CN115074121A - Preparation method of electrochemiluminescence wavelength-adjustable carbon quantum dot - Google Patents
Preparation method of electrochemiluminescence wavelength-adjustable carbon quantum dot Download PDFInfo
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Abstract
The invention discloses a preparation method of an electrochemiluminescence wavelength-adjustable carbon quantum dot, which comprises the following steps: dissolving 2-amino terephthalic acid in ultrapure water to obtain a precursor solution of the 2-amino terephthalic acid; mixing tetrakis (hydroxymethyl) phosphonium sulfate with the precursor solution; carrying out hydrothermal reaction on the mixed solution; centrifuging and filtering the hydrothermal reaction solution; adjusting the pH of the filtrate to be neutral and then dialyzing; rotary evaporation of the dialysate; freeze drying the concentrated solution; and dispersing the solid to obtain the carbon quantum dot solution. The invention can prepare the carbon quantum dots with continuously adjustable electrochemiluminescence wavelengths of 425nm, 535nm, 565nm, 610nm, 620nm and 645nm by mixing the reaction precursor solutions with different proportions, has the advantages of simple preparation process and large-scale preparation, and provides an important luminophor for developing an electrochemiluminescence instrument for simultaneously detecting multiple disease markers.
Description
Technical Field
The invention belongs to the preparation of carbon nano materials, and particularly relates to a preparation method of an electrochemiluminescence wavelength-adjustable carbon quantum dot.
Background
The appearance of carbon nanomaterials has had a great impact on the development of various areas of science and technology. As a novel carbon nano material, the carbon quantum dot has the advantages of small size, easy surface functionalization, stable optical performance, excellent biocompatibility and water solubility, and is widely concerned in various fields. The carbon quantum dots have good application prospects in the fields of luminescence, sensing, catalysis and the like.
Although the carbon quantum dots have excellent optical properties and wide application prospects, the carbon quantum dots are mainly focused on exploring the photoluminescence properties and the applications in corresponding fields, the exploration on the electrochemiluminescence properties of the carbon quantum dots is less, and the electrochemiluminescence wavelength of the carbon quantum dots is less regulated. Therefore, the development of an electrochemiluminescence apparatus for simultaneously detecting multiple disease markers is limited by the lack of luminophores with tunable luminescence wavelength.
Disclosure of Invention
The purpose of the invention is as follows: in view of the problems of the prior art, particularly wavelength-tunable emitters are rare. The invention provides a preparation method of an electrochemiluminescence wavelength-adjustable carbon quantum dot, and provides a brand-new preparation method of the electrochemiluminescence wavelength-adjustable carbon quantum dot, wherein the electrochemiluminescence wavelength of the prepared carbon quantum dot comprises 425nm, 535nm, 565nm, 610nm, 620nm and 645nm which are continuously adjustable, so that the problem that an electrochemiluminescence wavelength-adjustable luminous body is difficult to synthesize in the prior art is solved, and the electrochemiluminescence wavelength-adjustable carbon quantum dot has the advantages of simple preparation process and large-scale preparation.
The invention also provides a carbon quantum dot prepared by the preparation method of the electrochemiluminescence wavelength-adjustable carbon quantum dot and application of the carbon quantum dot.
The technical scheme is as follows: in order to achieve the above purpose, the invention provides a method for preparing an electrochemiluminescence wavelength-tunable carbon quantum dot, which comprises the following steps:
(1) dissolving 2-amino terephthalic acid in ultrapure water to obtain a precursor solution of the 2-amino terephthalic acid;
(2) mixing tetrakis (hydroxymethyl) phosphonium sulfate and a 2-amino terephthalic acid precursor solution to form a mixed solution;
(3) carrying out hydrothermal reaction on the mixed solution;
(4) centrifuging and filtering the hydrothermal reaction solution to obtain a filtrate;
(5) adjusting the pH of the filtrate to be neutral, and then dialyzing to obtain dialysate;
(6) carrying out rotary evaporation on the dialysate to obtain a concentrated solution;
(7) freeze-drying the concentrated solution to obtain a carbon quantum dot solid;
(8) and dispersing the solid in ultrapure water to obtain a carbon quantum dot solution.
