CN110003897B - Fluorescent carbon quantum dot and preparation method and application thereof - Google Patents
Fluorescent carbon quantum dot and preparation method and application thereof Download PDFInfo
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention relates to the field of nano materials, and discloses a fluorescent carbon quantum dot and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing the manure with deionized water, and reacting at the temperature of 130-190 ℃ under autogenous pressure for 0.5-6 h; (2) filtering the reaction solution prepared in the step (1), performing rotary evaporation concentration, performing column chromatography, drying the solution collected by the column chromatography through rotary evaporation, and mixing the dried product with deionized water to obtain a mixture; (3) performing suction filtration on the mixture prepared in the step (2), dialyzing the filtrate collected by the suction filtration by using a dialysis bag, and performing rotary evaporation on the dialyzed solution to dryness to obtain the fluorescent carbon quantum dots; wherein the manure comprises the following effective components in percentage by mass: organic matter > 45%. The carbon element in the manure is used as the carbon precursor for synthesizing the fluorescent carbon quantum dot, the preparation condition is green and environment-friendly, and the fluorescent carbon quantum dot is uniformly dispersed and has strong fluorescence characteristic.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a fluorescent carbon quantum dot and a preparation method and application thereof.
Background
The fluorescent carbon quantum dot is a novel nano material which is discovered for the first time by Scrivens and the like in 2004 for researching single-walled carbon nanotubes, compared with the traditional semiconductor quantum dot and organic dye, the fluorescent carbon quantum dot is used as a novel luminescent material, not only maintains the advantages of small toxicity, good biocompatibility and the like of a carbon material, but also has incomparable advantages of adjustable luminescent range, large two-photon absorption cross section, high fluorescent quantum efficiency, good light stability, no light flicker, easy functionalization, low price, easy large-scale synthesis and the like, basically does not damage cells, particularly has unique advantages when marking living organisms, and has been widely concerned at present. The average grain diameter of the fluorescent carbon quantum dots is less than 10nm, the fluorescent carbon quantum dots have long fluorescence life, are safer than the prior fluorescent materials, and have important value in the fields of fluorescent probe biological detection, biological sensing, biological analysis, biochemical analysis of metal cations and anions, biosensors, photoelectric conversion, photocatalysis and the like.
At present, the synthesis methods of fluorescent carbon quantum dots mainly comprise two main types, namely a top-down method and a bottom-up method. The top-down method mainly comprises arc discharge, laser ablation, electrochemical oxidation and the like, and the method usually needs severe experimental conditions, and has high cost, complex operation and lower yield; the bottom-up method mainly comprises a hydrothermal synthesis method, a microwave method, an ultrasonic method and the like, and has the advantages of simple experimental conditions, high yield and convenience for large-scale batch production. The hydrothermal processes of the prior art are widely used because of their particular advantages, but generally require the use of strong acids, bases or toxic reagents. Therefore, it is important to find cheap, easily available, natural and nontoxic raw materials and rapidly prepare the fluorescent carbon quantum dots with excellent optical properties by a simple and effective method. The method is an important subject to be solved in the field by searching cheap, easily-obtained, natural, nontoxic and environment-friendly raw materials as a carbon source of the fluorescent carbon quantum dot and avoiding introducing strong acid, strong base and toxic reagents in the preparation process, and the green preparation of the fluorescent carbon quantum dot is very important for the later biological application of the fluorescent carbon quantum dot.
Disclosure of Invention
The invention aims to solve the problem that the existing raw materials for preparing the fluorescent carbon quantum dots are high in price or small in quantity, and provides the fluorescent carbon quantum dots and the preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a fluorescent carbon quantum dot, comprising the following steps:
(1) mixing the manure with deionized water, and reacting at the temperature of 130-190 ℃ under autogenous pressure for 0.5-6 h;
(2) filtering the reaction solution prepared in the step (1), performing rotary evaporation concentration, performing column chromatography, performing rotary evaporation drying on the solution collected by the column chromatography, and mixing a dried product with deionized water to obtain a mixture;
(3) performing suction filtration on the mixture prepared in the step (2), dialyzing the filtrate collected by the suction filtration by using a dialysis bag, and performing rotary evaporation on the dialyzed solution to dryness to obtain fluorescent carbon quantum dots;
wherein the manure comprises the following effective components in percentage by mass: organic matter > 45%.
