CN110643359B - Fluorescent sensor for ascorbic acid detection and preparation method thereof - Google Patents

Fluorescent sensor for ascorbic acid detection and preparation method thereof Download PDF

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CN110643359B
CN110643359B CN201910837200.5A CN201910837200A CN110643359B CN 110643359 B CN110643359 B CN 110643359B CN 201910837200 A CN201910837200 A CN 201910837200A CN 110643359 B CN110643359 B CN 110643359B
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付海燕
时琼
佘远斌
兰薇
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Abstract

The invention discloses a fluorescent sensor for ascorbic acid detection and a preparation method thereof, wherein the fluorescent sensor is prepared by the following steps: 1) mixing carbon source powder and nitrogen source powder, grinding, heating and liquefying the mixed powder to prepare a precursor solution, adding a sodium hydroxide solution into the precursor solution to adjust the pH value, and filtering to obtain a nitrogen-doped carbon dot solution; 2) ultrasonically mixing a sodium hydroxide solution and a cobalt sulfate solution, adding hydrogen peroxide, ultrasonically reacting at room temperature, adjusting the pH value of a reaction system by using hydrochloric acid, centrifuging the solution, washing by using deionized water, and drying to obtain cobalt oxyhydroxide powder; 3) and (3) adding the powder in the step (2) into the solution in the step (1), and fully stirring and ultrasonically mixing at room temperature to obtain the fluorescent sensor for detecting the ascorbic acid. The fluorescent sensor disclosed by the invention is simple in preparation process, green and environment-friendly, strong in operability and low in cost, and can realize high-sensitivity detection of ascorbic acid.

Description

Fluorescent sensor for ascorbic acid detection and preparation method thereof
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a fluorescent sensor for ascorbic acid detection and a preparation method thereof.
Background
Ascorbic Acid (AA) is one of the most important neurochemicals in the brain system, and not only plays an antioxidant role in the intracellular antioxidant system, but also plays an important role in neuroprotection. Levels of AA are closely related to several diseases, for example, insufficient AA intake can cause symptoms of scurvy, while excessive AA intake can induce urinary calculi, diarrhea, and stomach twitch. Many methods such as electrochemistry, liquid chromatography, high performance liquid chromatography in combination with electrochemical detectors (HPLC-ED) have been developed for the determination of AA. The above methods are limited by the complicated sample separation process, the low time resolution or high cost of the large number of instruments, and AA degradation during the separation process.
Due to the inherent advantages of high sensitivity and high selectivity, fluorescent probe sensors have attracted increasing attention for the direct monitoring of target analytes in living cells, tissues and animals without the need for complex pre-treatments. Several effective organic fluorescent probes have been designed, such as a cobalt oxyhydroxide (CoOOH) modified persistent luminescent nanoparticle (Sr) designed by professor down dynasty2MgSi2O7：1％Eu，2％Dy)[Li,N.,Li,Y.,Han,Y.,Pan,W.,Zhang,T.,Tang,B.Anal.Chem.2014,86,3924-3930.]The Linnaqing team developed a Tris (hydroxymethyl) -aminomethane-derived Carbon Dot (CD) modified hexagonal cobalt oxyhydroxide (CoOOH) nanosheet (Tris-derived CDs-CoOOH) [ Li, LB., Wang, C., Liu, KY., Wang, YH., Liu, K., Lin, YQ.anal.Chem.2015,87(6): 3404-.]. However, the preparation of these nanoparticles is still complicated and has harsh synthesis conditions. Therefore, the ascorbic acid fluorescence sensor which is cheap, simple and strong in operability is further developed, and has important research and application significance.
Disclosure of Invention
The invention mainly aims to provide a fluorescent sensor for ascorbic acid detection and a preparation method thereof aiming at the defects in the prior art, so that the high specificity and high sensitivity detection of ascorbic acid can be realized, the related preparation method is simple, environment-friendly and high in operability, and a new thought and method can be provided for the field monitoring technology of ascorbic acid.