Wherein, in the step (1), 30-90 mg of 2-amino terephthalic acid is dissolved in 20mL of ultrapure water.
Preferably, 70mg of 2-aminoterephthalic acid is dissolved in 20mL of ultrapure water.
Wherein, in the step (2), the tetrakis (hydroxymethyl) phosphonium sulfate and the 2-amino terephthalic acid precursor solution are ultrasonically mixed according to the molar ratio of 0-4: 1.
Preferably, in the step (2), the tetrakis hydroxymethyl phosphonium sulfate and the 2-amino terephthalic acid precursor solution are ultrasonically mixed according to different molar ratios of 0:1,0.5:1,1:1,2:1,3:1 or 4:1, and the mixture is ultrasonically treated for 10-40 minutes under the condition that the ultrasonic power is 300-400W, so as to form 6 mixed solutions with different ratios.
Further, tetrakis (hydroxymethyl) phosphonium sulfate and 2-amino terephthalic acid precursor solution are mixed according to a molar ratio of 0:1,0.5:1,1:1,2:1,3:1,4:1, and the mixture is subjected to ultrasonic treatment for 30 minutes under the condition of ultrasonic power of 400W to form 6 parts of mixed solution in a corresponding ratio for standby.
And (4) carrying out hydrothermal reaction on the mixed solution in the step (3), wherein the hydrothermal reaction temperature is 100-200 ℃, and the hydrothermal reaction time is 4-12 hours, so as to obtain a hydrothermal reaction solution.
Preferably, 6 mixed solutions with different proportions are subjected to hydrothermal reaction at 180 ℃ for 8 hours to obtain 6 parts of hydrothermal reaction solution with corresponding proportion.
And (4) centrifuging the obtained hydrothermal reaction solution for 5 minutes under the condition of 3000-10000 rpm, and filtering the solution with large particles removed by using a 0.22-micrometer filter membrane to obtain a filtrate.
Preferably, 6 parts of the hydrothermal reaction solution obtained in the corresponding proportion are centrifuged at 5000rpm for 5 minutes, and the solution from which large particles are removed is filtered through a 0.22 μm filter to obtain 6 parts of a filtrate in the corresponding proportion.
And (3) adjusting the pH value of the filtrate to 7 by using a sodium hydroxide solution, dialyzing for 8-32 hours by using a dialysis bag with the shear molecular weight of 500-1000Da to obtain a first dialysate, and dialyzing for 72 hours by using a dialysis bag with the shear molecular weight of 3500-8000 Da to obtain a second dialysate.
Preferably, the pH of the filtrate is adjusted to 7 with 2M sodium hydroxide solution, and then dialyzed for 24 hours with a dialysis bag with a shear molecular weight of 500-1000Da to obtain a first dialysate, and dialyzed for 72 hours with a dialysis bag with a shear molecular weight of 3500Da to obtain 6 parts of a second dialysate in a corresponding ratio for later use.
And (3) carrying out rotary evaporation concentration on the dialysate at the constant temperature of 40-80 ℃ in the step (6) to obtain a concentrated solution.
Preferably, the second dialysate of 6 different proportions is concentrated by rotary evaporation at a constant temperature of 60 ℃ to obtain 6 parts of concentrated solution of corresponding proportions.
Preferably, the preparation method of the electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps:
(1) dissolving 2-amino terephthalic acid in ultrapure water to obtain a precursor solution of the 2-amino terephthalic acid;
(2) mixing tetrakis (hydroxymethyl) phosphonium sulfate and 2-amino terephthalic acid precursor solution according to a molar ratio of 0:1,0.5:1,1:1,2:1,3:1,4:1 to form 6 mixed solutions with different proportions;
(3) carrying out hydrothermal reaction on 6 mixed solutions with different proportions to obtain 6 parts of hydrothermal reaction solution with corresponding proportion;
(4) centrifuging and filtering the hydrothermal reaction solution to obtain a filtrate;
(5) adjusting the pH of the filtrate to be neutral, and then dialyzing to obtain dialysate;
(6) carrying out rotary evaporation on the dialysate to obtain a concentrated solution;
(7) freeze-drying the concentrated solution to obtain carbon quantum dot solids with corresponding electrochemiluminescence wavelengths;
(8) dispersing the solid in ultrapure water to obtain a carbon quantum dot solution with corresponding electrochemiluminescence wavelength;
(9) the carbon quantum dots with the electrochemiluminescence wavelengths of 425nm, 535nm, 565nm, 610nm, 620nm and 645nm can be prepared by changing the proportion of the reaction precursor solution.
