CN115818621A - Biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristic and preparation method and application thereof - Google Patents

Biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristic and preparation method and application thereof Download PDF

Info

Publication number
CN115818621A
CN115818621A CN202211498252.2A CN202211498252A CN115818621A CN 115818621 A CN115818621 A CN 115818621A CN 202211498252 A CN202211498252 A CN 202211498252A CN 115818621 A CN115818621 A CN 115818621A
Authority
CN
China
Prior art keywords
biomass
infrared
boron
carbon nano
nitrogen
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.)
Granted
Application number
CN202211498252.2A
Other languages
Chinese (zh)
Other versions
CN115818621B (en
Inventor
康伟伟
张瑞平
王宇航
郑子良
代蓉
吴疏桐
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.)
Shanxi Medical University
Original Assignee
Shanxi Medical 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 Shanxi Medical University filed Critical Shanxi Medical University
Priority to CN202211498252.2A priority Critical patent/CN115818621B/en
Publication of CN115818621A publication Critical patent/CN115818621A/en
Application granted granted Critical
Publication of CN115818621B publication Critical patent/CN115818621B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Luminescent Compositions (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to a biomass-derived carbon nano particle with near-infrared two-region light emission characteristics and a preparation method and application thereof, belonging to the technical field of carbon nano materials, wherein a nitrogen source, a boron source and a biomass carbon source are subjected to dehydration carbonization reaction in a polar solution to prepare boron/nitrogen co-doped carbon nano particles; and then, coating the carbon nano particles by using a film coating material to enhance the water solubility of the carbon nano particles. The prepared carbon nano particles can be excited under laser with the wavelength of 808nm, show obvious NIR-II emission from 900 to 1200nm, and have efficient photo-thermal conversion characteristics; the carbon nano-particles have good biocompatibility and can be applied to the technical fields of near-infrared two-region fluorescence biological imaging, cancer photo-thermal treatment and the like; meanwhile, the preparation method is simple, has lower process requirements and can realize quantitative production.