Preferably, the manure is one or more of fermented manure, biogas residue or finished manure of biogas residue.
Preferably, the temperature of the rotary evaporation is 55-70 ℃.
Preferably, in the step (1), the mass ratio of the manure to the deionized water is 1: 2-20.
Preferably, the column chromatography in step (2) adopts a wet method for loading, silica gel is used as a stationary phase, dichloromethane is used as a developing agent, and dichloromethane and absolute ethyl alcohol are used as eluents.
Preferably, the filter membrane pore size of the suction filtration in the step (3) is 0.22-0.45 μm.
Preferably, the cut-off amount of the dialysis bag in the step (3) is 1000-.
The invention also provides a fluorescent carbon quantum dot prepared by the preparation method.
The third aspect of the invention provides the fluorescent carbon quantum dots prepared by the preparation method in Fe3+Application in detection.
Through the technical scheme, the invention has the beneficial effects that: in the preparation method of the inventionThe raw materials are wide in source and low in price, the preparation conditions are green and environment-friendly, the particle size of the prepared fluorescent carbon quantum dot is (1.9 +/-1.05) nm, the fluorescent carbon quantum dot is uniformly dispersed, has a strong fluorescent characteristic, is good in biocompatibility and can be used for Fe3+Has good response and selectivity, and has application prospect in the fields of optical devices, cell imaging, drug transportation, biological detection, photocatalysis, solar cells, photoelectric devices, environmental science and the like.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a fluorescent carbon quantum dot prepared in example 1;
FIG. 2 is a particle size distribution diagram of the fluorescent carbon quantum dots prepared in example 1;
FIG. 3 is a UV absorption spectrum of the fluorescent carbon quantum dot prepared in example 1;
FIG. 4 is the emission spectra of the fluorescent carbon quantum dots prepared in example 1 at different excitation wavelengths;
FIG. 5 is an infrared spectrum of the fluorescent carbon quantum dots prepared in example 1;
FIG. 6 is the fluorescence intensity of the fluorescent carbon quantum dots prepared in example 2 at different NaCl concentrations;
FIG. 7 is the fluorescence intensity of the fluorescent carbon quantum dots prepared in example 2 at different pH;
FIG. 8 is a time scan of the fluorescent carbon quantum dots prepared in example 2;
FIG. 9 is the effect of different metal ions on the fluorescence intensity of the fluorescent carbon quantum dot solution prepared in example 1;
FIG. 10 shows the fluorescent carbon quantum dots prepared in example 1 with Fe3+And fitting curve and function graph corresponding to the fluorescence intensity change value of concentration change.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a preparation method of a fluorescent carbon quantum dot, which comprises the following steps:
(1) mixing the manure with deionized water, and reacting at the temperature of 130-190 ℃ under autogenous pressure for 0.5-6 h;
(2) filtering the reaction solution prepared in the step (1), performing rotary evaporation concentration, performing column chromatography, performing rotary evaporation drying on the solution collected by the column chromatography, and mixing a dried product with deionized water to obtain a mixture;
(3) performing suction filtration on the mixture prepared in the step (2), dialyzing the filtrate collected by the suction filtration by using a dialysis bag, and performing rotary evaporation on the dialyzed solution to dryness to obtain fluorescent carbon quantum dots;
wherein the manure comprises the following effective components in percentage by mass: organic matter > 45%. More preferably, the mass percentage of nitrogen + phosphorus (calculated as phosphorus pentoxide) + potassium (calculated as potassium oxide) in the manure is > 5%. In the present invention, the organic matter refers to an organic matter that can be decomposed by microorganisms, and the deionized water refers to pure water from which impurities in the form of ions have been removed.
