CN110615426A - Carbon nanodot with thermal activation near-infrared up-conversion luminescence characteristic and preparation method and application thereof - Google Patents
Carbon nanodot with thermal activation near-infrared up-conversion luminescence characteristic and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon nanodot with a thermal activation near-infrared up-conversion luminescence characteristic, and a preparation method and application thereof, and belongs to the technical field of carbon nanomaterials. The carbon nanodots are prepared by stripping red light emitting carbon nanodots and are formed by stacking single-layer or a small number of graphene-like sheet layers, and main absorption peaks and emission peaks of the carbon nanodots are located in a near infrared region. The up-conversion luminescence of the carbon nanodots is originated from the absorption of thermally activated single photons and can be realized under the excitation of a continuous laser light source; the up-conversion emission peak shifts blue with the temperature rise, and the peak intensity is enhanced; as the temperature decreases, the up-conversion emission gradually disappears and the down-conversion emission increases. The near-infrared luminescent up-conversion carbon nanodots can be used as a near-infrared imaging reagent to be applied to temperature-variable up-conversion fluorescence imaging and in-vivo conversion fluorescence imaging.
Description
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a carbon nano point with near-infrared absorption and near-infrared luminescence characteristics and thermal activation near-infrared up-conversion luminescence characteristics, and a preparation method and application thereof.
Background
The near-infrared (700-1700nm) bioluminescence imaging has higher tissue penetration depth and low autofluorescence, and has important significance for in-vivo fluorescence imaging. The interference of background fluorescence (Stokes luminescence) can be avoided by up-conversion near-infrared fluorescence imaging, and the signal-to-noise ratio of fluorescence imaging is further improved. The development of a fluorescence imaging reagent with near-infrared absorption emission characteristics, particularly near-infrared up-conversion luminescence characteristics, has important significance for clinical promotion of biological fluorescence imaging.
The carbon nano-dots (CDs) are easy to regulate and control in luminescence, high in fluorescence quantum efficiency, easy to prepare, good in biocompatibility and unique in application in the field of fluorescence imaging. However, due to the lack of effective energy band regulation means, the absorption and emission spectra of carbon nanodots in the prior art are still mainly distributed in the visible light region, and the types of carbon nanodots with main absorption and emission peaks located in the near infrared region are rare. Some carbon nanodots have up-conversion luminescence characteristics, and can realize red light-near infrared emission under the excitation of near infrared light (adv. mater.2017,29,1603443; Nanoscale2016,8,17350), but the up-conversion luminescence is realized through multi-photon absorption, an expensive femtosecond laser is needed as a light source, and the wide application of the carbon nanodots in vivo fluorescence imaging, especially in up-conversion imaging, is severely limited.
Therefore, there is a need to research a carbon nanodot having near infrared absorption and emission and near infrared up-conversion luminescence characteristics under continuous laser excitation.
Disclosure of Invention
In view of the above, the present invention provides a carbon nanodot with a thermally activated near-infrared up-conversion luminescence property, wherein the carbon nanodot has a main absorption and emission peak in the near-infrared region and has a near-infrared up-conversion luminescence under the excitation of continuous laser.
Another object of the present invention is to provide a method for preparing carbon nanodots having a thermally activated near-infrared up-conversion luminescence property;
another object of the present invention is to provide the use of carbon nanodots having a thermally activated near-infrared up-conversion luminescence property.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention firstly provides a carbon nanodot with thermal activation near-infrared up-conversion luminescence characteristics, which is prepared by stripping red light emitting carbon nanodots, and the main absorption and emission peaks of the carbon nanodot are positioned in a near-infrared region.
Preferably, the size distribution of the carbon nanodots with the thermal activation near-infrared up-conversion luminescence characteristic is 2-6nm, the height distribution is 0.4-2.0nm, and the carbon nanodots are formed by stacking single-layer small-amount graphene-like sheets.
Preferably, the size of the raw material, namely the red light emitting carbon nanodots, adopted by the invention is 4-11 nm, the height is 1-5 nm, and the shape is similar to a sphere.