Description

Biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of carbon nano materials, and particularly relates to a biomass-derived carbon nano particle with near-infrared two-region light emission characteristics, and a preparation method and application thereof.
Background
Fluorescence imaging is a non-invasive in vivo imaging technique that provides rapid feedback in real time, high sensitivity and harmless radiation, and thus has great advantages in visualizing the anatomy and function of organs. In recent years, the fluorescence imaging technology of the near infrared two-region (NIR-II, 1000-1700 nm) becomes a popular imaging technology for basic research and clinical application, and has strong application potential in the biomedical field. Compared to visible/near-infrared-first (NIR-I) based bioimaging, NIR-II fluorescence imaging provides high signal-to-noise ratio and high spatial and temporal resolution for deep tissue imaging due to its moderate tissue absorption and relatively low tissue scattering, minimized autofluorescence, and negligible phototoxicity to living cells, and enables direct visualization and real-time monitoring of deep biological structures and processes with clarity.
In recent years, fluorescent carbon nanomaterials emitting in the near infrared region have become promising candidates for biomedical assays and therapies due to minimal damage to biological matrices, large tissue penetration depths and minimal autofluorescence background of biological samples. However, most of the recently reported fluorescent Carbon Nanoparticles (CNPs) triggered by Ultraviolet (UV)/blue light exhibit NIR-I emission shorter than 820nm, seriously hindering their application in vivo. There is still a lack of efficient methods for preparing CNPs emitting NIR-II. Furthermore, in the only reports on CNPs emitting NIR-I, the preparation methods of these CNPs are complicated and the biocompatibility is not ideal. The selection of carbon sources is very important in the preparation of CNPs, and biomass carbon sources from nature have the advantages of low price, no toxicity, wide application and the like. Therefore, it is very important to develop NIR-triggered CNPs based on biomass carbon sources, having a simple preparation method, low process requirements, quantitative production, good biocompatibility, and NIR-II emission.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide biomass-derived carbon nanoparticles with near-infrared two-region light emission characteristics and a preparation method and application thereof.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a biomass-derived carbon nanoparticle having near-infrared two-region light emission characteristics, wherein: the biomass-derived carbon nanoparticles are composed of boron/nitrogen co-doped carbon nanoparticles and a coating material wrapped on the surface, the coating material is one or more of hyaluronic acid, bovine serum albumin, polyvinyl alcohol or polyvinylpyrrolidone, the crystal diameter of the biomass-derived carbon nanoparticles is 5-200nm, the biomass-derived carbon nanoparticles are excited under laser with the wavelength of 808nm, the biomass-derived carbon nanoparticles are emitted in an obvious near-infrared two-region with the wavelength of 900nm-1200 nm, and the peak center of a wave peak is 928nm.
Further, the nitrogen source is one or more of boron nitride, borazene, 3-aminobenzeneboronic acid, urea, melamine or ammonium citrate; the boron source is one or more of boron nitride, borazene, 3-aminophenylboronic acid, granular borax or anhydrous sodium tetraborate; the biomass carbon source is one or more of grapes, pears, watermelons, kiwi fruits, apples or strawberries.
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, squeezing a biomass carbon source to obtain juice, performing centrifugal separation on the obtained solution at the rotating speed of 3000 to 12000r/min, taking supernate, and discarding precipitates;
s2, dissolving a nitrogen source and a boron source into absolute ethyl alcohol together, wherein the mass volume ratio of the nitrogen source to the boron source to the absolute ethyl alcohol is (100 mg-1000 mg): (100 mg-1000 mg): 1mL, uniformly dispersing by using ultrasonic, wherein the frequency of ultrasonic dispersion is 50KHz, and the time of ultrasonic dispersion is 30-60min, then adding the obtained product into the supernatant obtained in the step S1, and stirring at the temperature of 28 ℃ for 5-30min to obtain a mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 3 to 10 hours at the temperature of 100 to 200 ℃, and then centrifugally separating and freeze-drying the obtained solution at the rotating speed of 5000 to 12000r/min to prepare boron/nitrogen co-doped carbon nano particle powder;
s4, adding the film coating material into deionized water, wherein the mass-volume ratio of the film coating material to the deionized water is (20 mg-100 mg): 1mL, stirring at high speed after ultrasonic dispersion until the solution is in a transparent state, wherein the ultrasonic dispersion frequency is 50KHz, the ultrasonic dispersion time is 5min, the stirring temperature is 28 ℃, and the stirring time is 5min, so as to prepare a film-coating material solution;
s5, preparing the boron/nitrogen co-doped carbon nano particle powder prepared in the step S3 into a uniformly dispersed boron/nitrogen co-doped carbon nano particle aqueous solution; then slowly dripping the boron/nitrogen co-doped carbon nanoparticle aqueous solution into the coating material solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 5 to 15h; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 5000 to 12000r/min, and thus the biomass-derived carbon nanoparticles with the near-infrared two-region light emission characteristic are prepared.
A biomass-derived carbon nanoparticle with near-infrared two-region light emission characteristics is applied to fluorescence imaging, photo-thermal therapy, infrared anti-counterfeiting or drug carriers.