The carbon quantum dot with the electrochemiluminescence wavelength adjustable, which is prepared by the preparation method of the carbon quantum dot with the electrochemiluminescence wavelength adjustable, is 425 nm-645 nm.
Preferably, the carbon quantum dots prepared by the preparation method of the carbon quantum dots with the adjustable electrochemiluminescence wavelength have the electrochemiluminescence wavelengths of 425nm, 535nm, 565nm, 610nm, 620nm and 645nm, and have the continuously adjustable characteristic.
The carbon quantum dot with adjustable electrochemiluminescence wavelength, which is prepared by the preparation method of the carbon quantum dot with adjustable electrochemiluminescence wavelength, is used as a luminophor to be applied to electrochemiluminescence for simultaneously detecting multiple disease markers.
The preparation method of the electrochemiluminescence wavelength-adjustable carbon quantum dot provides an important luminophor for developing an electrochemiluminescence instrument for simultaneously detecting multiple disease markers, and has potential application value in the fields of biological and medical inspection. The invention mainly provides a preparation method of an electrochemiluminescence wavelength-adjustable carbon quantum dot aiming at the difficulty in preparing an electrochemiluminescence wavelength-adjustable luminophor at present. The preparation method provides a core material-luminophor for developing an electrochemiluminescence instrument for simultaneously detecting multiple disease markers.
The invention adopts specific raw materials and a method, can regulate and control the electrochemical luminescence wavelength of the product by changing the proportion of the reaction raw materials, can prepare the luminophor with various electrochemical luminescence wavelengths, and effectively solves the problem that the prior luminophor with adjustable wavelength in the field is few. The invention not only uses brand-new raw materials, but also changes the proportion of the reaction raw materials to lead the electrochemiluminescence wavelength of the product to be different, and the whole method has great novelty.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the carbon quantum dots with the adjustable electrochemiluminescence wavelength, which are prepared by the invention, have the electrochemiluminescence wavelengths of 425nm, 535nm, 565nm, 610nm, 620nm and 645nm respectively, are continuously adjusted and controlled from 425nm to 645nm, and the adjustment and control range is 220nm, so that the carbon quantum dots are the luminophors with the largest electrochemiluminescence wavelength adjustment and control range reported at present, and when an electrochemiluminescence instrument for simultaneously detecting multiple markers is manufactured, the larger the adjustable wavelength range of the luminophors is, and the more excellent the selectivity and the sensitivity of the manufactured instrument for detecting the markers are.
2. The invention provides a preparation method of an electrochemiluminescence wavelength-adjustable carbon quantum dot, which is a brand-new method for preparing an electrochemiluminescence wavelength-adjustable luminous body, solves the problems that the electrochemiluminescence wavelength-adjustable luminous body is difficult to synthesize and the luminous body is few in the prior art, has the advantages of simple preparation process and large-scale preparation, and can provide luminous bodies with more wavelengths.
3. The carbon quantum dot with adjustable electrochemiluminescence wavelength, which is prepared by the invention, provides an important luminophor for developing an electrochemiluminescence instrument for simultaneously detecting multiple disease markers, and has potential application value in the fields of biological and medical inspection.
