CN105271174A - Ultra carbon nanodot with high near-infrared absorption performance, preparing method thereof and application thereof - Google Patents
Ultra carbon nanodot with high near-infrared absorption performance, preparing method thereof and application thereof Download PDFInfo
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Abstract
The invention discloses an ultra carbon nanodot with high near-infrared absorption performance, a preparing method thereof and an application thereof, and belongs to the technical field of carbon nanometer materials. The technical problems that the absorbing and the photothermal conversion efficiency of a carbon nanodot in the prior art in the near-infrared region are low are solved. The ultra carbon nanodot is composed of carbon nanodot bodies with electropositivity functional groups and electronegativity functional groups on the surfaces at the same time in an automatic assembling mode, absorption peaks exist in the spectral range of 70nm to 1,000 nm, and the photothermal conversion efficiency in the spectral range is 30% to 65%. The ultra carbon nanodot has the advantages of being small in size, high in water solubility and good in biocompatibility, further has high near-infrared absorption performance and efficient near-infrared photothermal conversion performance, can serve as a near-infrared photothermal conversion nanometer material and can be applied to the energy conversion field and the medical field.
Description
Technical field
The invention belongs to carbon nanomaterial technical field, be specifically related to a kind of super carbon nano dot with strong near infrared absorption and preparation method thereof and application.
Background technology
Photothermal deformation nano material is that one can absorb certain light, produces heat, thus cause the functional materials of high temperature in local by plasma resonance or energy jump.Wherein, the wavelength region due near infrared light imparts the optical security character of its uniqueness, and can pass through human body skin and dark tissue, therefore the photothermal deformation nano material of near infrared light has very large application potential in biomedicine.
Photo-thermal therapy method utilizes the material with high light thermal conversion efficiency, be injected into inside of human body, utilize targeting recognition technology to be gathered near tumor tissues, and be that heat energy is to kill a kind of methods for the treatment of of cancer cells by transform light energy under the irradiation of external light source (being generally near infrared light).In recent years, near infrared light heat cure, as the methods for the treatment of of a kind of local, accurate, little wound, has developed into a kind of anti-cancer therapies of great potential.
Photoacoustic imaging(PAI) utilizes photoacoustic effect to obtain biological tissue or the faultage image of material or a kind of formation method of three-dimensional image, and it has the advantage of optics and acoustics imaging concurrently, thus becomes a kind of imaging pattern comparing at present and have application prospect.Photoacoustic imaging(PAI) contrast medium is the contrast-enhancing agent of photoacoustic imaging(PAI), it is by changing acoustics and the optical characteristics of local organization, improve image contrast and resolving power, thus significantly strengthen the imaging effect of photoacoustic imaging(PAI), become a focus of current biological medical field research.Optical-thermal conversion material, due to its good near-infrared absorption performance and heat effect, in recent years, is used to biomedical imaging and diagnosis as photoacoustic imaging(PAI) contrast medium.
Carbon nano dot (Carbondots, CDs), has the excellent properties such as size is little, good water solubility, fluorescent stability are good, toxicity is low, good biocompatibility, cost are low, makes carbon nano dot unique advantage in the application of biomedical sector.But although carbon nano dot has good Photophysics, the absorption spectrum of carbon nano dot of the prior art is still mainly distributed in ultraviolet, blue light, green wavelength, only has minority energy of absorption edge to extend to ruddiness or near-infrared region.And due to the absorption low in near-infrared region of carbon nano dot, under near-infrared laser low power is irradiated, carbon nano dot is difficult to convert incident photon to enough heat, so photo-thermal conversion efficiency is lower, cannot killing and wounding cancer cells be realized, which limits the application of carbon nano dot in photo-thermal therapy and photoacoustic imaging(PAI) field.
Therefore, a kind of carbon nano dot with strong near infrared absorption and efficiency light thermal conversion efficiency of research is needed badly.
Summary of the invention
The object of the invention is to solve the technical problem that carbon nano dot of the prior art is low in the absorption of near-infrared region, near-infrared region photo-thermal conversion efficiency is low, a kind of super carbon nano dot with strong near infrared absorption and preparation method thereof and application are provided.
It is as follows that the present invention solves the problems of the technologies described above the technical scheme taked.
There is the super carbon nano dot of strong near infrared absorption, assembled with the carbon nano dot of electropositivity functional group and electronegativity functional group by surface simultaneously, in the spectral range of 470-1000nm, there is absorption peak, and the photo-thermal conversion efficiency in this spectral range is 30%-65%.
Preferably, described electropositivity functional group is amino and/or pyrryl, and described electronegativity functional group is one or more in pyridyl, carboxyl, hydroxyl.
Preferably, the absorption peak position of described super carbon nano dot is in the spectral range of 640-715nm, and peak width at half height is distributed in the spectral range of 170-250nm.