In the present invention, any filtration method may be used as the filtration method, for example, an atmospheric filter paper filtration or a suction filtration.
Preferably, the manure is one or more of fermented manure, biogas residue or finished manure of biogas residue.
The fermented manure is characterized in that chaff, peanut shells, straws, fallen leaves and the like are used as main carbon sources for microbial growth and metabolism, chicken, pig, cow, sheep manure, rice bran, animal bones and the like can be used as main nitrogen sources for microorganisms, organic matters are decomposed by the microorganisms during fermentation, and are subjected to stacking fermentation, so that the fermented manure is killed in the fermentation process of plant diseases and insect pests, and meanwhile, part of the organic matters are decomposed, and the available nutrients of plants are effectively increased.
The biogas residue is solid part obtained by solid-liquid separation of human, livestock, fowl feces and urine and crop straw after anaerobic reaction to generate biogas, wherein the content of organic matter containing humus is 40-60%, the content of total nitrogen is 1-2%, and the residue contains vitamins, hormone, etc., and can be used as feed and fertilizer.
The biogas residue finished manure is prepared by piling excrement, biogas residue, straw and the like in a fermentation tank, adding a decomposing agent, and fermenting at the temperature of about 0 ℃ for 10-15 days until the manure is completely decomposed. The process for preparing the biogas residue finished manure by taking the pig manure as the raw material comprises the following steps: firstly, determining the contents of total nitrogen and total carbon in the pig manure and the straws, calculating the carbon-nitrogen ratio of the two raw materials, and mixing the pig manure and the straws according to the carbon-nitrogen ratio of 20-40: 1. preparing with water content of 55-75%, composting, adding fast-decomposing microbial agent to accelerate decomposition, turning over every 2 days in the temperature rise period of the compost, when the temperature of the compost is reduced to 40 ℃, adding phosphate-solubilizing bacteria while turning over the compost, performing secondary fermentation, and turning over the compost every 5 days until the compost is completely decomposed.
Preferably, the temperature of the rotary evaporation is 55-70 ℃.
Preferably, in the step (1), the mass ratio of the manure to the deionized water is 1: 2-20.
Preferably, the column chromatography in step (2) adopts a wet method for loading, silica gel is used as a stationary phase, dichloromethane is used as a developing agent, and dichloromethane and absolute ethyl alcohol are used as eluents.
Preferably, the filter membrane pore size of the suction filtration in the step (3) is 0.22-0.45 μm.
Preferably, the cut-off amount of the dialysis bag in the step (3) is 1000-.
In a second aspect, the invention provides a fluorescent carbon quantum dot prepared by the preparation method.
In a third aspect, the invention provides a fluorescent carbon quantum dot prepared by the above preparation method in Fe3+Application in detection.
The present invention will be described in detail below by way of examples. In the following examples, the transmission electron microscope was FEI, Inc. of America, model Tecnai G2-20S-Twin; the ultraviolet spectrophotometer is available from Chishanghai science and technology company, and has a model number of UV-2450; the fluorescence spectrophotometer is Shanghai spectrometer, and the model is F-2500; the infrared spectrometer is a German Bruker company with the model of ALPHA; dichloromethane, absolute ethyl alcohol, hydrochloric acid, sodium chloride, sodium dihydrogen phosphate and disodium hydrogen phosphate which are all of analytical grade and purchased from national medicine group chemical reagent company Limited; fermented manure, biogas residue and biogas residue finished manure are provided by research center of pig farm waste harmless treatment and resource utilization engineering technology in Hunan province.