Drawings
FIG. 1 is a transmission electron micrograph of carbon quantum dots 1(CQDs1) prepared according to the present invention;
FIG. 2 is a transmission electron micrograph of carbon quantum dots 2(CQDs2) prepared according to the present invention;
FIG. 3 is a transmission electron micrograph of carbon quantum dots 3(CQDs3) prepared according to the present invention;
FIG. 4 is a transmission electron micrograph of carbon quantum dots 4(CQDs4) prepared according to the present invention;
FIG. 5 is a transmission electron micrograph of carbon quantum dots 5(CQDs5) prepared according to the present invention;
FIG. 6 is a transmission electron micrograph of carbon quantum dots 6(CQDs6) prepared according to the present invention;
FIG. 7 is a graph of electrochemiluminescence spectra of carbon quantum dots 1(CQDs1) prepared according to the present invention;
FIG. 8 is a graph of electrochemiluminescence spectra of carbon quantum dots 2(CQDs2) prepared according to the present invention;
FIG. 9 is a graph of electrochemiluminescence spectra of carbon quantum dots 3(CQDs3) prepared according to the present invention;
FIG. 10 is a graph of electrochemiluminescence spectra of carbon quantum dots 4(CQDs4) prepared according to the present invention;
FIG. 11 is a graph of electrochemiluminescence spectra of carbon quantum dots 5(CQDs5) prepared according to the present invention;
FIG. 12 is an electrochemiluminescence spectrum of carbon quantum dots 6(CQDs6) prepared according to the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures, in which specific conditions are not indicated in the examples, are generally carried out under conventional conditions or conditions recommended by the manufacturer.
Tetrakis (75% aqueous solution) methylphosphonate, Shanghai Aladdin Biotech, Inc.
2-aminoterephthalic acid (> 98.0%, HPLC) solid, manufacturer: shanghai Aladdin Biotechnology Ltd.
Example 1
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 30mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% aqueous solution) and a 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 10 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for standby; s3, carrying out hydrothermal reaction on the 6 mixed solutions in different proportions, wherein the hydrothermal reaction temperature is 100 ℃, and the hydrothermal reaction time is 4 hours, so as to obtain 6 parts of hydrothermal reaction solution in corresponding proportion; s4, centrifuging 6 parts of hydrothermal reaction solution with corresponding proportion for 5 minutes at 3000rpm, and filtering the solution with large particles removed by a 0.22-micron filter membrane to obtain 6 parts of filtrate with corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 8 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of dialysate I with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 3500Da to obtain 6 parts of dialysate II with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at a constant temperature of 40 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated liquid in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; and S8, respectively dispersing the solid in ultrapure water to obtain 6 carbon quantum dot solutions with different electrochemiluminescence wavelengths.
Example 2
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 40mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% aqueous solution) and a 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 15 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for standby; s3, carrying out hydrothermal reaction on the 6 mixed solutions in different proportions, wherein the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 6 hours, so as to obtain 6 parts of hydrothermal reaction solution in corresponding proportion; s4, centrifuging the obtained 6 parts of hydrothermal reaction solution in a corresponding proportion for 5 minutes at 3000rpm, and filtering the solution from which large particles are removed by using a 0.22-micron filter membrane to obtain 6 parts of filtrate in a corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 12 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of dialysate I with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 3500Da to obtain 6 parts of dialysate II with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at a constant temperature of 40 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated solution in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; and S8, respectively dispersing the solid in ultrapure water to obtain carbon quantum dot solutions with 6 different electrochemiluminescence wavelengths.
Example 3
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 50mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% aqueous solution) and a 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 20 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for standby; s3, carrying out hydrothermal reaction on the 6 mixed solutions with different proportions, wherein the hydrothermal reaction temperature is 140 ℃, and the hydrothermal reaction time is 8 hours, so as to obtain 6 parts of hydrothermal reaction solution with corresponding proportion; s4, centrifuging 6 parts of the obtained hydrothermal reaction solution with the corresponding proportion for 5 minutes at 5000rpm, and filtering the solution with large particles removed by a 0.22-micron filter membrane to obtain 6 parts of filtrate with the corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 16 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of first dialysate with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 3500Da to obtain 6 parts of second dialysate with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at the constant temperature of 60 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated liquid in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; and S8, respectively dispersing the solid in ultrapure water to obtain carbon quantum dot solutions with 6 different electrochemiluminescence wavelengths.
