CN108913132B - Preparation method of dual-emission carbon-based nanoprobe and product thereof - Google Patents

Preparation method of dual-emission carbon-based nanoprobe and product thereof Download PDF

Info

Publication number
CN108913132B
CN108913132B CN201810800874.3A CN201810800874A CN108913132B CN 108913132 B CN108913132 B CN 108913132B CN 201810800874 A CN201810800874 A CN 201810800874A CN 108913132 B CN108913132 B CN 108913132B
Authority
CN
China
Prior art keywords
carbon
solution
dual
temperature
emission
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810800874.3A
Other languages
Chinese (zh)
Other versions
CN108913132A (en
Inventor
王婵
宋启军
胡昙昙
陈月月
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangnan University
Original Assignee
Jiangnan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Priority to CN201810800874.3A priority Critical patent/CN108913132B/en
Publication of CN108913132A publication Critical patent/CN108913132A/en
Application granted granted Critical
Publication of CN108913132B publication Critical patent/CN108913132B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01KMEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G01K11/16Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Biophysics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a preparation method of a dual-emission carbon-based nano probe prepared by an electrostatic interaction induced self-assembly method and application of a product of the dual-emission carbon-based nano probe in temperature detection inside and outside an organism, and belongs to the technical field of colorimetric fluorescence detection. The invention comprises the synthesis of blue fluorescent carbon dots (B-CDs) which are not temperature sensitive and have negative charges on the surface, the preparation of red fluorescent carbon dots (R-CDs) which have temperature sensitivity and have positive charges on the surface and the preparation of a dual-emission carbon-based fluorescent nano probe. The dual-emission carbon-based fluorescence nanoprobe obtained by the invention has different responsivities to different temperatures by utilizing the dual-emission carbon-based fluorescence nanoprobe, presents different composite fluorescence color changes, can be used for naked eye colorimetric detection of the temperature inside and outside an organism, has high sensitivity (0.93%/° C) and operation repeatability, and provides convenience for aspects of biological imaging, temperature sensing, environmental monitoring, food safety and the like.