Example 1
(1) Mixing 2.5g of fermented manure (wherein the organic matter content is 46%, nitrogen + phosphorus (calculated by phosphorus pentoxide) + potassium (calculated by potassium oxide) is 6%) with 50mL of deionized water, reacting for 4h at the temperature of 150 ℃, standing and cooling to room temperature;
(2) filtering the reaction solution prepared in the step (1) by using filter paper frequently, performing rotary evaporation and concentration on the filtrate at 60 ℃ to obtain about 1mL of a carbon quantum dot primary product, performing wet loading on the carbon quantum dot primary product solution by using silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as eluents, performing column chromatography on the carbon quantum dot primary product solution, performing rotary evaporation and drying on the solution collected by the column chromatography at 60 ℃, and re-dissolving the dried product by using 10mL of deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a filter membrane of 0.22 mu m, dialyzing the filtrate collected by suction filtration for 24h by using a dialysis bag with the cut-off of 3500Da (changing the dialyzate every 6 h), and carrying out rotary evaporation on the dialyzed solution at the temperature of 60 ℃ to dryness to obtain 120 mu g of fluorescent carbon quantum dots.
Transmission Electron Microscopy (TEM), ultraviolet absorption spectroscopy, fluorescence spectroscopy and infrared spectroscopy were performed on the fluorescent carbon quantum dots prepared in example 1, and the analysis results are shown in fig. 1 to 5.
The size and the appearance characteristics of the prepared fluorescent carbon quantum dots are characterized through a Transmission Electron Microscope (TEM), the result shows that the prepared fluorescent carbon quantum dots are spherical and have good dispersibility (shown in figure 1), the particle sizes of 118 fluorescent carbon quantum dots are measured to obtain corresponding particle size distribution (shown in figure 2), the particle sizes of the fluorescent carbon quantum dots are (1.9 +/-1.05) nm, and the sizes of the fluorescent carbon quantum dots are uniform.
The solution color of the fluorescent carbon quantum dots under sunlight is yellow, the solution color of the fluorescent carbon quantum dots under 273nm ultraviolet light is blue, the ultraviolet absorption spectrum of the fluorescent carbon quantum dots is shown in figure 3, the absorption peak of the absorption spectrum of the fluorescent carbon quantum dots at 273nm is weaker, and the fact that the pi → pi transition of conjugated carbon-carbon double bonds of the fluorescent carbon quantum dots is stronger than that of the fluorescent carbon quantum dots.
As can be seen from fig. 4, as the excitation wavelength of the fluorescence spectrum increases from 360nm to 440nm, the maximum fluorescence emission intensity of the fluorescent carbon quantum dot decreases from 339a.u. to 37a.u., the emission peak of the fluorescent carbon quantum dot is strongest when the excitation wavelength is 434nm, the maximum excitation wavelength of the fluorescent carbon quantum dot is 358nm, the maximum emission wavelength is 434nm, and the emission wavelength shows a significant red shift phenomenon as the excitation wavelength increases.
The infrared spectrum of the fluorescent carbon quantum dots is 3424cm as shown in FIG. 5-11635cm as the peak of O-H stretching vibration-1Is C ═ C stretching vibration peak, 1385cm-1The stretching vibration peak of-COOH indicates that some carboxylic acids, alcohols and unsaturated hydrocarbons may be contained in the fluorescent carbon quantum dot, and the peak value is 1163--1Ether (C-O) stretching vibration peak is formed, which indicates that organic matters (such as phenols and alcohols) containing hydroxyl are subjected to dehydration reaction to generate ether substances; at 2980 and 2834cm-1Has C-H stretching vibration absorption peak at 1200cm-1Has C-N stretching vibration peak.
Example 2
(1) Mixing 2.5g of biogas residue (wherein the organic matter content is 50%, nitrogen + phosphorus (calculated by phosphorus pentoxide) + potassium (calculated by potassium oxide) is 8%) with 25mL of deionized water, reacting for 2h at 190 ℃, standing and cooling to room temperature;
(2) filtering the reaction solution prepared in the step (1) by using filter paper frequently, performing rotary evaporation concentration on the filtrate at 55 ℃ to obtain about 1mL of a carbon quantum dot primary product, performing wet loading on the carbon quantum dot primary product solution by using silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as eluents, performing column chromatography on the carbon quantum dot primary product solution, performing rotary drying on the solution collected by the column chromatography at 55 ℃, and redissolving the dried product by using 10mL of deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a filter membrane of 0.45 mu m, dialyzing the filtrate collected by suction filtration for 20h by using a dialysis bag with the cut-off quantity of 2000Da (changing the dialyzate every 4 h), and carrying out rotary evaporation on the dialyzed solution at the temperature of 55 ℃ to dryness to obtain 100 mu g of fluorescent carbon quantum dots.