Compared with the prior art, the invention has the beneficial effects that:
1. the biomass-derived carbon nano particles with the near-infrared two-region light emission characteristic are formed by dehydration carbonization reaction of a nitrogen source, a boron source and a biomass carbon source in a polar solution; the prepared biomass-derived carbon nanoparticles can be excited under laser with the wavelength of 808nm, and exhibit obvious NIR-II emission from 900 to 1200nm, and have efficient photo-thermal conversion characteristics;
2. the biomass-derived carbon nanoparticles have low toxicity and good biocompatibility;
3. the invention has low manufacturing cost and simple preparation method, and can be used for preparing biomass-derived carbon nanoparticles in large scale.
Drawings
FIG. 1 is a transmission electron micrograph (TME) of the CNPs synthesized in example 1;
FIG. 2 is a hydrated particle size histogram of the CNPs synthesized in example 1;
FIG. 3 is a Fourier Infrared (FTIR) absorption spectrum of the CNPs synthesized in example 1;
FIG. 4 is a NIR-II fluorescence spectrum and a fluorescence spectrum thereof of CNPs synthesized in example 1;
FIG. 5 is a visible-near infrared two-domain absorption spectrum of the CNPs synthesized in example 1;
FIG. 6 is a chart of Balb/c mouse NIR-II fluorescence in vivo imaging of CNPs synthesized in example 1;
fig. 7 is a graph showing photothermal properties of the CNPs synthesized in example 1.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
Example 1
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 35mL of watermelon juice into a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 4000r/min, taking supernate, and removing sediment;
s2, adding 1800mg of boron nitride into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring the mixture at the stirring temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 180 ℃, and then performing centrifugal separation and freeze drying on the obtained solution at the centrifugal separation rotating speed of 6000r/min to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of bovine serum albumin into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 50KHz, the dispersion time is 5min, and stirring the mixture for 5min at 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 6000r/min, and the bovine serum albumin coated carbon nano-particles with the near-infrared two-region light emission characteristic are prepared, and can be applied to fluorescence imaging, photothermal therapy, infrared anti-counterfeiting or drug carriers.
In this example 1, the prepared bovine serum albumin-coated carbon nanoparticles were dissolved in deionized water, and administered by rat tail intravenous injection to detect the imaging performance of the carbon nanoparticles.
Fig. 1 is a Transmission Electron Microscope (TEM) image of the CNPs synthesized in example 1. As can be seen, the synthesized CNPs have regular morphology, uniform particle size distribution and a diameter of about 38nm.
Fig. 2 is a hydrated particle size histogram of the CNPs synthesized in example 1. As can be seen from the graph, the synthesized CNPs have uniform particle size, and about 94.7% of the CNPs have a hydrated particle size of 190nm.
Fig. 3 is a fourier infrared (FTIR) absorption spectrum of the CNPs synthesized in example 1. As can be seen, 3218cm -1 、2912cm -1 、1498cm -1 、1074cm -1 And 751cm -1 Absorption peaks at the position of the compound are respectively belonging to N-H, C-H, B-O, C-O and B-O-B telescopic vibration, which proves that the B/N-CNPs are successfully synthesized, and the surface of the compound is rich in functional groups containing oxygen, nitrogen and boron.
FIG. 4 is a NIR-II fluorescence spectrum and a fluorescence spectrum thereof of CNPs synthesized in example 1. As can be seen, the synthesized CNPs exhibited significant NIR-II emission at wavelengths from 900 to 1200nm with a peak centered at 928nm.
Fig. 5 is a visible-near infrared two-domain absorption spectrum of the CNPs synthesized in example 1. As can be seen, two distinct absorption peaks are shown at about 230nm and 285nm in the UV region, and one at about 1153nm in the NIR-II region.
FIG. 6 is a chart of Balb/c mouse NIR-II fluorescence in vivo imaging of CNPs synthesized in example 1. As can be seen from the figure, after Balb/c mice are administrated in the tail vein, the fluorescence intensity of the lung and the liver of the mice is still kept at a higher level for 6h, and particularly, the lung targeting imaging capability is better.
Fig. 7 is a graph showing photothermal properties of the CNPs synthesized in example 1. As can be seen from the graph, solutions of CNPs of different concentrations all exhibited rapid temperature rise under irradiation of laser light having a wavelength of 1064nm, whereas the temperature of pure water remained almost unchanged.
Example 2
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 35mL of kiwi fruit juice in a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 4000r/min, taking supernate, and removing sediment;
s2, adding 1800mg of boron nitride into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring the mixture at the stirring temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 180 ℃, and then performing centrifugal separation and freeze drying on the obtained solution at the centrifugal separation rotating speed of 6000r/min to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of bovine serum albumin into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolving and dispersing, wherein the frequency is 50KHz, the dispersing time is 5min, and stirring the mixture for 5min at the temperature of 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying at the rotating speed of 6000r/min to prepare the bovine serum albumin coated carbon nano-particles with the near-infrared two-region light emission characteristic.