In order to achieve the purpose, the invention adopts the technical scheme that:
a fluorescent sensor for ascorbic acid detection is prepared by the following steps:
1) mixing carbon source powder and nitrogen source powder, fully grinding to obtain mixed powder, heating the mixed powder to liquefy the mixed powder to obtain precursor solution, dripping the obtained precursor solution into sodium hydroxide solution under the condition of vigorous stirring, adjusting the pH value of a reaction system to 6.8-11.0, cooling to room temperature to obtain suspension, and filtering the obtained suspension by using a microfiltration membrane to obtain a nitrogen-doped carbon dot solution;
2) ultrasonically mixing a sodium hydroxide solution and a cobalt sulfate solution at room temperature to obtain a cobalt hydroxide solution, then adding hydrogen peroxide into the cobalt hydroxide solution, ultrasonically reacting at room temperature, adjusting the pH value of a reaction system to 7-8 by using hydrochloric acid to obtain a cobalt oxyhydroxide suspension, and then centrifuging, washing and drying the suspension to obtain cobalt oxyhydroxide powder;
3) dissolving the cobalt oxyhydroxide powder obtained in the step 2) in absolute ethyl alcohol, adding the obtained solution into the nitrogen-doped carbon dot solution obtained in the step 1), fully stirring at room temperature, ultrasonically mixing, and diluting with deionized water as required to obtain the fluorescent sensor for ascorbic acid detection.
According to the scheme, the carbon source powder in the step 1) is glucose or citric acid monohydrate, and the nitrogen source powder is amino acid and derivatives thereof. Preferably, the nitrogen source powder is selected from glutamic acid, phenylalanine, leucine, valine, isoleucine, glutamine, glutathione.
According to the scheme, the mass ratio of the carbon source powder to the nitrogen source powder in the step 1) is 1: 0.05 to 0.8.
According to the scheme, the heating treatment temperature in the step 1) is 150-250 ℃, and the heating treatment time is 0.5-2 min.
According to the scheme, the concentration of the sodium hydroxide solution in the step 1) is 0.1M, and the volume ratio of the precursor solution to the sodium hydroxide solution is 1: 25-40.
According to the scheme, the aperture of the microfiltration membrane in the step 1) is 0.22 mu m.
According to the scheme, the fluorescence yield of the nitrogen-doped carbon dots in the nitrogen-doped carbon dot solution in the step 1) is 58.2-66.7%.
According to the scheme, the concentration of the sodium hydroxide solution in the step 2) is 1.0-2.5M, and the concentration of the cobalt sulfate solution is 5 multiplied by 10-3～10-2M, sodium hydroxide in sodium hydroxide solution and sulfur in cobalt sulfate solutionThe molar ratio of cobalt acid is 1: 8X 10-3～40×10-3。
According to the scheme, the ultrasonic reaction time in the step 2) is 2-8 min.
According to the scheme, the centrifugal rotating speed in the step 2) is 12000r/min, and the centrifugal time is 10-15 min.
According to the scheme, the molar ratio of the cobalt oxyhydroxide to the nitrogen-doped carbon dots in the ascorbic acid detection fluorescence sensor obtained in the step 3) is 1: 0.01 to 0.34.
According to the scheme, the ultrasonic mixing time in the step 3) is 10-15 min.
The invention also provides a preparation method of the fluorescent sensor for ascorbic acid detection, which comprises the following steps:
1) mixing carbon source powder and nitrogen source powder, fully grinding to obtain mixed powder, heating the mixed powder to liquefy the mixed powder to obtain precursor solution, dripping the obtained precursor solution into sodium hydroxide solution under the condition of vigorous stirring, adjusting the pH value of a reaction system to 6.8-11.0, cooling to room temperature to obtain suspension, and filtering the obtained suspension by using a microfiltration membrane to obtain a nitrogen-doped carbon dot solution;
2) ultrasonically mixing a sodium hydroxide solution and a cobalt sulfate solution at room temperature to obtain a cobalt hydroxide solution, then adding hydrogen peroxide into the cobalt hydroxide solution, ultrasonically reacting at room temperature, adjusting the pH value of a reaction system to 7-8 by using hydrochloric acid to obtain a cobalt oxyhydroxide suspension, and then centrifuging, washing and drying the suspension to obtain cobalt oxyhydroxide powder;
3) dissolving the cobalt oxyhydroxide powder obtained in the step 2) in absolute ethyl alcohol, adding the obtained solution into the nitrogen-doped carbon dot solution obtained in the step 1), fully stirring at room temperature, ultrasonically mixing, and diluting with deionized water as required to obtain the fluorescent sensor for ascorbic acid detection.