Preferably, the main absorption peak of the carbon nanodot of the present invention is located at 680-900 nm.
Preferably, the carbon nanodots of the invention have down-conversion emission peak positions within the spectral range of 740-770 nm under the excitation of near infrared light.
Preferably, the up-conversion emission peak position of the carbon nanodot is in a spectral range of 760-790 nm under the excitation of 808nm continuous laser.
Preferably, the red light-emitting carbon nanodots adopted by the invention are stripped in a polar aprotic solvent and react with an electron-withdrawing group to generate near-infrared absorption and emission, wherein the electron-withdrawing group is selected from one or more of carbonyl, sulfonyl, sulfoxide, cyano and hydroxyl.
Specifically, the carbon nano-dots of the invention can realize near-infrared luminescence by the action of the compound containing electron-withdrawing groups on the surface or the polymer containing electron-withdrawing groups.
More preferably, the compound containing an electron-withdrawing group is selected from one or more of N, N '-dimethylformamide, N' -dimethylacetamide and dimethylsulfoxide.
More preferably, the polymer containing electron withdrawing groups is selected from polyvinylpyrrolidone.
Preferably, the peeling method of the present invention is one of microwave heating or ultrasound.
The invention also provides a preparation method of the carbon nanodot with the thermal activation near-infrared up-conversion luminescence characteristic, which comprises the following steps:
dissolving red light-emitting carbon nanodots in a polar aprotic solvent, and stripping the red light-emitting carbon nanodots through microwave heating or ultrasonic to obtain near-infrared up-conversion luminescent carbon nanodots stacked in a single-layer-few graphene-like sheet layer; the polar aprotic solvent is selected from one or more of N, N '-dimethylformamide, N' -dimethylacetamide and dimethyl sulfoxide; the reaction time is 0.5-1.5 h.
Preferably, the red light emitting carbon nanodots are prepared by:
carrying out solvothermal reaction on polycarboxyl organic acid and urea to obtain carbon nanodots;
the polycarboxy organic acid is selected from citric acid and/or citrazinic acid.
Preferably, the temperature of the solvothermal reaction is 160-220 ℃, and the time of the solvothermal reaction is 4-24 h.
The invention also provides the application of the carbon nanodot or the carbon nanodot prepared by the preparation method in up-conversion fluorescence imaging reagents and anti-counterfeiting reagents.
Compared with the prior art, the invention has the technical effects that:
the main absorption and emission peaks of the carbon nanodot provided by the invention are positioned in a near infrared region, and the carbon nanodot is prepared by stripping red light emission carbon nanodots in a polar aprotic solvent; the carbon nanodots prepared after stripping have a single-layer or small-amount graphene-like sheet layer stacking structure, so that the original inner sheet layer is changed into an outer sheet layer, and the outer plane and the edge of the sheet layer are acted with electron acceptor groups, so that the absorption in a near infrared region becomes a main absorption peak (adv. mater.2018,30,1705913) and the near infrared Stokes emission is realized. Because the interior and the edge of the sheet layer and the action of the electron hand groups respectively form an inner conjugated state and an edge conjugated state, under the excitation of 808nm laser, electrons in a ground state absorb photons to jump to an excited state in the edge conjugated state, and simultaneously absorb heat to further jump to an excited state in the inner conjugated state, and finally return to the ground state in a form of up-conversion luminescence, wherein an up-conversion luminescence mechanism is thermal activation excited state electron transfer and is single photon absorption, and a continuous laser can be used for excitation; the reported conversion luminescence on the carbon nanodots is realized by multiphoton absorption, and a femtosecond pulse laser is required for excitation. The experimental results show that: under the excitation of near infrared light, the down-conversion emission peak position of the carbon nano-dots is in the spectral range of 740-770 nm; under the excitation of continuous laser at 808nm, the up-conversion excitation peak position is in the spectral range of 760-790 nm. The temperature is increased, the up-conversion emission peak position is blue-shifted, the intensity is improved, and the down-conversion emission intensity is reduced; the temperature is reduced, the up-conversion emission peak position is red-shifted, the intensity is reduced, and the down-conversion emission intensity is improved. Therefore, the carbon nanodots can be used as dyes to realize temperature-variable upconversion fluorescence imaging, can be used as a fluorescence imaging reagent, an anti-counterfeiting reagent or an encryption reagent, and has wide application prospects in-vivo fluorescence imaging, especially in upconversion imaging.