Example 3
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 35mL of grape juice in a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 4000r/min, taking supernate, and discarding precipitates;
s2, adding 1800mg of boron nitride into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring at the temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 180 ℃, and then carrying out centrifugal separation and freeze drying on the obtained solution, wherein the centrifugal separation rotating speed is 6000r/min, so as to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of bovine serum albumin into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 50KHz, the dispersion time is 5min, and stirring the mixture for 5min at 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 6000r/min, and the bovine serum albumin coated carbon nano-particles with the near-infrared two-region light emission characteristic are prepared.
Example 4
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 35mL of strawberry juice into a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 4000r/min, taking supernate, and discarding precipitates;
s2, adding 1800mg of boron nitride into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring the mixture at the stirring temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 180 ℃, and then performing centrifugal separation and freeze drying on the obtained solution at the centrifugal separation rotating speed of 6000r/min to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of bovine serum albumin into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 50KHz, the dispersion time is 5min, and stirring the mixture for 5min at 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 6000r/min, and the bovine serum albumin coated carbon nano-particles with the near-infrared two-region light emission characteristic are prepared.
Example 5
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 40mL of watermelon juice into a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 5000r/min, taking supernate, and discarding precipitates;
s2, adding 1800mg of boron nitride into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring at the temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 200 ℃, and then performing centrifugal separation and freeze drying on the obtained solution at the centrifugal separation rotating speed of 6000r/min to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of bovine serum albumin into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 50KHz, the dispersion time is 5min, and stirring the mixture for 5min at 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 6000r/min, and the bovine serum albumin coated carbon nano-particles with the near-infrared two-region light emission characteristic are prepared.
Example 6
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 35mL of watermelon juice into a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 4000r/min, taking supernate, and removing precipitates;
s2, adding 1800mg of boron nitride into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring the mixture at the stirring temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 180 ℃, and then performing centrifugal separation and freeze drying on the obtained solution at the centrifugal separation rotating speed of 6000r/min to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of bovine serum albumin into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 50KHz, the dispersion time is 5min, and stirring the mixture for 5min at 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of the B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 6000r/min, and the bovine serum albumin coated carbon nano-particles with the near-infrared two-region light emission characteristic are prepared.
Example 7
A preparation method of biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristics comprises the following steps:
s1, placing 35mL of watermelon juice into a centrifugal tube for centrifugal separation, wherein the centrifugal separation rotating speed is 4000r/min, taking supernate, and removing sediment;
s2, adding 1500mg of 3-aminophenylboronic acid into 5mL of absolute ethyl alcohol, placing the mixture into an ultrasonic dispersion instrument for ultrasonic dispersion uniformly, wherein the ultrasonic dispersion frequency is 50KHz, and the ultrasonic dispersion time is 50min, then adding the mixture into the supernatant prepared in the step S1, and stirring the mixture at the stirring temperature of 28 ℃ for 5min to prepare a milky mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 8 hours at the temperature of 180 ℃, and then performing centrifugal separation and freeze drying on the obtained solution at the centrifugal separation rotating speed of 6000r/min to prepare boron/nitrogen co-doped carbon nano particle powder (B/N-CNPs);
s4, adding 1200mg of hyaluronic acid into 200mL of deionized water, placing the mixture into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 50KHz, the dispersion time is 5min, and stirring the mixture for 5min at 28 ℃ until the solution is in a transparent state to prepare a bovine serum albumin aqueous solution;
s5, adding 400mg of B/N-CNPs powder prepared in the step S3 into 40mL of deionized water to prepare a B/N-CNPs aqueous solution which is uniformly dispersed and has the mass concentration of 10 mg/mL; then slowly dripping the B/N-CNPs aqueous solution into the bovine serum albumin aqueous solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 10 hours; and finally, washing, centrifugally separating, freezing and drying, wherein the rotational speed of centrifugal separation is 6000r/min, and the hyaluronic acid coated carbon nano-particles with the near-infrared two-region light emission characteristic are prepared.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (4)