Description

Preparation method of dual-emission carbon-based nanoprobe and product thereof
Technical Field
The invention particularly relates to a preparation method of a dual-emission carbon-based nano material for temperature sensing and application of the dual-emission carbon-based nano material in detection of temperature change in a biological environment, and belongs to the technical field of fluorescent nano materials.
Background
The temperature plays a crucial role in physiological and biochemical actions and processes in organisms, and the accurate measurement of the temperature plays a significant role, so that the temperature measurement technology is promoted from the traditional invasive temperature sensors, namely thermocouples and thermistors, to non-invasive nano thermometers. Among them, the fluorescence nano thermometer has received wide attention due to its high temporal and spatial resolution and the integrated function of imaging and temperature sensing, and has been successfully applied to the aspects of bio-imaging, temperature sensing, environmental monitoring or food safety.
At present, commonly used fluorescent nano materials include semiconductor quantum dots, metal nanoclusters, carbon nano materials, rare earth doped nano particles and the like. Research has demonstrated the ability of AuNCs to detect changes in cell temperature. However, in complex environments, these single-emission fluorescence nanothermometers have poor stability and cannot accurately reflect changes in local temperature and temperature gradients in nano-or sub-nano regions. This inherent limitation has prompted the development of new fluorescent nanothermometers. Compared with the single-emission fluorescence nanometer thermometer, the sensitivity and the stability of the double-emission fluorescence nanometer thermometer are greatly improved due to the existence of the self-reference substance and the improvement of the material performance.
Carbon Dots (CDs) are a class of fluorescent nanomaterials without heavy metals, and have been widely used in many fields, especially in biological imaging and sensors, due to their inherent advantages, such as low cost, good biocompatibility, good stability, etc. To date, it has been reported that CDs-based fluorescence nanothermometers (single or dual emission) have been used for accurate temperature detection. For example, the CDs/Au NCs dual-emission fluorescent nano hybrid material can realize accurate measurement of physiological temperature in the range of 25-45 ℃. However, compatibility and interference between the two substances become the primary considerations for binary heterogeneous nanocomposites (CDs/AuNCs and CDs/QDs). The emergence of the double-carbon-point nano material not only solves the problems, but also further reduces the toxicity and the preparation cost of the nano material.
At present, the technologies for preparing dual carbon dots (CDs/CDs) nano materials mainly include chemical bond crosslinking and template-based self-assembly. However, these processes are complex and uncontrollable, ultimately leading to a decrease in quantum efficiency. Therefore, there is a need for developing a new temperature sensing material with low toxicity, stability, low cost, and simple preparation process.
Disclosure of Invention
The invention aims to construct a blue light-emitting carbon dot (B-CDs) and red light-emitting carbon dot (O-CDs) composite double-fluorescent carbon-based nano probe by a self-assembly method induced by electrostatic interaction, and the probe has the characteristics of stable structure, environmental friendliness, simple preparation process and the like, and can be used for temperature detection in organisms.
In order to realize the purpose of the invention, the invention provides a preparation method of a dual-emission carbon-based nanoprobe for temperature sensing, which comprises the following specific steps:
dissolving the red and blue fluorescent carbon dots according to the mass ratio of (1-3) to 1 to prepare aqueous solution, stirring for 3-5h, removing unassembled carbon dots, collecting the solution, and drying to obtain solid, namely the dual-emission carbon-based nano probe.
Further, the dissolution process is performed at room temperature.
Further, the drying mode is one of freeze drying, vacuum drying, reduced pressure boiling drying or normal pressure drying.
Furthermore, the drying mode is preferably freeze drying, and the drying temperature is-30 to-50 ℃.
Further, the drying time is 24-72 h.
Further, the mode for removing the unassembled carbon spots is dialysis, and the selected dialysis membrane is a 3500Da dialysis membrane.
Furthermore, the particle size distribution range of the obtained dual-emission carbon-based nano probe is 20-25 nm.
The preparation method of the red fluorescent carbon dot comprises the following steps:
preparing a carbon source solution, adding a nitrogen-containing compound, dissolving the mixture of the carbon source solution and the nitrogen-containing compound in an organic solvent, transferring the prepared solution to a reaction kettle, heating at the constant temperature of 160-200 ℃ for 6-10h, adding an alkaline solution, stirring, separating and removing supernatant, collecting precipitate, dissolving the precipitate in an acidic solution, stirring, separating and collecting precipitate, dissolving the precipitate in water, separating twice to remove precipitate, collecting supernatant, and drying to obtain the red fluorescent carbon dot.
Further, in the preparation process of the red fluorescent carbon dot, the molar ratio of the carbon source to the nitrogen-containing compound is 1: (5-10).
Further, in the preparation process of the red fluorescent carbon dot, the solvent is one or more than two of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or methyl formamide.
Further, in the preparation process of the red fluorescent carbon dot, the alkaline solution is one of a sodium hydroxide solution or a potassium hydroxide solution, the concentration is 50mg/m L, and the volume is 40m L.