Example 4
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 60mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% water solution) and 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 25 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for later use; s3, carrying out hydrothermal reaction on the 6 mixed solutions in different proportions, wherein the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 8 hours, so as to obtain 6 parts of hydrothermal reaction solution in corresponding proportion; s4, centrifuging the obtained 6 parts of hydrothermal reaction solution in a corresponding proportion for 5 minutes at 5000rpm, and filtering the solution from which large particles are removed by using a 0.22-micron filter membrane to obtain 6 parts of filtrate in a corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 20 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of dialysate I with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 5000Da to obtain 6 parts of dialysate II with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at the constant temperature of 60 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated liquid in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; and S8, respectively dispersing the solid in ultrapure water to obtain 6 carbon quantum dot solutions with different electrochemiluminescence wavelengths.
Example 5
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 70mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% aqueous solution) and a 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 30 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for standby; s3, carrying out hydrothermal reaction on the 6 mixed solutions in different proportions, wherein the hydrothermal reaction temperature is 180 ℃, and the hydrothermal reaction time is 8 hours, so as to obtain 6 parts of hydrothermal reaction solution in corresponding proportion; s4, centrifuging 6 parts of the obtained hydrothermal reaction solution with the corresponding proportion for 5 minutes at 5000rpm, and filtering the solution with large particles removed by a 0.22-micron filter membrane to obtain 6 parts of filtrate with the corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 24 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of first dialysate with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 3500Da to obtain 6 parts of second dialysate with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at the constant temperature of 60 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated liquid in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; s8, respectively dispersing the solid in ultrapure water to obtain carbon quantum dot solutions (CQDs1-6) with 6 different electrochemiluminescence wavelengths.
Transmission electron micrographs of the electrochemiluminescence wavelength tunable carbon quantum dots prepared in example 5 are shown in fig. 1 to 6. Fig. 1 to fig. 6 prove that the invention successfully synthesizes the electrochemiluminescence wavelength-tunable carbon quantum dots. Fig. 7 to 12 are electrochemiluminescence spectra of the synthesized carbon quantum dots, which demonstrate that the synthesized carbon quantum dots with 6 different electrochemiluminescence wavelengths can adjust the electrochemiluminescence wavelength from 425nm, 535nm, 565nm, 610nm, 620nm to 645nm, and the 6 wavelengths constitute the continuously adjusted carbon quantum dots.
Example 6
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 80mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% aqueous solution) and a 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 35 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for standby; s3, carrying out hydrothermal reaction on the 6 mixed solutions in different proportions, wherein the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 10 hours, so as to obtain 6 parts of hydrothermal reaction solution in corresponding proportion; s4, centrifuging 6 parts of hydrothermal reaction solution with corresponding proportion for 5 minutes at 7000rpm, and filtering the solution with large particles removed by a 0.22-micron filter membrane to obtain 6 parts of filtrate with corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 28 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of first dialysate with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 5000Da to obtain 6 parts of second dialysate with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at the constant temperature of 60 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated liquid in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; and S8, respectively dispersing the solid in ultrapure water to obtain carbon quantum dot solutions with 6 different electrochemiluminescence wavelengths.
Example 7
A preparation method of an electrochemiluminescence wavelength-tunable carbon quantum dot comprises the following steps: s1, dissolving 90mg of 2-aminoterephthalic acid in 20mL of ultrapure water to obtain a precursor solution of the 2-aminoterephthalic acid; s2, mixing tetrakis (hydroxymethyl) phosphonium sulfate (75% water solution) and 2-amino terephthalic acid precursor solution according to the molar ratio of the tetrakis (hydroxymethyl) phosphonium sulfate to the 2-amino terephthalic acid of 0:1,0.5:1,1:1,2:1,3:1,4:1 respectively, and carrying out ultrasonic treatment for 40 minutes under the condition of the ultrasonic power of 400W to form 6 mixed solutions with different proportions for later use; s3, carrying out hydrothermal reaction on the 6 mixed solutions with different proportions, wherein the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 12 hours, so as to obtain 6 parts of hydrothermal reaction solution with corresponding proportion; s4, centrifuging 6 parts of the obtained hydrothermal reaction solution in a corresponding proportion for 5 minutes under the condition of 10000rpm, and filtering the solution with large particles removed by a 0.22-micron filter membrane to obtain 6 parts of filtrate in a corresponding proportion; s5, adjusting the pH value of 6 parts of filtrate with a sodium hydroxide solution with the concentration of 2M to 7, dialyzing for 32 hours by using a dialysis bag with the shearing molecular weight of 500-1000Da to obtain 6 parts of first dialysate with the corresponding proportion, and dialyzing for 72 hours by using a dialysis bag with the shearing molecular weight of 8000Da to obtain 6 parts of second dialysate with the corresponding proportion for later use; s6, carrying out rotary evaporation concentration on 6 parts of dialysate II in a corresponding proportion at the constant temperature of 80 ℃ to obtain 6 parts of concentrated solution in a corresponding proportion; s7, freeze-drying 6 parts of concentrated liquid in a corresponding proportion to obtain 6 carbon quantum dot solids with different electrochemiluminescence wavelengths; and S8, respectively dispersing the solid in ultrapure water to obtain carbon quantum dot solutions with 6 different electrochemiluminescence wavelengths.