1. A biomass-derived carbon nanoparticle having near-infrared two-region light emission characteristics, comprising: the biomass-derived carbon nanoparticles are composed of boron/nitrogen co-doped carbon nanoparticles and a coating material wrapped on the surface, the coating material is one or more of hyaluronic acid, bovine serum albumin, polyvinyl alcohol or polyvinylpyrrolidone, the crystal diameter of the biomass-derived carbon nanoparticles is 5-200nm, the biomass-derived carbon nanoparticles are excited under laser with the wavelength of 808nm, the biomass-derived carbon nanoparticles are emitted in an obvious near infrared two-region with the wavelength of 900nm-1200 nm, and the peak central wavelength of a peak is 928nm.
2. The biomass-derived carbon nanoparticle with near-infrared two-region light emission characteristics according to claim 1, wherein: the nitrogen source is one or more of boron nitride, borazene, 3-aminobenzeneboronic acid, urea, melamine or ammonium citrate; the boron source is one or more of boron nitride, borazene, 3-aminophenylboronic acid, granular borax or anhydrous sodium tetraborate; the biomass carbon source is one or more of grapes, pears, watermelons, kiwi fruits, apples or strawberries.
3. A method for preparing biomass-derived carbon nanoparticles having near-infrared two-region light emission characteristics according to claim 1 or 2, comprising the steps of:
s1, squeezing a biomass carbon source to obtain juice, performing centrifugal separation on the obtained solution at the rotating speed of 3000 to 12000r/min, taking supernate, and discarding precipitates;
s2, dissolving the nitrogen source and the boron source into absolute ethyl alcohol together, wherein the mass-volume ratio of the nitrogen source to the boron source to the absolute ethyl alcohol is (100 mg-1000 mg): (100 mg-1000 mg): 1mL, uniformly dispersing by using ultrasonic, wherein the frequency of ultrasonic dispersion is 50KHz, and the time of ultrasonic dispersion is 30-60min, then adding the obtained product into the supernatant obtained in the step S1, and stirring at the temperature of 28 ℃ for 5-30min to obtain a mixed solution;
s3, transferring the mixed solution prepared in the step S2 into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 3 to 10 hours at the temperature of 100 to 200 ℃, and then centrifugally separating and freeze-drying the obtained solution at the rotating speed of 5000 to 12000r/min to prepare boron/nitrogen co-doped carbon nano particle powder;
s4, adding the film coating material into deionized water, wherein the mass-volume ratio of the film coating material to the deionized water is (20 mg-100 mg): 1mL, stirring at high speed after ultrasonic dispersion until the solution is in a transparent state, wherein the ultrasonic dispersion frequency is 50KHz, the ultrasonic dispersion time is 5min, the stirring temperature is 28 ℃, and the stirring time is 5min, so as to prepare a film-coating material solution;
s5, preparing the boron/nitrogen co-doped carbon nano particle powder prepared in the step S3 into a uniformly dispersed boron/nitrogen co-doped carbon nano particle aqueous solution; then slowly dripping the boron/nitrogen co-doped carbon nanoparticle aqueous solution into the coating material solution prepared in the step S4, and fully stirring at the stirring temperature of 28 ℃ for 5 to 15h; and finally, washing, centrifugally separating, and freeze-drying at the rotation speed of 5000 to 12000r/min to prepare the biomass-derived carbon nanoparticles with the near-infrared two-region light emission characteristic.
4. Use of biomass-derived carbon nanoparticles having near-infrared two-region light emission properties according to claim 1 or 2, wherein: the biomass-derived carbon nanoparticles are applied to fluorescence imaging, photothermal therapy, infrared anti-counterfeiting or drug carriers.
CN202211498252.2A 2022-11-28 2022-11-28 Biomass-derived carbon nano particle with near infrared two-region light emission characteristic and preparation method and application thereof Active CN115818621B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211498252.2A CN115818621B (en) 2022-11-28 2022-11-28 Biomass-derived carbon nano particle with near infrared two-region light emission characteristic and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211498252.2A CN115818621B (en) 2022-11-28 2022-11-28 Biomass-derived carbon nano particle with near infrared two-region light emission characteristic and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115818621A true CN115818621A (en) 2023-03-21
CN115818621B CN115818621B (en) 2024-04-05