Further, in the preparation process of the red fluorescent carbon dot, the acid solution is one of a dilute hydrochloric acid solution, a dilute nitric acid solution or a dilute sulfuric acid solution, the concentration is 5%, and the volume is 50m L.
Further, in the preparation process of the red fluorescent carbon dots, the separation mode is centrifugal separation, wherein the centrifugal speed is 16000r/min, and the centrifugal time is 10 min.
Further, in the preparation process of the red fluorescent carbon dots, the drying mode is one of freeze drying, vacuum sealing drying or normal pressure drying.
Further, in the preparation process of the red fluorescent carbon dots, the carbon source is one or more than two of citric acid, p-phenylenediamine, terephthalic acid, o-phenylenediamine, m-phenylenediamine, melamine, glucose, fructose, sucrose, lactic acid, polyvinyl alcohol, polyacrylic acid, polyethyleneimine, chitosan, cellulose, lemon or shaddock peel.
Further, in the preparation process of the red fluorescent carbon dot, the carbon source is preferably citric acid, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine or melamine.
Further, in the preparation process of the red fluorescent carbon dot, the concentration of the carbon source solution is 0.05-0.1g/m L.
Further, in the preparation process of the red fluorescent carbon dot, the nitrogen-containing compound is one or more than two of urea, thiourea, ethylenediamine, semicarbazide, triethylene tetramine, diphenylamino urea, tryptophan, glutathione, histidine, arginine, glycine or cysteine.
Further, in the preparation process of the red fluorescent carbon dot, the nitrogen-containing compound is preferably urea, thiourea, ethylenediamine or semicarbazide.
Furthermore, the particle size distribution range of the red fluorescent carbon dots is 3-5nm, the maximum emission wavelength is 580-590nm, the temperature response range is-20-120 ℃, and the temperature sensitivity is 0.87%/DEG C.
The preparation method of the blue fluorescent carbon dot comprises the following steps:
preparing a carbon source solution, adding a nitrogen-containing compound, transferring the mixture of the carbon source solution and the nitrogen-containing compound into a reaction kettle, and heating for 6-8h at constant temperature of 120-160 ℃; and taking out the product, filtering to remove large-particle precipitates, collecting supernatant, dialyzing for 72 hours by using a dialysis membrane, collecting dialyzed solution, and removing water solvent by rotary evaporation to obtain solid powder, namely blue fluorescent carbon dots (B-CDs).
Further, in the preparation process of the blue fluorescent carbon dots, a 0.22 μm filter membrane is used in the filtration mode, and the dialysis membrane is a 3500Da dialysis membrane.
Further, in the preparation process of the blue fluorescent carbon dot, the molar ratio of the carbon source to the nitrogen-containing compound is 1: (1-3).
Further, in the preparation process of the blue fluorescent carbon dot, the carbon source is one or more than two of citric acid, m-phenylenediamine, melamine, glucose, fructose, sucrose, lactic acid, polyvinyl alcohol, polyacrylic acid, polyethyleneimine, chitosan, cellulose, lemon or shaddock peel.
Further, in the preparation process of the blue fluorescent carbon dot, the carbon source is preferably citric acid, glucose, fructose or melamine.
Further, in the preparation process of the blue fluorescent carbon dot, the nitrogen-containing compound is one or more than two of urea, thiourea, ethylenediamine, semicarbazide, triethylene tetramine, diphenylamino urea, tryptophan, glutathione, histidine, arginine, glycine or cysteine.
Further, in the preparation process of the blue fluorescent carbon dot, the nitrogen-containing compound is preferably urea, thiourea, ethylenediamine or semicarbazide.
Further, in the preparation process of the blue fluorescent carbon dot, the concentration of the carbon source solution is 0.05-0.1g/m L.
The particle size distribution range of the blue fluorescent carbon dots (B-CDs) obtained by the steps is 1-3nm, and the maximum emission wavelength is 400-470 nm.
The double-emitting carbon-based nano probe prepared by the preparation method for the double-emitting carbon-based nano probe for temperature sensing is characterized in that the surface of a blue carbon dot is negatively charged, the surface of a red carbon dot is positively charged, and the two carbon dots can be spontaneously assembled to form double-carbon-dot nano particles through simple electrostatic interaction.
Further, the product has dual-emission properties, and emission peaks are respectively positioned at 440nm and 590 nm.
Further, the temperature sensitivity of the above product was 0.93%/deg.C.
Furthermore, the temperature response range of the product is-20-120 ℃.
The invention has the following beneficial technical effects:
1) the preparation method is simple and low in cost;
2) the particle sizes of the blue fluorescent carbon dots and the red fluorescent carbon dots are smaller and are in the range of 1-5 nm; the particle size distribution range of the dual-emission carbon-based nano probe is 20-25nm, the particle size of the product is uniform, and the product has good dispersibility;
3) the surface of the blue fluorescent carbon dot contains a large amount of hydroxyl and carboxyl, and is negatively charged, and the surface of the red fluorescent carbon dot contains a large amount of amino and is positively charged, so that the blue fluorescent carbon dot and the red fluorescent carbon dot can form stably existing dual-emission carbon-based nanoparticles in a simple electrostatic interaction induced self-assembly mode without adding a template or a carrier material;
4) the fluorescent material has strong dual-fluorescence emission, and the fluorescence quantum efficiency is 15.4%;