Claims (10)
1. A preparation method of an electrochemiluminescence wavelength-adjustable carbon quantum dot is characterized by comprising the following steps:
(1) dissolving 2-amino terephthalic acid in ultrapure water to obtain a precursor solution of the 2-amino terephthalic acid;
(2) mixing tetrakis (hydroxymethyl) phosphonium sulfate and a 2-amino terephthalic acid precursor solution to form a mixed solution;
(3) carrying out hydrothermal reaction on the mixed solution;
(4) centrifuging and filtering the hydrothermal reaction solution to obtain a filtrate;
(5) adjusting the pH of the filtrate to be neutral, and then dialyzing to obtain dialysate;
(6) carrying out rotary evaporation on the dialysate to obtain a concentrated solution;
(7) freeze-drying the concentrated solution to obtain a carbon quantum dot solid;
(8) and dispersing the solid in ultrapure water to obtain a carbon quantum dot solution.
2. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein in the step (1), 30-90 mg of 2-amino terephthalic acid is dissolved in 20mL of ultrapure water.
3. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein in the step (2), tetrakis hydroxymethyl phosphonium sulfate and 2-aminoterephthalic acid are ultrasonically mixed according to a molar ratio of 0-4: 1.
4. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein in the step (2), tetrakis hydroxymethyl phosphonium sulfate and 2-aminoterephthalic acid are ultrasonically mixed according to different molar ratios of 0:1,0.5:1,1:1,2:1,3:1 or 4:1, and the mixture is ultrasonically treated for 10-40 minutes under the condition that the ultrasonic power is 300-400W, so as to form 6 mixed solutions with different ratios.
5. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein the mixed solution is subjected to a hydrothermal reaction in the step (3), wherein the hydrothermal reaction temperature is 100-200 ℃ and the hydrothermal reaction time is 4-12 hours, so as to obtain a hydrothermal reaction solution.
6. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein the hydrothermal reaction solution obtained in the step (4) is centrifuged at 3000-10000 rpm for 5 minutes, and the solution from which large particles are removed is filtered by a 0.22 μm filter membrane to obtain a filtrate.
7. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein in the step (5), the pH of the filtrate is adjusted to be neutral by using a sodium hydroxide solution, and then the filtrate is dialyzed for 8-32 hours by using a dialysis bag with the shear molecular weight of 500-1000Da to obtain a first dialysate, and the dialysate is dialyzed for 72 hours by using a dialysis bag with the shear molecular weight of 3500-8000 Da to obtain a second dialysate.
8. The method for preparing the electrochemiluminescence wavelength-tunable carbon quantum dot according to claim 1, wherein in the step (6), the dialysate is subjected to rotary evaporation concentration preferably at a constant temperature of 40-80 ℃ to obtain a concentrated solution.
9. The carbon quantum dot with the electrochemiluminescence wavelength adjustable, prepared by the method for preparing the carbon quantum dot with the electrochemiluminescence wavelength adjustable according to claim 1, wherein the electrochemiluminescence wavelength of the carbon quantum dot is 425 nm-645 nm.
10. An application of the electrochemiluminescence wavelength tunable carbon quantum dot prepared by the preparation method of the electrochemiluminescence wavelength tunable carbon quantum dot according to claim 1 as a luminophore in electrochemiluminescence for simultaneously detecting multiple disease markers.
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