Drawings
In order to more clearly illustrate the embodiments of the present application or technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
Fig. 1 is a transmission electron micrograph (a), a carbon nanodot size distribution diagram (b), and a high-resolution transmission electron micrograph (c) of a near-infrared upconversion luminescent carbon nanodot according to example 1 of the present invention;
fig. 2 is a graph showing (a) an atomic force microscope photograph of the near-infrared up-conversion luminescent carbon nanodots of example 1 of the present invention, (b) height distribution of the red-light carbon nanodots (before peeling) and the near-infrared up-conversion luminescent carbon nanodots (after peeling);
FIG. 3 shows (a) absorption and down-conversion emission spectra and (b) up-conversion emission spectra of near-infrared up-conversion luminescent carbon nanodots in example 1 of the present invention;
FIG. 4 is a graph showing the variation of upconversion luminescent intensity with excitation power of (a) upconversion luminescent spectra under different excitation light powers and (b) near-infrared upconversion luminescent carbon nanodots in example 1 according to the present invention;
fig. 5 is an emission spectrum of 808nm laser excitation during (a) temperature rise and (b) temperature drop of the near-infrared upconversion luminescent carbon nanodots in example 1 of the present invention;
FIG. 6 is an upconversion emission spectrum with near-infrared upconversion luminescent carbon nanodots according to example 2 of the present invention;
fig. 7 is a temperature-variable upconversion imaging picture of a luminescent carbon nanodot/PVP composite having near-infrared upconversion in example 3 of the present invention;
FIG. 8 is a graph showing the variation of the 740nm luminescence intensity with temperature under the excitation of 808nm of the near-infrared up-conversion luminescent carbon nanodot/PVP composite thin film in example 3 of the present invention;
FIG. 9 shows the upconversion emission spectrum of the carbon nanodots in DMA according to example 4 of the present invention;
FIG. 10 is a photograph of near-infrared up-conversion imaging of a mouse living body having near-infrared up-conversion luminescent carbon nanodots as an imaging agent in example 4 of the present invention.
Detailed Description
The invention provides a carbon nanodot with thermal activation near-infrared up-conversion luminescence characteristics, wherein the main absorption and emission peak of the carbon nanodot is positioned in a near-infrared region and is prepared by stripping red light emission carbon nanodots; the compound with electron-withdrawing group on the surface or the polymer with electron-withdrawing group can realize near infrared down-conversion and up-conversion luminescence.
The stripping method is one of microwave heating and ultrasonic.
The electron-withdrawing group is selected from one or more of carbonyl, sulfuryl, sulfoxide, cyano and hydroxyl.
The compound containing the electron-withdrawing group is selected from one or more of N, N '-Dimethylformamide (DMF), N' -Dimethylacetamide (DMA) and dimethyl sulfoxide (DMSO).
The polymer containing an electron withdrawing group is selected from polyvinylpyrrolidone (PVP).
The source of the red light emitting carbon nanodots is not particularly limited in the present invention, and the red light emitting carbon nanodots can be prepared by themselves using carbon nanodots well known to those skilled in the art or well known preparation methods. Those skilled in the art can refer to patents and literature (a modified carbon nanodot having near infrared absorption and near infrared emission, a method for preparing the same, and applications thereof, CN 201711115759; Toward efficiency orange emission carbon nanodotts and surface charges engineering, SongnanQu, DiLi, WenyuJi, PengtaoJing, Dong Hang, LeiLiu, HaiboZeng, Dezhanshen, Advanced Materials, 2016, 28, 3516-3521; Tailoningcolorects from N-dopete quantized carbon nanodots for biological applications, Dan Qu, Zaizian, Jue, Zhang.