5) the double-emitting carbon-based nano temperature sensor can be applied to temperature detection, can be switched between a low temperature (15 ℃) and a high temperature (85 ℃) and has high repeatability (basically unchanged after being repeatedly used for 8 times) and sensitivity (0.93%/DEG C);
6) the product is used as a temperature sensing material, has a wide response range, obviously improves the sensitivity due to the introduction of a self-reference substance, has high repeated operability, and can be applied to non-contact detection of solution and intracellular temperature change.
Drawings
FIG. 1 is a TEM image of a red fluorescent carbon dot of example 1;
FIG. 2 is a TEM image of a blue fluorescent carbon dot of example 1;
FIG. 3 is a TEM image of the dual-emission carbon-based fluorescent nanomaterial of example 1;
FIG. 4 is a fluorescence spectrum of the product of example 1;
FIG. 5 is a graph showing fluorescence intensity of the temperature sensor of example 1 during temperature increase from 15 ℃ to 85 ℃;
FIG. 6 is a graph showing the reproducibility of the temperature sensor of example 1;
FIG. 7 is a graph showing fluorescence intensity during temperature increase from 15 ℃ to 85 ℃ of the temperature sensor of comparative example 1;
fig. 8 is a reproducibility test chart of the temperature sensor of comparative example 1.
Detailed Description
The invention is further described with reference to specific examples.
Transmission electron microscopy: tecnai GI F20U-TWIN transmission electron microscope (200KV accelerating voltage).
Fluorescence spectrometer, Horiba JobinYvon Fluoromax 4C-L (France) spectrophotometer
And (3) repeatability test: and controlling the temperature to be 15 ℃ by using an additional temperature sensing controller, measuring the fluorescence intensity of the double peaks of the nano probe, increasing the temperature to 85 ℃, measuring the fluorescence intensity of the double peaks of the nano probe, reducing the temperature to 15 ℃, measuring the fluorescence intensity, circularly repeating the temperature increase and reduction for 8 times, and processing the obtained data to obtain a repeatability test spectrogram.
Measuring an emission wavelength; measured using a fluorescence spectrometer.
And (3) particle size analysis: the analysis and statistics of the transmission electron microscope image can be obtained.
Example 1
Weighing 1g of citric acid and 2g of urea, dissolving in 20m of L N, N-Dimethylformamide (DMF), transferring the prepared solution into a reaction kettle, heating at a constant temperature of 200 ℃ for 8h to obtain a black viscous solution, adding 40m of L sodium hydroxide solution (50mg/m L) into the mixed solution, removing supernatant through centrifugation (16000r/min, 10min), collecting precipitate, dissolving in dilute hydrochloric acid solution (50m L, 5%), stirring for 10min, removing supernatant through centrifugation (16000r/min, 10min), collecting precipitate, dissolving in deionized water, centrifuging (16000r/min, 10min) twice to remove precipitate, collecting supernatant, freeze-drying at-35 ℃ for 72h to obtain red fluorescent carbon dots, re-dispersing the product in water, and obtaining a transmission electron microscope image of the product, wherein the particle size of the product is uniform, 3-5nm and has good dispersibility.
Weighing 1g of citric acid and 0.8 g of urea, dissolving in 10m L deionized water, transferring the solution into a reaction kettle, heating at a constant temperature of 120 ℃ for 8 hours to obtain a dark blue transparent solution, filtering the mixed solution by using a 0.22 mu m filter membrane to remove large particulate matters, dialyzing the filtered solution by using a 3500Da dialysis membrane, collecting dialysate, removing an aqueous solvent by rotary evaporation to obtain a product, and redispersing the product in water, wherein the transmission electron microscope picture of the product is shown in figure 2, the particle size of the product is uniform and is 1-3nm, and the product has good dispersibility.
Respectively weighing 10mg of red fluorescent carbon dot powder and 5mg of blue fluorescent carbon dot powder, dissolving the red fluorescent carbon dot powder and the blue fluorescent carbon dot powder in 5m L deionized water, stirring the solution at room temperature for 3 hours to ensure that two carbon dots are fully contacted, finally dialyzing the solution by using a 3500Da dialysis membrane, collecting the solution in a dialysis bag, freeze-drying the solution into powder to obtain a product, re-dispersing the product in an aqueous solution to form a temperature sensor with the concentration of 10mg/m L, and using a transmission electron microscope to show that the particle size of the product is uniform and is 15-20 nm.
The fluorescence property of the double-emission carbon-based material is tested by a fluorescence spectrometer, the result is shown in figure 4, the maximum emission wavelengths of the double-emission carbon-based material are respectively positioned at 590nm and 440nm and respectively correspond to the maximum emission wavelengths of a red fluorescence carbon dot and a blue fluorescence carbon dot, a 3m L aqueous solution of the double-emission carbon-based fluorescence nano material is taken to form a temperature sensor, a fluorescence spectrum instrument is used for testing the fluorescence intensity change of the double-emission carbon-based nano probe in the temperature rising process from 15 ℃ to 85 ℃, the sensitivity of the temperature is tested, the result is shown in figure 5, the average temperature change rate is-0.93%/° C, figure 6 is used for testing the stability of the temperature sensor, the product is repeatedly tested at 15 ℃ and 85 ℃, and the result shows that the temperature sensor can be switched between low temperature and high temperature, the corresponding fluorescence intensity at each temperature is basically kept unchanged, and the temperature can be repeatedly used for 8 times.
Example 2