Preferably, described surface is prepared with the carbon nano dot of electropositivity and electronegativity functional group simultaneously by the following method:
Step one, by carbon source and urea in mass ratio 2:1-1:4 be dissolved in deionized water, obtain clear solution;
Or, by carbon source and ammoniacal liquor in mass ratio 2:1-1:4 be dissolved in deionized water, obtain clear solution;
Step 2, the clear solution of step one gained is placed in reaction unit, react 4-10h at 160-200 DEG C, reacted solution, after freeze-drying, obtains yellow carbon nano dot powder, is surface simultaneously with the carbon nano dot of electropositivity and electronegativity functional group.
Preferred, described carbon source is citric acid.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption, that surface is placed in Aquo System with the carbon nano dot of electropositivity functional group and electronegativity functional group simultaneously, color to carbon nano dot becomes black, the black solid obtained, and is super carbon nano dot.
Preferably, described Aquo System is the one in the mixing solutions of damp atmosphere, neutral aqueous solution, water and organic solvent.
Preferably, the method also comprises, and will obtain black solid redispersion in water, successively after dialysis, freeze-drying, obtains super carbon nano dot.
The present invention also provides the above-mentioned application of super carbon nano dot as optical-thermal conversion material with strong near infrared absorption.
Preferably, described super carbon nano dot can as photoacoustic imaging(PAI) contrast medium, photothermal deformation agent or paint additive.
Compared with prior art, the invention has the beneficial effects as follows:
1, super carbon nano dot of the present invention not only possesses little, the water-soluble height of size;
2, super carbon nano dot biocompatibility of the present invention is high, and when concentration is up to 400ppm, after HeLa cell cultivates 24h wherein, survival rate still remains on more than 85%;
3, super carbon nano dot of the present invention possesses strong near-infrared absorption and efficient near infrared light thermal conversion performance, has strong absorption peak and photo-thermal conversion efficiency reaches 30%-65% in the spectral range of 470-1000nm;
4, the preparation method of super carbon nano dot of the present invention achieves the self-assembly that water molecules exists lower carbon nano dot, and preparation method is simple, cheap;
5, the super carbon nano dot prepared of the present invention is owing to possessing the high conversion efficiency of highly water-soluble, good biocompatibility and near-infrared region, can as near infrared light thermal conversion materials application in Energy conversion field and medical field, as as photoacoustic imaging(PAI) contrast medium, for photoacoustic imaging(PAI), be used for killing cancer cells in photo-thermal therapy as photothermal deformation agent, improve the photothermal deformation performance of coating and film as paint additive.
Accompanying drawing explanation
In Fig. 1, (a) and (c) are respectively the solid state of carbon nano dot and the photo of solution state of embodiment 1 under sun exposure; B () and (d) are respectively the solid state of super carbon nano dot and the photo of solution state of embodiment 1 under sun exposure;
Fig. 2 is the ultraviolet-visible-infrared absorption spectrum of the carbon nano dot (curve 1) of the embodiment of the present invention 1 and the super carbon nano dot (curve 2) of embodiment 1;
Fig. 3 is the Fourier transform infrared spectroscopy of the carbon nano dot of the embodiment of the present invention 1 and the super carbon nano dot of embodiment 1;
In Fig. 4, the atomic force microscopy of the carbon nano dot that (a) is embodiment 1, (b) is the height map of Selected Particles in (a), and (c) is the size distribution plot of carbon nano dot in (a);
In Fig. 5, the atomic force microscopy of the super carbon nano dot that (a) is embodiment 1, (b) is the height map of Selected Particles in (a), and (c) is the size distribution plot of carbon nano dot in (a);
In Fig. 6, (a) and (b) is respectively the carbon nano dot of embodiment 1 and the high resolution transmission electron microscopy photo of super carbon nano dot;
Fig. 7 is the photo-thermal temperature variation-time curve of the super carbon nano dot dispersion liquid of the different concns of embodiment 8;
Fig. 8 is the photo-thermal temperature variation-time curve of super carbon nano dot dispersion liquid under the laser radiation of different capacity density of embodiment 9;
Fig. 9 is the photo-thermal temperature variation-time curve of the super carbon nano dot dispersion liquid of the different concns of embodiment 10;
In Figure 10, the super carbon nano dot dispersion liquid that (a) is embodiment 11 is down to the temperature variation-time curve in the process of room temperature after laser radiation to temperature, and (b) bears logarithmic curve for m-cooling motivating force during temperature descending section in this process;
Figure 11 is the survival rate histogram of HeLa cell in the super carbon nano dot dispersion liquid of different concns of embodiment 12;
Figure 12 is the HeLa cell side survival rate histogram in varied situations of embodiment 13.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just to further illustrate the features and advantages of the present invention instead of limiting to the claimed invention.
Inventive principle of the present invention: the preparation method of super carbon nano dot of the present invention, have employed the carbon nano dot that surface has electropositivity functional group and electronegativity functional group simultaneously, carbon nano dot is made to have the characteristic of surface charge skewness, and then stronger electrostatic interaction is produced between carbon nano dot, provide the motivating force of carbon nano dot self-assembly, achieve carbon nano dot and carry out self-assembly under water existent condition, and then obtain super carbon nano dot.And due to the introducing of electropositivity and electronegativity functional group, two new surface levels are defined on carbon nano dot surface, because the space of electric charge is discrete, the transition of electron of carbon nano dot its own face energy inter-stage is prohibited, and in super carbon nano dot after self-assembly, define the surface electronic transition between adjacent carbons nano dot, and then make super carbon nano dot of the present invention define strong absorption peak in near-infrared region, possess strong near-infrared absorption and efficient near infrared light thermal conversion performance.