Family

ID=85532017

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211498252.2A Active CN115818621B (en) 2022-11-28 2022-11-28 Biomass-derived carbon nano particle with near infrared two-region light emission characteristic and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115818621B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116836700A (en) * 2023-06-29 2023-10-03 辽宁大学 Preparation method of hyaluronic acid modified red light carbon dots HA-R-CDs and application of hyaluronic acid modified red light carbon dots HA-R-CDs in lung cancer cell targeted imaging

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408984A (en) * 2013-08-22 2013-11-27 广东普加福光电科技有限公司 Optical coating composition, fluorescent optical membrane and preparation method thereof
US20180201512A1 (en) * 2017-01-16 2018-07-19 Winsky Technology Hong Kong Limited Yolk-shell-structured material, anode material, anode, battery, and method of forming same
CN109385276A (en) * 2018-12-20 2019-02-26 南京大学 High-performance feux rouges carbon quantum dot material and preparation method thereof and bio-imaging application
WO2019153742A1 (en) * 2018-02-12 2019-08-15 有研稀土新材料股份有限公司 Near-infrared luminescent material and light-emitting device prepared using near-infrared luminescent material
CN110257050A (en) * 2019-05-13 2019-09-20 闽南师范大学 A kind of nitrogen sulphur codope carbon nano-particles and the application in the detection of 2,4,6- trinitrophenol
CN110484238A (en) * 2019-08-15 2019-11-22 五邑大学 A kind of polymeric PTC materials method promoting carbon dots stability
WO2020045466A1 (en) * 2018-08-31 2020-03-05 日産化学株式会社 Method for producing photoluminescent nanocarbon
CN111847424A (en) * 2020-06-24 2020-10-30 华南师范大学 Red light carbon quantum dot with narrow spectrum emission and hydrothermal preparation method and application thereof
JP2021017411A (en) * 2019-07-19 2021-02-15 国立研究開発法人産業技術総合研究所 Photoresponsive compound, dispersant containing this photoresponsive compound, and method of producing nanocarbon material film using this dispersant
CN112451665A (en) * 2020-11-26 2021-03-09 山西医科大学 Novel NIR-II diagnosis and treatment integrated silicon-carbon nanoprobe and preparation method thereof
KR20210030034A (en) * 2019-09-09 2021-03-17 한국교통대학교산학협력단 Electro Chemical wireless diagnosing method using Carbon quantum dot
US20210269711A1 (en) * 2020-02-28 2021-09-02 Texas Christian University Near-infrared emissive graphene quantum dots method of manufacture and uses thereof
CN113583670A (en) * 2021-09-15 2021-11-02 山西医科大学第二医院 Orange light carbon quantum dot and preparation and application thereof
CN114181696A (en) * 2021-12-01 2022-03-15 潍坊医学院 Double-color near-infrared emission carbon nano-dot fluorescent nano-material and synthetic method and application thereof
CN114544974A (en) * 2022-02-25 2022-05-27 广东昊朗医疗科技有限责任公司 Carbon quantum dot microsphere-based fluorescence immunochromatographic reagent card and preparation method and application thereof
CN114921245A (en) * 2022-04-28 2022-08-19 澳门大学 Near-infrared carbon dots and preparation method and application thereof

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408984A (en) * 2013-08-22 2013-11-27 广东普加福光电科技有限公司 Optical coating composition, fluorescent optical membrane and preparation method thereof
US20180201512A1 (en) * 2017-01-16 2018-07-19 Winsky Technology Hong Kong Limited Yolk-shell-structured material, anode material, anode, battery, and method of forming same
WO2019153742A1 (en) * 2018-02-12 2019-08-15 有研稀土新材料股份有限公司 Near-infrared luminescent material and light-emitting device prepared using near-infrared luminescent material
WO2020045466A1 (en) * 2018-08-31 2020-03-05 日産化学株式会社 Method for producing photoluminescent nanocarbon
CN109385276A (en) * 2018-12-20 2019-02-26 南京大学 High-performance feux rouges carbon quantum dot material and preparation method thereof and bio-imaging application
CN110257050A (en) * 2019-05-13 2019-09-20 闽南师范大学 A kind of nitrogen sulphur codope carbon nano-particles and the application in the detection of 2,4,6- trinitrophenol
JP2021017411A (en) * 2019-07-19 2021-02-15 国立研究開発法人産業技術総合研究所 Photoresponsive compound, dispersant containing this photoresponsive compound, and method of producing nanocarbon material film using this dispersant
CN110484238A (en) * 2019-08-15 2019-11-22 五邑大学 A kind of polymeric PTC materials method promoting carbon dots stability
KR20210030034A (en) * 2019-09-09 2021-03-17 한국교통대학교산학협력단 Electro Chemical wireless diagnosing method using Carbon quantum dot
US20210269711A1 (en) * 2020-02-28 2021-09-02 Texas Christian University Near-infrared emissive graphene quantum dots method of manufacture and uses thereof
CN111847424A (en) * 2020-06-24 2020-10-30 华南师范大学 Red light carbon quantum dot with narrow spectrum emission and hydrothermal preparation method and application thereof
CN112451665A (en) * 2020-11-26 2021-03-09 山西医科大学 Novel NIR-II diagnosis and treatment integrated silicon-carbon nanoprobe and preparation method thereof
CN113583670A (en) * 2021-09-15 2021-11-02 山西医科大学第二医院 Orange light carbon quantum dot and preparation and application thereof
CN114181696A (en) * 2021-12-01 2022-03-15 潍坊医学院 Double-color near-infrared emission carbon nano-dot fluorescent nano-material and synthetic method and application thereof
CN114544974A (en) * 2022-02-25 2022-05-27 广东昊朗医疗科技有限责任公司 Carbon quantum dot microsphere-based fluorescence immunochromatographic reagent card and preparation method and application thereof
CN114921245A (en) * 2022-04-28 2022-08-19 澳门大学 Near-infrared carbon dots and preparation method and application thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
LI LI-PING: "Near-infrared emission carbon dots for bio-imaging applications", 新型炭材料, vol. 36, no. 3, pages 632 - 638, XP086638397, DOI: 10.1016/S1872-5805(21)60041-0 *
孙莉娜;李?;郭汉涛;黄庭庭;姚碧霞;翁文;: "氮、铁共掺杂碳纳米粒子的制备及在过氧化氢和葡萄糖检测中的应用", 应用化学, no. 03 *
孙莉娜;李龑;郭汉涛;黄庭庭;姚碧霞;翁文;: "氮、铁共掺杂碳纳米粒子的制备及在过氧化氢和葡萄糖检测中的应用", 应用化学, no. 03, 10 March 2020 (2020-03-10) *
彭锦雯;杜肖龙;陈妍;孙鹏飞;邓卫星;范曲立;: "近红外二区荧光纳米探针的制备及其在生物成像中的应用", 高分子学报, no. 11 *
李洪仁;候秀丽;孙传东;林姝怡;闫萧月;: "氮掺杂碳纳米粒子的合成及纺织品防伪鉴定", 沈阳大学学报(自然科学版), no. 06 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116836700A (en) * 2023-06-29 2023-10-03 辽宁大学 Preparation method of hyaluronic acid modified red light carbon dots HA-R-CDs and application of hyaluronic acid modified red light carbon dots HA-R-CDs in lung cancer cell targeted imaging
CN116836700B (en) * 2023-06-29 2024-05-31 辽宁大学 Preparation method of hyaluronic acid modified red light carbon dots HA-R-CDs and application of hyaluronic acid modified red light carbon dots HA-R-CDs in lung cancer cell targeted imaging