Weighing 0.6g of p-phenylenediamine and 2g of urea, dissolving in 20m of L N, N-Dimethylformamide (DMF), transferring the prepared solution into a reaction kettle, heating at the constant temperature of 200 ℃ for 8 hours to obtain a black viscous solution, adding 40m of L potassium hydroxide solution (50mg/m L) into the mixed solution, removing supernatant through centrifugation (16000r/min and 10min), collecting precipitate, dissolving in a dilute nitric acid solution (50m L and 5%), stirring for 10 minutes, removing supernatant through centrifugation (16000r/min and 10min), collecting precipitate, dissolving in deionized water, centrifuging (16000r/min and 10min) twice to remove precipitate, collecting supernatant, and freeze-drying at-50 ℃ for 45 hours to obtain the red fluorescent carbon dot.
Weighing 1g of glucose and 0.5g of urea, dissolving in 10m L deionized water, transferring the solution into a reaction kettle, heating at the constant temperature of 120 ℃ for 8 hours to obtain a blue transparent solution, filtering the mixed solution by using a 0.22 mu m filter membrane to remove large particulate matters, dialyzing the filtered solution by using a 3500Da dialysis membrane, collecting dialysate, and removing a water solvent by rotary evaporation to obtain a product.
Weighing 6mg of red luminescent carbon dot powder and 2mg of blue luminescent carbon dot powder respectively, dissolving in 5m L deionized water, stirring the solution at room temperature for 3 hours so that the two carbon dots are fully contacted, finally dialyzing the solution by using a 3500Da dialysis membrane, collecting the solution in a dialysis bag, freeze-drying the solution into powder, namely obtaining a product, and re-dispersing the product in an aqueous solution to form the temperature sensor with the concentration of 10mg/m L.
Example 3
Weighing 0.5g of o-phenylenediamine and 2g of ethylenediamine, dissolving in 20m L of dimethyl sulfoxide (DMSO), transferring the prepared solution into a reaction kettle, heating at the constant temperature of 200 ℃ for 8 hours to obtain a black viscous solution, adding 40m L of sodium hydroxide solution (50mg/m L) into the mixed solution, removing supernatant through centrifugation (16000r/min, 10min), collecting precipitate, dissolving in dilute hydrochloric acid solution (50m L, 5%), stirring for 10min, removing supernatant through centrifugation (16000r/min, 10min), collecting precipitate, dissolving in deionized water, centrifuging (16000r/min, 10min) twice to remove precipitate, collecting supernatant, and performing vacuum drying to obtain the red fluorescent carbon dot.
Weighing 1g of fructose and 0.5g of urea, dissolving in 10m L deionized water, transferring the solution into a reaction kettle, heating at the constant temperature of 120 ℃ for 8 hours to obtain a blue-green transparent solution, filtering the mixed solution by using a 0.22 mu m filter membrane to remove large particulate matters, dialyzing the filtered solution by using a 3500Da dialysis membrane, collecting dialysate, and removing a water solvent by rotary evaporation to obtain a product.
Respectively weighing 10mg of red luminous carbon dot powder and 5mg of blue luminous carbon dot powder, dissolving the red luminous carbon dot powder and the blue luminous carbon dot powder in 5m L deionized water, stirring the solution at room temperature for 3 hours so that the two carbon dots are fully contacted, finally dialyzing the solution by using a 3500Da dialysis membrane, collecting the solution in a dialysis bag, freeze-drying the solution into powder, namely obtaining a product, and re-dispersing the product in an aqueous solution to form the temperature sensor with the concentration of 10mg/m L.
Comparative example 1: properties of the product obtained in the absence of a self-reference substance
Weighing 0.6g of p-phenylenediamine and 2g of urea, dissolving in 20m of L N, N-Dimethylformamide (DMF), transferring the prepared solution into a reaction kettle, heating at the constant temperature of 200 ℃ for 8 hours to obtain a black viscous solution, adding 40m of L sodium hydroxide solution (50mg/m L) into the mixed solution, removing supernatant through centrifugation (16000r/min, 10min), collecting precipitate, dissolving in dilute hydrochloric acid solution (50m L, 5%), stirring for 10min, removing supernatant through centrifugation (16000r/min, 10min), collecting precipitate, dissolving in deionized water, centrifuging (16000r/min, 10min) twice to remove precipitate, collecting supernatant, and freeze-drying at-50 ℃ for 35 hours to obtain the red fluorescent carbon dot.
50mg of red fluorescent carbon dot powder is weighed and dissolved in 5m L deionized water, then the solution is stirred for 3 hours at room temperature to form a temperature sensor with the concentration of 10mg/m L, the transmission electron microscope of the temperature sensor is shown in figure 1, and the particle size of the product is uniform and is 3-5 nm.
The fluorescence property of the single-emission carbon-based material is tested by a fluorescence spectrometer, the result is shown in fig. 4, the maximum emission wavelength of the single-emission carbon-based material is 590nm, 3m L of aqueous solution of the double-emission carbon-based fluorescent nano material is used for forming a temperature sensor, a fluorescence spectrometer is used for testing the change of the fluorescence intensity of the double-emission carbon-based nano probe in the temperature rising process from 15 ℃ to 85 ℃, the sensitivity of the temperature is tested, the result is shown in fig. 7, the average temperature change rate is-0.87%/° c, fig. 8 is used for testing the stability of the temperature sensor, the product is repeatedly tested at 15 ℃ and 85 ℃, and the result shows that compared with the temperature sensor in example 1, the stability of the temperature sensor is influenced by low/high temperature switching, the corresponding fluorescence intensities at different temperatures are changed, and the repeatability is poor.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (4)