Example 3
(1) Mixing 2.5g of biogas residue finished manure (wherein the content of organic matters is 55%, nitrogen and phosphorus (calculated by phosphorus pentoxide) + potassium (calculated by potassium oxide) is 7%) with 5mL of deionized water, reacting for 6h at the temperature of 130 ℃, standing and cooling to room temperature;
(2) carrying out suction filtration on the reaction liquid prepared in the step (1), carrying out rotary evaporation and concentration on the filtrate at 70 ℃ to obtain a carbon quantum dot primary product, carrying out wet loading on a carbon quantum dot primary product solution by taking silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as an eluent, carrying out column chromatography on the carbon quantum dot primary product solution, carrying out rotary drying on the solution collected by the column chromatography at 70 ℃, and redissolving the dried product by 10ml of deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a filter membrane of 0.22 mu m, dialyzing the filtrate collected by suction filtration for 22h by using a dialysis bag with the cut-off quantity of 1000Da (changing the dialyzate every 5 h), and carrying out rotary evaporation on the dialyzed solution at 70 ℃ to dryness to obtain 105 mu g of fluorescent carbon quantum dots.
Example 4
(1) Mixing 1g of fermented manure and 1.5g of biogas residue finished manure (wherein the organic matter content is 51%, nitrogen and phosphorus (calculated as phosphorus pentoxide) + potassium (calculated as potassium oxide)) with 45mL of deionized water, reacting for 1h at the temperature of 170 ℃, standing and cooling to room temperature;
(2) filtering the reaction solution prepared in the step (1) by using filter press paper, concentrating the filtrate at 50 ℃ to obtain a carbon quantum dot primary product, performing wet loading on the carbon quantum dot primary product solution by using silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as an eluent, performing column chromatography on the carbon quantum dot primary product solution, performing rotary drying on the solution collected by the column chromatography at 50 ℃, and redissolving the dried product by using deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a filter membrane of 0.45 mu m, dialyzing the filtrate collected by suction filtration for 24h by using a dialysis bag with the cut-off of 3500Da (changing the dialyzate every 5 h), and carrying out rotary evaporation on the dialyzed solution at 50 ℃ to dryness to obtain 90 mu g of fluorescent carbon quantum dots.
Example 5
(1) Mixing 1.5g of biogas residue and 1g of biogas residue finished manure (wherein the content of organic matters is 52%, nitrogen and phosphorus (calculated as phosphorus pentoxide) + potassium (calculated as potassium oxide) is 7%) with 70mL of deionized water, reacting for 0.5h at 160 ℃, standing and cooling to room temperature;
(2) performing suction filtration on the reaction liquid prepared in the step (1), performing rotary evaporation concentration on the filtrate at 55 ℃ to obtain a carbon quantum dot primary product, performing wet loading on the carbon quantum dot primary product solution by using silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as eluents, performing column chromatography on the carbon quantum dot primary product solution, performing rotary drying on the solution collected by the column chromatography at 55 ℃, and re-dissolving the dried product with deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a filter membrane of 0.22 mu m, dialyzing the filtrate collected by suction filtration for 20h by using a dialysis bag with the cut-off quantity of 3000Da (changing the dialyzate every 5 h), and carrying out rotary evaporation on the dialyzed solution at the temperature of 55 ℃ to dryness to obtain 85 mu g of fluorescent carbon quantum dots.