The principle of the invention is as follows: the fluorescence sensor is constructed by fluorescence resonance energy transfer between the nitrogen-doped carbon dots and the CoOOH, and the ascorbic acid is finally detected quickly and simply at low cost by using the redox reaction of the CoOOH and the ascorbic acid.
Compared with the prior art, the invention has the beneficial effects that:
1) the nitrogen-doped carbon dot-CoOOH fluorescence sensor provided by the invention has excellent sensitivity and high specificity on ascorbic acid, is beneficial to online detection of the biological process of ascorbic acid in physiological and pathological researches, and has important application prospects.
2) The nitrogen-doped carbon dot-CoOOH fluorescent sensor adopts a simple synthesis method, and the related preparation method is simple and easy to operate, has low raw material cost, and is suitable for popularization and application.
Drawings
FIG. 1 is a transmission electron microscope image of a nitrogen-doped carbon dot solution obtained in example 1 of the present invention;
FIG. 2 is a mid-infrared spectrum of CoOOH obtained in example 1;
FIG. 3 shows CoSO obtained in example 14And the ultraviolet spectrum of CoOOH;
FIG. 4 is a graph of the fluorescence emission spectrum of nitrogen-doped carbon dots obtained in example 2 and the UV spectrum of CoOOH;
FIG. 5 is a graph showing the fluorescence intensity of the mixed solution of N-doped carbon dots and CoOOH in the presence of interfering amino acids, glucose fructose and metal ions for detecting AA ascorbic acid in example 3;
FIG. 6 is a graph showing the change in fluorescence intensity of the diluted mixed solution of N-doped carbon dot-CoOOH with different concentrations of AA ascorbic acid in example 4;
FIG. 7 shows the change in fluorescence intensity (F-F) of the AA ascorbic acid solution of example 4 in the range of 5 to 800M0) A linear graph of (a);
FIG. 8 is the change in fluorescence intensity (F-F) of the AA ascorbic acid solution of example 4 in the range of 5-200M0) Linear graph of (a).
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A nitrogen-doped carbon dot-CoOOH fluorescence sensor for ascorbic acid detection is prepared by the following steps:
1) placing 1g of citric acid monohydrate powder and 0.05g of glutamic acid powder in a mortar for fully grinding to obtain mixed powder, heating the mixed powder on an electric heating sleeve at 250 ℃ for 0.5min to liquefy the mixed powder to obtain a precursor solution, dripping the precursor solution into 40mL of 0.1M sodium hydroxide solution under the condition of vigorous stirring, adjusting the pH value of a reaction system to 9.0 by using the sodium hydroxide solution, cooling to room temperature to obtain a suspension, and then passing the suspension through a 0.22 mu M microporous filter membrane to obtain a nitrogen-doped carbon dot solution (the fluorescence yield of the nitrogen-doped carbon dots is 58.2 percent);
2) ultrasonically mixing 250 mu L of 1.0M sodium hydroxide solution and 1mL of 10mM cobalt sulfate solution at room temperature to obtain a cobalt hydroxide solution, then adding 2mL of 30% hydrogen peroxide into the cobalt hydroxide solution, ultrasonically reacting for 2min at room temperature, adjusting the pH value of a reaction system to 7 by using hydrochloric acid to obtain a cobalt oxyhydroxide suspension, centrifuging the suspension at 12000r/min for 10min, washing with deionized water for 3 times, and drying to obtain cobalt oxyhydroxide powder;
3) take 5.8X 10-4Dissolving CoOOH powder prepared in step 2) with 1mL of anhydrous ethanol, and adding into 20mL of nitrogen-doped carbon dot solution (with concentration of 5 × 10) prepared in step 1)-5M) and ultrasonically mixing for 10min to obtain a mixed solution, namely the nitrogen-doped carbon dot-CoOOH fluorescent sensor for ascorbic acid detection.