1. A method for preparing a dual emission carbon-based nanoprobe for temperature sensing, the method comprising the steps of: dissolving the red and blue fluorescent carbon dots according to the mass ratio of (1-3) to (1) to prepare an aqueous solution, stirring for 3-5h, removing unassembled carbon dots, collecting the solution, and drying to obtain a solid, namely the dual-emission carbon-based nano probe, wherein the dual-emission carbon-based nano probe is obtained by self-assembling the red and blue fluorescent carbon dots through electrostatic interaction induction; wherein the content of the first and second substances,
the preparation method of the red fluorescent carbon dots comprises the following steps: preparing a carbon source solution, adding a nitrogen-containing compound, dissolving the mixture of the carbon source solution and the nitrogen-containing compound in an organic solvent, transferring the prepared solution into a reaction kettle, heating at the constant temperature of 160-200 ℃ for 6-10h, adding an alkaline solution, stirring, separating and removing a supernatant, collecting a precipitate, dissolving the precipitate in an acidic solution, stirring, separating and collecting the precipitate, dissolving the precipitate in water, separating twice to remove the precipitate, collecting the supernatant, and drying to obtain a red fluorescent carbon dot;
the preparation method of the blue fluorescent carbon dot comprises the following steps: preparing a carbon source solution, adding a nitrogen-containing compound, transferring the mixture of the carbon source solution and the nitrogen-containing compound into a reaction kettle, and heating for 6-8h at constant temperature of 120-160 ℃; taking out the product, filtering to remove large-particle precipitates, collecting supernatant, dialyzing for 72 hours by using a dialysis membrane, collecting dialyzed solution, and removing water solvent by rotary evaporation to obtain solid powder, namely the blue fluorescent carbon dots;
the carbon source used in the preparation process of the red fluorescent carbon dots is citric acid, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine or melamine; the nitrogen-containing compound is urea, thiourea, ethylenediamine or semicarbazide; the organic solvent is one or more than two of dimethylformamide, dimethyl sulfoxide or methyl formamide; the alkaline solution is one of a sodium hydroxide solution or a potassium hydroxide solution; the acid solution is one of a dilute hydrochloric acid solution, a dilute nitric acid solution or a dilute sulfuric acid solution;
the carbon source used in the preparation process of the blue fluorescent carbon dots is citric acid, glucose, fructose or melamine; the nitrogen-containing compound is urea, thiourea, ethylenediamine or semicarbazide;
the molar ratio of the carbon source to the nitrogen-containing compound in the red fluorescent carbon dot preparation process is 1 (5-10), the molar ratio of the carbon source to the nitrogen-containing compound in the blue fluorescent carbon dot preparation process is 1 (1-3), and the concentration of the carbon source in the two carbon dot preparation processes is 0.05-0.1g/m L.
2. The method of claim 1, wherein the removing of the unassembled carbon spots is dialysis, and the drying is one of freeze drying, vacuum drying, boiling drying under reduced pressure, or drying under atmospheric pressure.
3. The dual emission carbon-based nanoprobe prepared by the method for preparing the dual emission carbon-based nanoprobe for temperature sensing according to claim 1 or 2.
4. Use of the dual emission carbon-based nanoprobe of claim 3 for temperature sensing.
CN201810800874.3A 2018-07-20 2018-07-20 Preparation method of dual-emission carbon-based nanoprobe and product thereof Active CN108913132B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810800874.3A CN108913132B (en) 2018-07-20 2018-07-20 Preparation method of dual-emission carbon-based nanoprobe and product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810800874.3A CN108913132B (en) 2018-07-20 2018-07-20 Preparation method of dual-emission carbon-based nanoprobe and product thereof