The carbon nanodots emitting red light are used as raw materials, the sizes of the carbon nanodots are preferably 4-11 nm, and the heights of the carbon nanodots are preferably 1-5 nm. The carbon nanodots are spherical-like in shape and are formed by stacking single layers or a small number of graphene-like sheets.
The main absorption peak of the carbon nanodot is 680-900 nm; the up-conversion luminescence is originated from the absorption of thermally activated single photons and can be realized under the excitation of a continuous laser light source; preferably, the upconversion excitation light is 808nm continuous laser; preferably, the up-conversion emission peak position is in a spectral range of 760-790 nm. The carbon nanodots are excited by near infrared light, and the down-conversion emission peak position is in the spectral range of 740-770 nm.
The invention provides a preparation method of the near-infrared up-conversion luminescent carbon nanodots, which comprises the following steps:
(1) dissolving the red light-emitting carbon nanodots in a polar aprotic solvent for stripping, and purifying to obtain the near-infrared up-conversion luminescent carbon nanodots
(2) The up-conversion luminescent carbon nano-dots are mixed with a raw material containing an electron-withdrawing group, wherein the raw material containing the electron-withdrawing group is a compound containing the electron-withdrawing group or a polymer containing the electron-withdrawing group, and the near-infrared up-conversion and down-conversion luminescence are realized.
In the invention, the size distribution of the up-conversion luminescent carbon nano-dots is 2-6nm, the height distribution is 0.4-2.0nm, and the up-conversion luminescent carbon nano-dots are formed by stacking 1-3 layers of graphene sheets;
in the invention, the main absorption peak of the up-conversion luminescent carbon nanodots is positioned at 680-900 nm;
in the invention, the down-conversion emission peak position of the up-conversion luminescent carbon nano-dots is in the spectral range of 740-770 nm;
in the invention, the up-conversion luminescent carbon nanodots are excited by 808nm continuous laser, and the up-conversion emission peak position is in the spectral range of 760-790 nm;
in the invention, the reaction time is preferably 0.5-1.5 h. The reaction is in the form of ultrasonic or microwave heating; the reaction temperature during ultrasonic treatment is preferably 20-40 ℃; the reaction temperature during heating is preferably 70-100 ℃.
In the invention, the up-conversion luminescence mechanism of the carbon nanodots is heat-activated excited-state charge transfer, so that the up-conversion luminescence intensity is enhanced along with the rise of temperature, and the temperature-variable up-conversion fluorescence imaging and the living body near-infrared up-conversion fluorescence imaging can be realized, and the carbon nanodots can be further used as near-infrared optical imaging reagents to be applied to anti-counterfeiting and living body imaging.
The invention provides an application of the carbon nanodot or the carbon nanodot prepared by the preparation method in temperature-variable up-conversion imaging and in vivo-conversion imaging.
In order to make the technical solutions of the present invention better understood, those skilled in the art will now describe the present invention in further detail with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The near-infrared up-conversion luminescent carbon nanodots are prepared by heating and stripping red light emitting carbon nanodots in DMF (dimethyl formamide) in a microwave manner.
The preparation method of the near-infrared up-conversion luminescent carbon nanodots comprises the following steps:
dissolving 5mg of red light-emitting carbon nanodots (CD) in 100mLDMF, reacting in a microwave reactor at 100 ℃ for 70min, performing rotary evaporation to remove DMF to obtain black solids, and washing the solids twice with ethanol to obtain black powder, namely the near-infrared upconversion luminescent carbon nanodots (NIR-CD).