FIG. 1 is a transmission electron micrograph of the N-doped carbon dot solution obtained in step 1) of this example, which shows that the size of the N-doped carbon dots is between 3 nm and 7 nm.
Performing potassium bromide tabletting on the cobalt oxyhydroxide powder obtained in the step 2), and recording that the cobalt oxyhydroxide is 400-4000cm-1Mid-infrared spectrogram in the range, 3453cm, as shown in FIG. 2-1Asymmetric stretching vibration attributed to-OH, and 2930cm-1Attributing to O-H stretching vibration, the powder is 1629cm-1And 659cm-1Are respectively Co ═ O and Co-O2-Another 1050cm of telescopic vibration form-1The stretching vibration pattern attributed to C-O indicated that the synthesized product was a CoOOH powder.
FIG. 3 shows CoSO in step 2) of this example4And oxidation of hydroxyl groupsThe ultraviolet spectrum of cobalt CoOOH shows CoSO at 400nm4The optimum absorption wavelength of CoOOH at 520nm has strong ultraviolet absorption, indicating that CoOOH has been successfully synthesized.
Example 2
A nitrogen-doped carbon dot-CoOOH nanosheet fluorescence sensor for ascorbic acid detection is prepared by the following steps:
1) placing 1g of citric acid monohydrate powder and 0.8g of glutamine powder in a mortar for fully grinding to obtain mixed powder, heating the mixed powder on an electric heating jacket at 150 ℃ for 2min to liquefy the mixed powder to obtain a precursor solution, dripping the precursor solution into 40mL of 0.1M sodium hydroxide solution under the condition of vigorous stirring, adjusting the pH value of a reaction system to 11.0 by using the sodium hydroxide solution, cooling to room temperature to obtain a suspension, and then passing the suspension through a 0.22 mu M microporous filter membrane to obtain a nitrogen-doped carbon dot solution (the fluorescence yield of the measured nitrogen-doped carbon dots is 66.7%);
2) ultrasonically mixing 250 mu L of 2.5M sodium hydroxide solution and 1mL of 5mM cobalt sulfate solution at room temperature to obtain a cobalt hydroxide solution, then adding 2mL of 30% hydrogen peroxide into the cobalt hydroxide solution, ultrasonically reacting at room temperature for 5min, adjusting the pH value of a reaction system to 8 by using hydrochloric acid to obtain a cobalt oxyhydroxide suspension, centrifuging the suspension at 12000r/min for 10min, washing with deionized water for 3 times, and drying to obtain cobalt oxyhydroxide powder;
3) take 1.6X 10-3Dissolving CoOOH powder prepared in step 2) with 1mL of anhydrous ethanol, and adding into 20mL of nitrogen-doped carbon dot solution (with concentration of 3 × 10) prepared in step 1)-4M) and ultrasonically mixing for 10min to obtain a mixed solution, namely the nitrogen-doped carbon dot-CoOOH fluorescent sensor for ascorbic acid detection.
FIG. 4 is a fluorescence emission spectrum of the nitrogen-doped carbon dot obtained in step 1) and an ultraviolet spectrum of the cobalt oxyhydroxide obtained in step 2) of this embodiment, which shows that the nitrogen-doped carbon dot has strong fluorescence at 350nm of 320-; the CoOOH has strong ultraviolet absorption at 330-500nm, and a fluorescence resonance energy transfer process can occur due to the existence of a remarkable absorption overlapping region between the CoOOH and the CoOOH.