Publications (2)

Publication Number Publication Date
CN108913132A CN108913132A (en) 2018-11-30
CN108913132B true CN108913132B (en) 2020-08-04

Family

ID=64415337

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810800874.3A Active CN108913132B (en) 2018-07-20 2018-07-20 Preparation method of dual-emission carbon-based nanoprobe and product thereof

Country Status (1)

Country Link
CN (1) CN108913132B (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109439321B (en) * 2018-12-04 2022-03-15 广东省计量科学研究院(华南国家计量测试中心) Carbon quantum dot using silkworm excrement as raw material, preparation method and application thereof
CN109490269B (en) * 2018-12-07 2020-07-24 吉林大学 Preparation method of dual-emission colorimetric fluorescent nano-microsphere and application of dual-emission colorimetric fluorescent nano-microsphere in bacterial detection
CN109777407A (en) * 2019-02-18 2019-05-21 东北林业大学 A kind of double transmitting carbon quantum dots and its organic compound film, preparation method and application with pH sensibility
CN110316718B (en) * 2019-06-28 2021-04-06 重庆文理学院 Double-emission red fluorescent carbon quantum dot and preparation method thereof
CN110373184A (en) * 2019-06-28 2019-10-25 湖北大学 A kind of synthetic method of high yield red fluorescence carbon quantum dot material
CN110499153B (en) * 2019-07-15 2022-08-19 郑州大学 Mitochondria-positioned carbon dot, preparation method and application of mitochondria-positioned carbon dot in silver ion detection
WO2021054462A1 (en) * 2019-09-20 2021-03-25 国立大学法人金沢大学 Method for producing luminescent nanocarbons
CN111232952B (en) * 2020-01-13 2022-10-14 辽宁大学 Preparation method of carbon nanodots and application of carbon nanodots as acid-base indicator
CN111440343B (en) * 2020-06-03 2022-10-04 齐鲁工业大学 Preparation method of fluorescence-enhanced copper cluster and nano-cellulose composite film
CN111944522B (en) * 2020-07-28 2022-11-08 盐城工学院 Preparation method and application of single-component carbon-based solid white luminescent nano material
CN112697757B (en) * 2020-12-10 2024-05-03 浙江理工大学 Preparation method of fluorescence sensor for instant detection of Cr (VI) and product thereof
CN114958357B (en) * 2021-02-20 2023-04-28 重庆医科大学 Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof
CN113004577B (en) * 2021-03-09 2022-07-12 太原理工大学 Shape memory composite hydrogel and preparation method and application thereof
CN113563876B (en) 2021-07-06 2022-09-27 江南大学 Enhanced yellow light carbon dot and preparation method and application thereof
CN113388389B (en) * 2021-07-23 2022-03-29 齐鲁工业大学 Fluorescent carbon nanodot, preparation method and application thereof in cell nucleus targeted imaging
CN113583657B (en) * 2021-09-01 2022-07-19 郑州大学 Cell nucleus targeting carbon dot, preparation and application
CN114229827A (en) * 2021-10-25 2022-03-25 广东石油化工学院 Carbon nanodot, dual-mode probe prepared based on carbon nanodot and application of dual-mode probe
CN114015440B (en) * 2021-12-10 2023-05-09 兰州大学 Fluorescent carbon dot for temperature sensing and preparation method thereof
CN114570350B (en) * 2022-03-07 2022-09-06 华北电力大学 Carbon dot/silicon dioxide composite material, preparation method and application thereof
CN114591737B (en) * 2022-03-16 2023-12-01 北京化工大学 Multicolor fluorescent carbon dot, preparation method and application thereof
CN115368476B (en) * 2022-08-11 2023-12-15 陕西科技大学 Method for modifying cellulose based on microwave carbon quantum dots
CN116200191A (en) * 2022-08-31 2023-06-02 新疆大学 Preparation method and application of multicolor carbon point oilfield tracer
CN116515480A (en) * 2023-04-06 2023-08-01 东南大学 Green synthesis method of lemon peel-based red fluorescent carbon quantum dots