Example 1 is described with reference to FIGS. 1 to 5:
luminescence by near-infrared upconversion of example 1The carbon nanodots are characterized by a Transmission Electron Microscope (TEM) and an Atomic Force Microscope (AFM), the results are shown in FIGS. 1-2, TEM pictures show that the size distribution of the carbon nanodots is 2-6nm, and the carbon nanodots can be observed in a high-resolution transmission electron microscope pictureThe surface lattice (lattice spacing is 0.21nm), and an AFM (atomic force microscopy) picture shows that the height of the carbon nano-dots is distributed in the range of 0.4-2.0nm, which indicates that the near-infrared up-conversion luminescent carbon nano-dots are formed by stacking 1-3 layers of graphene-like sheets.
The absorption spectrum and fluorescence emission spectrum analysis of the DMF solution of the near-infrared up-conversion luminescent carbon nanodots of example 1 showed that the main absorption peak of the carbon nanodots is in the near-infrared region and the absorption peak position is 724nm, as shown in fig. 3. Under the excitation of 732nm, the emission peak position is 771nm, and the fluorescence quantum efficiency is 11%; under the excitation of 808nm, the up-conversion emission peak position is 787nm at room temperature.
The result of the upconversion emission spectrum test of the DMF solution of the near-infrared upconversion luminescent carbon nanodots of example 1 under excitation of different powers is shown in fig. 4, and the upconversion emission peak intensity and the excitation light power have a linear relationship, which proves that the upconversion emission process is a single photon absorption process.
As a result of performing temperature-variable fluorescence emission spectroscopy on the DMF solution of the near-infrared up-conversion luminescent carbon nanodots of example 1, as shown in fig. 5, the up-conversion emission peak intensity increases with increasing temperature, the emission peak position blue-shifts with increasing temperature (765 nm at 378K), the up-conversion emission peak intensity gradually decreases and disappears when the temperature decreases, and the down-conversion emission peak intensity gradually increases (825 nm at 213K).
Example 2
The near-infrared up-conversion luminescent carbon nanodots are prepared by ultrasonically treating red light emitting carbon nanodots in DMSO (dimethyl sulfoxide).
The preparation method of the near-infrared up-conversion luminescent carbon nanodots comprises the following steps:
dissolving 5mg of red light-emitting carbon nanodots in 100mLDMSO, performing ultrasonic treatment in an ultrasonic cell disruptor (500W) for 15min, freeze-drying to remove DMSO to obtain black solids, and washing the solids twice with ethanol to obtain black powder which is the near-infrared up-conversion luminescent carbon nanodots.
Example 2 is illustrated in connection with fig. 6:
fluorescence emission spectrum analysis was performed on the DMSO solution of the near-infrared up-conversion luminescent carbon nanodots of example 2, and the result is shown in fig. 6, where the up-conversion luminescence peak position is 784 nm.
Example 3
The application of the near-infrared up-conversion luminescent carbon nanodots as a fluorescence imaging reagent in temperature-variable up-conversion fluorescence imaging is as follows:
the application of the carbon nanodots with near-infrared absorption and near-infrared luminescence under near-infrared excitation as a fluorescence imaging reagent comprises the following steps:
and mixing the near-infrared up-conversion emission carbon nano-dots prepared in the example 1 with PVP to prepare ink, writing L on a glass sheet, and drying to obtain the carbon nano-dot/PVP compound film. The letters are placed on a hot table to be heated and then cooled, and are imaged under a cmos camera through a 770nm short-wave pass filter under the excitation of a 808nm laser, a photo is shown in fig. 7, letter up-conversion luminescence can be observed at room temperature, the letter luminescence is enhanced along with the temperature rise, and the letter luminescence is weakened when the temperature is reduced to the room temperature. The upconversion luminescence spectrum of the carbon nanodot/PVP composite film is further tested through a 770nm short-wave pass filter, and the result is shown in fig. 8, wherein fig. 8 is a graph of the luminescence intensity at 740nm along with the temperature change of the film, and the upconversion luminescence of the carbon nanodot/PVP composite film is enhanced along with the temperature increase and is reduced along with the temperature decrease. The result shows that the near-infrared up-conversion luminescent carbon nanodots can be used for temperature-variable up-conversion imaging and can be used as a fluorescence imaging reagent for anti-counterfeiting.