Example 6
(1) Mixing 1g of fermented manure and 1.5g of biogas residue (wherein the content of organic matters is 48%, nitrogen and phosphorus (calculated as phosphorus pentoxide) + potassium (calculated as potassium oxide)) with 35mL of deionized water, reacting for 1h at 140 ℃, and standing to reduce the temperature to room temperature;
(2) carrying out suction filtration on the reaction liquid prepared in the step (1), concentrating the filtrate at 65 ℃ to obtain a carbon quantum dot primary product, carrying out wet-process sample loading on the carbon quantum dot primary product solution by using silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as eluents, carrying out column chromatography on the carbon quantum dot primary product solution, carrying out rotary drying on the solution collected by the column chromatography at 65 ℃, and re-dissolving the dried product with deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a 0.22-micron filter membrane, dialyzing the filtrate collected by suction filtration for 21h by using a dialysis bag with the cut-off quantity of 2000Da, and carrying out rotary evaporation on the dialyzed solution at the temperature of 65 ℃ to dryness to obtain 70 mu g of fluorescent carbon quantum dots.
Example 7
(1) Adding 2.5g of biogas residue finished manure (wherein the content of organic matters is 55%, nitrogen, phosphorus (calculated by phosphorus pentoxide) and potassium (calculated by potassium oxide) are 7%) into 40mL of deionized water, reacting for 5h at the temperature of 180 ℃, standing and cooling to room temperature;
(2) carrying out suction filtration on the reaction liquid prepared in the step (1), concentrating the filtrate at 60 ℃ to obtain a carbon quantum dot primary product, carrying out wet-process sample loading on the carbon quantum dot primary product solution by using silica gel as a stationary phase, dichloromethane as a developing agent and dichloromethane and absolute ethyl alcohol as an eluent, carrying out column chromatography on the carbon quantum dot primary product solution, carrying out rotary drying on the solution collected by the column chromatography at 60 ℃, and redissolving the solution by using deionized water to obtain a mixture;
(3) and (3) carrying out suction filtration on the mixture prepared in the step (2) by using a filter membrane of 0.65 mu m, dialyzing the filtrate collected by suction filtration for 24h by using a dialysis bag with the cut-off of 3000Da (changing the dialyzate every 4 h), and carrying out rotary evaporation on the dialyzed solution at the temperature of 60 ℃ to dryness to obtain 85 mu g of fluorescent carbon quantum dots.
Experimental example 1
And (3) adding 3mL of sodium chloride solutions with the concentrations of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L and 0.5mol/L into 100 mu g of the fluorescent carbon quantum dots prepared in the example 2 respectively, uniformly mixing, measuring the fluorescence intensity of the fluorescent carbon quantum dots in the sodium chloride solution by using a fluorescence spectrophotometer, and analyzing results are shown in figure 6, which shows that the prepared fluorescent carbon quantum dots have good salt resistance.
The fluorescence intensity of the fluorescent carbon quantum dots at different pH values was as shown in fig. 7, and no significant change was observed in the pH range of 2 to 7, indicating that the obtained fluorescent carbon quantum dots had good acid resistance, when 100 μ g of the fluorescent carbon quantum dots obtained in example 2 were added to 3mL of PBS buffer solution having different pH values, in which PBS buffer solution having pH 5, pH 6, pH 7, pH 8, pH 9, pH 10, pH 11, pH 12 and pH 13 was prepared.
The specific measurement process of the change of the fluorescence intensity of the fluorescent carbon quantum dots along with time is as follows: the change of the fluorescence intensity of the prepared fluorescent carbon quantum dot with time is shown in figure 8 by adding 3mL of deionized water into 100 mu g of the fluorescent carbon quantum dot prepared in the example 2, and the fluorescence intensity of the prepared fluorescent carbon quantum dot is stable within the range of 0-1800 s.