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004051207A1 (en) * 2002-12-04 2004-06-17 National Institute For Materials Science Temperature-sensing element and method of manufacturing the element, and nano-thermometer
CN106566536A (en) * 2016-10-27 2017-04-19 华南农业大学 Red light-blue light dual-emission composited optical transfer material, and preparation method and application of red light-blue light dual-emission composited optical transfer material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105419794B (en) * 2015-12-30 2017-12-15 中国科学院长春光学精密机械与物理研究所 A kind of orange light transmitting carbon nano dot and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004051207A1 (en) * 2002-12-04 2004-06-17 National Institute For Materials Science Temperature-sensing element and method of manufacturing the element, and nano-thermometer
CN106566536A (en) * 2016-10-27 2017-04-19 华南农业大学 Red light-blue light dual-emission composited optical transfer material, and preparation method and application of red light-blue light dual-emission composited optical transfer material

Also Published As

Publication number Publication date
CN108913132A (en) 2018-11-30

Similar Documents

Publication Publication Date Title
CN108913132B (en) Preparation method of dual-emission carbon-based nanoprobe and product thereof
Gong et al. A review of fluorescent signal-based lateral flow immunochromatographic strips
Gao et al. Carbon dots with red emission as a fluorescent and colorimeteric dual-readout probe for the detection of chromium (vi) and cysteine and its logic gate operation
Qiao et al. Smart choice of carbon dots as a dual-mode onsite nanoplatform for the trace level detection of Cr2O72
Ma et al. Dye-conjugated upconversion nanoparticles for ratiometric imaging of intracellular pH values
CN106987245B (en) Manganese dioxide nanosheet modified up-conversion luminescent nanomaterial, preparation method thereof, detection method of hydrogen peroxide or choline and application thereof
CN103788944A (en) Simple green synthesis method of nitrogen-doped carbon quantum dots
Lv et al. A new visual immunoassay for prostate-specific antigen using near-infrared excited Cu x S nanocrystals and imaging on a smartphone
CN108456518B (en) Rare earth nano particle with strong red fluorescence, preparation method thereof and application thereof in cell imaging
Wei et al. Dual functional carbonaceous nanodots exist in a cup of tea
CN108929672A (en) It is a kind of using shrimp shell as carbon quantum dot of carbon source and preparation method thereof and detection ascorbic acid in application
CN110157412B (en) Long-life room temperature phosphorescent material and preparation method thereof
Duan et al. CdTe quantum dots@ luminol as signal amplification system for chrysoidine with chemiluminescence-chitosan/graphene oxide-magnetite-molecularly imprinting sensor
Hu et al. A rapid and sensitive turn-on fluorescent probe for ascorbic acid detection based on carbon dots–MnO 2 nanocomposites
Ma et al. A label-free electrochemiluminescence immunosensor based on EuPO4 nanowire for the ultrasensitive detection of Prostate specific antigen
Wang et al. Surface state-controlled C-dot/C-dot based dual-emission fluorescent nanothermometers for intra-cellular thermometry
Ooyama et al. Aggregation-induced emission (AIE) characteristic of water-soluble tetraphenylethene (TPE) bearing four sulfonate salts
Wang et al. Carbon quantum dots prepared by pyrolysis: investigation of the luminescence mechanism and application as fluorescent probes
CN106829920A (en) A kind of green fluorescence carbon quantum dot material and preparation method thereof
Tian et al. Novel ratiometric probe based on the use of rare earth-carbon dots nanocomposite for the visual determination of doxycycline
Duan et al. Dual-emitting zein-protected gold nanoclusters for ratiometric fluorescence detection of Hg 2+/Ag+ ions in both aqueous solution and self-assembled protein film
Wei et al. A single component self-assembled thermally activated delayed fluorescence nanoprobe
CN108872162B (en) Analysis method for detecting carcinoembryonic antigen photoelectrochemical aptamer based on heterojunction composite material
CN114540022B (en) Preparation of cellulose-based carbon quantum dot and application of cellulose-based carbon quantum dot in uric acid detection
CN114609107A (en) Fluorescent probe based on red light carbon quantum dots and application of fluorescent probe in detection of ethanol concentration in ethanol-water system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant