL1wt% H 2 PtCl 6 .6H 2 Mixing the O solution, boiling for 20min, and cooling to obtain an Au-Pt nano enzyme solution;
(c) Mixing the Au-Pt nanoenzyme solution with a sodium acetate buffer solution, a cysteine solution, a copper sulfate solution and a glyphosate solution, incubating for 1h, adding a TMB color developing agent, incubating and developing to obtain an inhibition system; the volume ratio of the Au-Pt nanoenzyme solution to the sodium acetate buffer solution, the cysteine solution, the copper sulfate solution and the glyphosate solution is 50; the concentration of the sodium acetate buffer solution is 50mM, the concentration of the cysteine solution is 5mM, and the concentration of the copper sulfate solution is 5mM;
(d) Mixing the inhibition system with an Au-Ag nano-chain composite SERS substrate solution, and performing an SERS test with the intensity of 100% and the integration time of 7500ms; taking the logarithm value of the glyphosate concentration as the abscissa and 1605cm -1 The peak value of the characteristic peak of the OxTMB is taken as a vertical coordinate to draw a standard curve, and the glyphosate concentration is measured and calculated by utilizing the standard curve; the volume ratio of the inhibition system to the Au-Ag nano-chain composite SERS substrate solution is 1:4;
the preparation method of the Au-Ag nano-chain composite SERS substrate comprises the following steps: (1) Mixing a silver nitrate aqueous solution, a trisodium citrate aqueous solution, a sodium borohydride aqueous solution and water, and stirring to obtain an Ag nuclear solution; the molar ratio of silver nitrate to trisodium citrate to sodium borohydride in the aqueous silver nitrate solution, aqueous trisodium citrate solution and aqueous sodium borohydride solution during mixing is 1; the volume ratio of the total volume of the silver nitrate aqueous solution, the trisodium citrate aqueous solution and the sodium borohydride aqueous solution to the water is 6.5;
(2) Mixing the Ag nuclear solution with HAuCl 4 Mixing the aqueous solution under stirring, heating to boil, adding the ascorbic acid aqueous solution, continuously boiling for 10min, and cooling to obtain the Au-Ag nano-chain composite SERS substrate; the Ag nuclear solution and HAuCl 4 The volume ratio of the aqueous solution to the ascorbic acid aqueous solution is 25:24: (2-10); the HAuCl 4 HAuCl in aqueous solution 4 Has a concentration of 0.465mM, and has a concentration of 0.1M ascorbic acid in the aqueous ascorbic acid solution;
the Au-Ag nanochain composite SERS substrate has a nano chain structure, and only has SERS signals to an oxidation product OxTMB and does not have SERS signals to TMB in a target reaction system.
2. The method as claimed in claim 1, wherein the standard curve of step (d) is Y =5160.83X + 43858.30R 2 ＝0.995。
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| Anxin Jiao等.Construction of pure worm-like AuAg nanochains for ultrasensitive SERS detection of pesticide residues on apple surfaces.《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》.2019,第209卷241-247. * |
| Mein Jin Tan等.Metal carbonyl-gold nanoparticle conjugates for highly sensitive SERS detection of organophosphorus pesticides.《Biosensors and Bioelectronics》.2017,第96卷167-172. * |
| 涂琴等.利用金纳米颗粒原位检测植物组织中的草甘膦.《中国化学会第一届农业化学学术讨论会论文集》.2019,102. * |
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