Also Published As

Publication number Publication date
CN115818621B (en) 2024-04-05

Similar Documents

Publication Publication Date Title
Xue et al. Dual functionalized natural biomass carbon dots from lychee exocarp for cancer cell targetable near-infrared fluorescence imaging and photodynamic therapy
Zhou et al. Recent insights into near-infrared light-responsive carbon dots for bioimaging and cancer phototherapy
CN104591124A (en) Preparation method for fluorescent carbon quantum dot with vitamin as carbon source
CN108130069B (en) Rare earth up-conversion nano diagnosis and treatment agent and preparation method thereof
CN113773667B (en) Organic small molecule near infrared two-region fluorescent dye and preparation method and application thereof
CN104083771A (en) Fluorescence resonance energy transfer-based tumor imaging and therapeutic targeting system and construction method thereof
CN111978556B (en) Preparation method and application of selenizing ZIF-67
CN114106581B (en) Organic micromolecular dye, J aggregation nano particles, and preparation methods and application thereof
CN114455567B (en) Preparation method and application of carbon nano particles
CN109504363B (en) Preparation method and application of near-infrared two-region imaging contrast agent
CN115818621B (en) Biomass-derived carbon nano particle with near infrared two-region light emission characteristic and preparation method and application thereof
NL2026426B1 (en) Fluorine-containing graphene quantum dots, preparation method and application thereof as photosensitiser for photodanamic therapy
CN108949151B (en) Up-conversion luminescence nano composite material with transition metal disulfide growing on surface, preparation method and application
CN109331182B (en) Polydopamine-modified conductive polymer nano material and preparation method and application thereof
CN106882791B (en) The preparation method and applications of water dispersible carbon nano-onions
CN105288625B (en) A kind of porous Bi2Se3Nanosponges material, its preparation method and application
CN106970059B (en) Preparation and application of two-photon fluorescent probe
CN104258424A (en) Compound nano diagnosis and treatment preparation and preparation method thereof
CN110339356B (en) Carbon nanodot reagent, preparation method and application thereof
CN108421040B (en) Conjugated polymer nanometer photosensitive material with two-photon imaging and photodynamic curative effects, and preparation and application thereof
CN111686250A (en) Mitochondrion targeted photothermal therapeutic agent and preparation and application thereof
CN107961375B (en) Metal sulfide nano material and preparation method and application thereof
CN106902351A (en) The preparation method and application of CG J aggregations
CN109810702B (en) Nano fluorescent probe with good biocompatibility and preparation method thereof
CN112451685B (en) Composite nano-particle with photoacoustic development and photothermal treatment functions

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