Example 4
The application of the near-infrared up-conversion luminescent carbon nanodots as a fluorescence imaging reagent in-vivo conversion near-infrared fluorescence imaging comprises the following steps:
dissolving the near-infrared up-conversion luminescent carbon nanodots into DMA (direct memory access), wherein the concentration is 40ppm, taking 40 microliter of the solution, injecting the solution into C57 mice subcutaneously, and imaging under the excitation of a continuous laser at 808nm through a 770nm short-wave pass filter under a cmos camera, as shown in figures 9-10, wherein figure 9 is an up-conversion luminescent spectrum of the carbon nanodots in the DMA, and figure 10 is a near-infrared up-conversion imaging photo of the mice, which shows that the near-infrared up-conversion luminescent carbon nanodots can be applied to living body imaging by using the near-infrared up-conversion imaging agent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A carbon nano-point with the thermal activation near-infrared up-conversion luminescence characteristic is prepared from red light emitting carbon nano-point through stripping, and its main absorption and emission peaks are in near-infrared region.
2. The carbon nanodot with thermally activated near-infrared up-conversion luminescence property according to claim 1, wherein the size distribution is 2 to 6nm, the height distribution is 0.4 to 2.0nm, and the carbon nanodot is formed by stacking a single layer and a small amount of graphene-like sheets.
3. The carbon nanodot with thermally activated near-infrared up-conversion luminescence property according to claim 1, wherein the red light emitting carbon nanodot has a size of 4 to 11nm, a height of 1 to 5nm, and a shape of quasi-spherical shape.
4. The carbon nanodot with thermally activated near-infrared up-conversion luminescence property according to claim 1, wherein the main absorption peak of the carbon nanodot is 680-900 nm.
5. The carbon nanodot with the thermally activated near-infrared up-conversion luminescence property of claim 1, wherein the carbon nanodot has a down-conversion emission peak position in the 740-770 nm spectral range under the excitation of near-infrared light.
6. The carbon nanodot with the thermal activation near infrared up-conversion luminescence property of claim 1, wherein the carbon nanodot has an up-conversion emission peak in the spectral range of 760-790 nm under the continuous laser excitation of 808 nm.
7. The carbon nanodot with thermally activated near-infrared up-conversion luminescence property according to claim 1, wherein the red light emitting carbon nanodot is exfoliated in a polar aprotic solvent, and reacts with an electron withdrawing group to generate near-infrared absorption and emission, wherein the electron withdrawing group is selected from one or more of carbonyl, sulfone, sulfoxide, cyano and hydroxyl.
8. The carbon nanodot with thermally activated near infrared up-conversion luminescence property according to claim 1, wherein the peeling method is one of microwave heating or ultrasound.
9. A method for preparing a carbon nanodot having a thermally activated near infrared up-conversion luminescence property according to any one of claims 1 to 8, comprising the steps of:
dissolving red light-emitting carbon nanodots in a polar aprotic solvent, and stripping the red light-emitting carbon nanodots through microwave heating or ultrasonic to obtain near-infrared up-conversion luminescent carbon nanodots stacked in a single-layer-few graphene-like sheet layer; the polar aprotic solvent is selected from one or more of N, N '-dimethylformamide, N' -dimethylacetamide and dimethyl sulfoxide; the reaction time is 0.5-1.5 h.
10. Use of the carbon nanodot according to any one of claims 1 to 8 or the carbon nanodot prepared by the preparation method according to claim 9 in up-conversion fluorescence imaging agents and anti-counterfeiting agents.
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| CN113403068A (en) * | 2021-06-16 | 2021-09-17 | 澳门大学 | Fused carbon dot, 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 |
| CN116445159A (en) * | 2023-04-26 | 2023-07-18 | 澳门大学 | Near-infrared luminous carbon dot and preparation method and application thereof |
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