Example 3
The nitrogen-doped carbon dot-CoOOH fluorescent sensor obtained in the embodiment 2 of the invention is applied to an anti-interference experiment for detecting ascorbic acid AA, and the specific steps comprise: several 200. mu.L portions of N-doped carbon dot-CoOOH fluorescent sensor (wherein the concentration of N-doped carbon dots is 5.0 × 10)-5g/mL, CoOOH concentration of 5.8X 10-4M) diluting to 1mL by deionized water to obtain a plurality of diluted nitrogen-doped carbon dot-CoOOH mixed solutions, and using the mixed solutions in the following detection tests:
adding 100 μ L of 2mM ascorbic acid AA solution into a diluted nitrogen-doped carbon dot-CoOOH mixed solution, reacting for 5 minutes, and recording the fluorescence intensity of the solution at an excitation wavelength of 340nm, wherein the fluorescence intensity is recorded as F0Separately, 50. mu.L of another interfering substance (each selected from proline Pro, cysteine Cys, histidine His, isoleucine Leu, aspartic acid Asp, serine Ser, alanine Ala, glutamic acid Glu, glucose Glc, fructose Fru, and a metal ion solution (Na) was prepared at a concentration of 40mM+，K+，Ca2 +) Respectively taking one of the interferents and 50 mu L of 4mM ascorbic acid AA solution, adding the interferent and the solution into a diluted nitrogen-doped carbon dot-CoOOH mixed solution, reacting for 5 minutes, recording the fluorescence intensity F of each solution at an excitation wavelength of 340nm, and inspecting the influence of different interferents on the fluorescence intensity of the nitrogen-doped carbon dot-CoOOH fluorescence sensor for detecting the ascorbic acid AA.
Fig. 5 is a fluorescence intensity curve of the mixed solution of nitrogen-doped carbon dot and CoOOH in the embodiment for detecting ascorbic acid AA in the presence of interferent amino acid, glucose fructose, and metal ions, and a test result shows that even if the concentration of the interferent is 10 times that of the ascorbic acid, the fluorescence intensity of the nitrogen-doped carbon dot and CoOOH is hardly affected, which indicates that the nitrogen-doped carbon dot-CoOOH fluorescence sensor obtained in the present invention has high anti-interference capability in detecting ascorbic acid AA.
Example 4
The nitrogen-doped carbon dot-CoOOH fluorescent sensor obtained in the embodiment 2 of the invention is applied to ascorbic acid AA detection, and the specific steps comprise: diluting 200 mu L of nitrogen-doped carbon dot-CoOOH fluorescent sensor to 1mL by using deionized water to obtain a plurality of groups of diluted nitrogen-doped carbon dots-The fluorescence intensity of the diluted nitrogen-doped carbon dot-CoOOH mixed solution is F at the excitation wavelength of 340nm (the excitation wavelength is 340nm, and the emission wavelength is 360-600 nm)0(ii) a Preparing a plurality of 100 mu L ascorbic acid AA solutions with different concentrations by using ascorbic acid, respectively adding the ascorbic acid AA solutions into the diluted nitrogen-doped carbon dot-CoOOH mixed solution, reacting for 5 minutes, and recording the fluorescence intensity F of the mixed solution at the excitation wavelength of 340 nm.
FIG. 6 is a curve showing the change of fluorescence intensity after ascorbic acid AA with different concentrations is added into a diluted mixed solution of nitrogen-doped carbon dot-CoOOH, and test results show that the fluorescence intensity of the nitrogen-doped carbon dot-CoOOH fluorescence sensor obtained by the invention is gradually enhanced with the increase of the concentration of ascorbic acid AA (5-200 μ M), and the concentration detection of ascorbic acid AA with 5-200 μ M can be realized.
FIG. 7 shows the change in fluorescence intensity (F-F) of AA ascorbic acid solution at a concentration in the range of 5-800M0) The linear graph shows that the concentration of the ascorbic acid AA solution is in a linear relationship with the change value of the fluorescence intensity within the range of 5-200M, and the concentration of the ascorbic acid AA solution is within the range of 5-200M0) The linear graph is shown in FIG. 8, and the test result shows that the nitrogen-doped carbon dot-CoOOH fluorescence sensor prepared by the embodiment of the invention can realize high-sensitivity detection of ascorbic acid AA in the concentration range of 5-200 μ M.
The invention can be realized by all the listed raw materials, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials; the examples are not to be construed as limiting the scope of the invention. The upper and lower limit values and interval values of the process parameters can realize the invention, and the embodiments are not listed.