Experimental example 2
10 parts of 25. mu.g of the fluorescent carbon quantum dot prepared in example 1 were mixed with 600. mu.L of water, and then 3. mu.L of different ionic solutions having an ionic concentration of 0.01mol/L, respectively, were added, the ionic species including Ca2+、Fe2+、Na+、Pb2+、Cd2+、Fe3+、K+、Cu2+、Al3+、Mg2+When the change in fluorescence intensity of the fluorescent carbon quantum dots was observed, as shown in FIG. 9, it was found that Fe was added3+Then, the fluorescence of the fluorescent carbon quantum dots is almost quenched, and the characteristic has a remarkable response and can be used for detecting Fe3+。
Fe3+Measurement of detection limit: the fluorescent carbon quantum dots (300. mu.g) prepared in example 1 were taken and the volume was adjusted to 600. mu.L, and the fluorescence intensity was measured to be I0Respectively taking 1.5 muL, 2.5 muL, 3.5 muL, 4.5 muL and 5.5 muL of Fe with the concentration of 0.1mol/L3+Adding the solution into 300 mu L of the fluorescent carbon quantum dot solution, adding water to a constant volume of 1000 mu L, and measuring the fluorescence intensity to be I. By means of In(i.e. I)0-I) is the ordinate, Fe3+The concentration is the abscissa, and the pair of fluorescent carbon quantum dots to Fe is measured3+The result is shown in FIG. 10, the fluorescent carbon quantum dots are changed with Fe3+The function corresponding to the fitted curve corresponding to the change in fluorescence intensity with change in concentration is-128.8 x +293.2, R20.9852, linear range of 0.15-0.55mmol/L, fluorescent carbon quantum dot to Fe3+The detection limit of (A) is 0.15 mmol/L.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (6)
1. Fluorescent carbon quantum dots in Fe3+The application in detection is characterized in that the preparation method of the fluorescent carbon quantum dot comprises the following steps:
(1) mixing the manure with deionized water, and reacting at the temperature of 130-190 ℃ under autogenous pressure for 0.5-6 h;
(2) filtering the reaction solution prepared in the step (1), performing rotary evaporation concentration, performing column chromatography, drying the solution collected by the column chromatography through rotary evaporation, and mixing the dried product with deionized water to obtain a mixture;
(3) performing suction filtration on the mixture prepared in the step (2), dialyzing the filtrate collected by the suction filtration by using a dialysis bag, and performing rotary evaporation on the dialyzed solution to dryness to obtain the fluorescent carbon quantum dots;
the manure is one or more of fermented manure, biogas residue or finished manure of biogas residue, and the effective components in the manure are as follows by mass percent: organic matter > 45%.
2. The fluorescent carbon quantum dots of claim 1 in Fe3+Use in assays, characterized in that the temperature of the rotary evaporation is between 55 and 70 ℃.
3. The fluorescent carbon quantum dots of claim 1 in Fe3+The application in detection is characterized in that in the step (1), the mass ratio of the manure to the deionized water is 1: 2-20.
4. The fluorescent carbon quantum dots of claim 1 in Fe3+The application of the detection is characterized in that the column chromatography in the step (2) adopts wet-process sample loading, silica gel is used as a stationary phase, dichloromethane is used as a developing agent, and dichloromethane and anhydrous ethyl acetate are usedAlcohol is used as eluent.
5. The fluorescent carbon quantum dots of claim 1 in Fe3+The application in detection is characterized in that the aperture of the filter membrane subjected to suction filtration in the step (3) is 0.22-0.45 μm.
6. The fluorescent carbon quantum dots of claim 1 in Fe3+The application in detection is characterized in that the interception amount of the dialysis bag in the step (3) is 1000-.
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| CN107311145A (en) * | 2017-08-29 | 2017-11-03 | 湖南农业大学 | A kind of fluorescent carbon point for the method and its preparation that fluorescent carbon point is prepared by raw material of silkworm excrement |
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| CN104861968A (en) * | 2015-05-11 | 2015-08-26 | 南昌大学 | Preparation method for fluorescent carbon quantum dots by taking urine as raw material |
| CN107311145A (en) * | 2017-08-29 | 2017-11-03 | 湖南农业大学 | A kind of fluorescent carbon point for the method and its preparation that fluorescent carbon point is prepared by raw material of silkworm excrement |
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