Claims (7)

1. A fluorescence sensor for ascorbic acid detection is characterized in that the preparation method comprises the following steps:
1) mixing carbon source powder and nitrogen source powder, fully grinding to obtain mixed powder, heating the mixed powder at the temperature of 150-250 ℃ for 0.5-2 min to liquefy the mixed powder to obtain precursor solution, dripping the precursor solution into sodium hydroxide solution under the condition of vigorous stirring, adjusting the pH value of a reaction system to 6.8-11.0, cooling to room temperature to obtain turbid liquid, and filtering the turbid liquid by using a microfiltration membrane to obtain nitrogen-doped carbon dot solution, wherein the fluorescence yield of nitrogen-doped carbon dots in the nitrogen-doped carbon dot solution is 58.2-66.7%;
2) ultrasonically mixing a sodium hydroxide solution and a cobalt sulfate solution at room temperature to obtain a cobalt hydroxide solution, then adding hydrogen peroxide into the cobalt hydroxide solution, ultrasonically reacting at room temperature, adjusting the pH value of a reaction system to 7-8 by using hydrochloric acid to obtain a cobalt oxyhydroxide suspension, and then centrifuging, washing and drying the suspension to obtain cobalt oxyhydroxide powder;
3) dissolving the cobalt oxyhydroxide powder obtained in the step 2) in absolute ethyl alcohol, adding the obtained solution into the nitrogen-doped carbon dot solution obtained in the step 1), fully stirring at room temperature, ultrasonically mixing, and diluting with deionized water as required to obtain a fluorescent sensor for ascorbic acid detection;
step 1), the carbon source powder is glucose or citric acid monohydrate, and the nitrogen source powder is amino acid and derivatives thereof; the mass ratio of the carbon source powder to the nitrogen source powder is 1: 0.05 to 0.8;
step 1), the concentration of the sodium hydroxide solution is 0.1M, and the volume ratio of the precursor solution to the sodium hydroxide solution is 1: 25-40.
2. The fluorescence sensor for ascorbic acid detection according to claim 1, wherein the pore size of the microfiltration membrane of step 1) is 0.22 μm.
3. The fluorescence sensor for ascorbic acid detection according to claim 1, wherein the concentration of the sodium hydroxide solution in step 2) is 1.0 to 2.5M, and the concentration of the cobalt sulfate solution is 5 x 10-3~10-2M, the molar ratio of sodium hydroxide in the sodium hydroxide solution to cobalt sulfate in the cobalt sulfate solution is 1: 8X 10-3~40×10-3。
4. The fluorescence sensor for ascorbic acid detection according to claim 1, wherein the ultrasonic reaction time in step 2) is 2-8 min; in the step 2), the centrifugal rotating speed is 12000r/min, and the centrifugal time is 10-15 min.
5. The fluorescence sensor for ascorbic acid detection according to claim 1, wherein the molar ratio of cobalt oxyhydroxide to nitrogen-doped carbon dots in the fluorescence sensor for ascorbic acid detection obtained in step 3) is 1: 0.01 to 0.34.
6. The fluorescence sensor for ascorbic acid detection according to claim 1, wherein the ultrasonic mixing time in step 3) is 10 to 15 min.
7. A method for preparing a fluorescence sensor for ascorbic acid detection according to any of claims 1 to 6, comprising the following steps:
1) mixing carbon source powder and nitrogen source powder, fully grinding to obtain mixed powder, heating the mixed powder to liquefy the mixed powder to obtain precursor solution, dripping the obtained precursor solution into sodium hydroxide solution under the condition of vigorous stirring, adjusting the pH value of a reaction system to 6.8-11.0, cooling to room temperature to obtain suspension, and filtering the obtained suspension by using a microfiltration membrane to obtain a nitrogen-doped carbon dot solution;
2) ultrasonically mixing a sodium hydroxide solution and a cobalt sulfate solution at room temperature to obtain a cobalt hydroxide solution, then adding hydrogen peroxide into the cobalt hydroxide solution, ultrasonically reacting at room temperature, adjusting the pH value of a reaction system to 7-8 by using hydrochloric acid to obtain a cobalt oxyhydroxide suspension, and then centrifuging, washing and drying the suspension to obtain cobalt oxyhydroxide powder;
3) dissolving the cobalt oxyhydroxide powder obtained in the step 2) in absolute ethyl alcohol, adding the obtained solution into the nitrogen-doped carbon dot solution obtained in the step 1), fully stirring at room temperature, ultrasonically mixing, and diluting with deionized water as required to obtain the fluorescent sensor for ascorbic acid detection.
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