The super carbon nano dot with strong near infrared absorption of the present invention, surface is simultaneously with the group of electropositivity functional group and the self-assembly of electronegativity functional group, wherein, electropositivity functional group can be amino and/or pyrryl, and electronegativity functional group can be one or more in pyridyl, carboxyl, hydroxyl.This super carbon nano dot has strong absorption peak in the spectral range of 470-1000nm, and the photo-thermal conversion efficiency in this spectral range is 30%-65%.Generally, absorb peak position in the spectral range of 640-715nm, peak width at half height is distributed in the spectral range of 170-250nm.
The preparation method with the super carbon nano dot of strong near infrared absorption of the present invention, surface is placed in Aquo System with the carbon nano dot of electropositivity functional group and electronegativity functional group simultaneously, carbon nano dot issues in molecularity is conigenous assembling, until the color of carbon nano dot (yellow powder) becomes black, the black solid obtained, is super carbon nano dot.Super carbon nano dot is purified by dialysing in aqueous.Purification process can be: be scattered in by black solid in water, and dialysis is purified, and final freeze-drying obtains black-and-blue solid, is the super carbon nano dot solid after purification.
Wherein, the distribution of sizes of carbon nano dot is not particularly limited, and is generally 1-5nm.Aquo System is not particularly limited, as long as there is water molecules to exist, water molecules content is higher, and the variable color of carbon nano dot is fast, and water molecules content is lower, and the variable color of carbon nano dot is slow.General selection Aquo System is the one in the mixing solutions of damp atmosphere, neutral aqueous solution, water and organic solvent.The relative humidity of usual damp atmosphere generally selects 10-60%, is generally 7 days to 30 days storage period.Dialysis is purified and is usually used Mw=1000 dialysis tubing, and dialyse 8h at 0 DEG C, and water generally adopts deionized water.When to adopt in the mixing solutions of neutral aqueous solution, water and organic solvent a kind of for Aquo System, after the color (yellow powder) of carbon nano dot becomes black, usually solution is dried, the black solid obtained.
Surface in the present invention is simultaneously prior art with the carbon nano dot of electropositivity and electronegativity functional group, can be obtained, as prepared by hydrothermal method by those skilled in the art's well-known way.Specifically can refer to document (HighlyluminescentS, Nco-dopedgraphenequantumdotswithbroadvisibleabsorptionba ndsforvisiblelightphotocatalysts, DanQu, MinZheng, PengDu, YueZhou, LigongZhang, DiLi, HuaqiaoTan, ZhaoZhao, ZhigangXie, ZaichengSun, Nanoscale, 2013,5,12272; Engineeringsurfacestatesofcarbondotstoachievecontrollabl eluminescenceforsolid-luminescentcompositesandsensitiveB e
2+detection, XiaomingLi, ShengliZhang, SergeiA.Kulinich, YanliLiu, HaiboZeng, ScientificReports, 2014,4,4976).Present embodiment provides a kind of preparation method, but is not limited thereto:
Step one, by carbon source and urea in mass ratio 2:1-1:4 be dissolved in deionized water, obtain clear solution; Or by carbon source and ammoniacal liquor in mass ratio 2:1-1:4 be dissolved in deionized water, obtain clear solution;
Carbon source can know carbon source for those skilled in the art such as citric acid, ethylenediamine tetraacetic acid (EDTA), glycerine, glucose, fructose, sucrose, chitosan or starch, is not particularly limited, optimization citric acid;
Step 2, the clear solution of step one gained is placed in autoclave (tetrafluoroethylene autoclave, 50ml), 4-10h is reacted at 160-200 DEG C, reacted solution is through freeze-drying (general employing-40 DEG C), obtain yellow carbon nano dot powder, be surface simultaneously with the carbon nano dot of electropositivity and electronegativity functional group.
The aqueous dispersions of super carbon nano dot of the present invention produces obvious photo-thermal effect under near-infrared laser irradiates, and aqueous dispersions temperature improves with super carbon nano dot concentration and laser power density and raises.The super carbon nano dot so of the present invention with strong near infrared absorption can as near infrared light thermal conversion applications to nanostructures.Specifically do not limit, the using method of the optical-thermal conversion material conventionally uses.As can as photothermal deformation agent, for photo-thermal therapy; Can as photoacoustic imaging(PAI) contrast medium, for photoacoustic imaging(PAI); May be used for paint additive, improve the photothermal deformation performance of coating and film.
Be further elaborated to the present invention below in conjunction with embodiment, chemical feedstocks involved in embodiment is commercially available, and without the need to purification processes.In addition; for easy to operate; the surface adopted in the present embodiment is prepared through laboratory according to existing method with the carbon nano dot of electropositivity functional group and electronegativity functional group simultaneously; but it should be noted that; the present invention is not limited to this method, the surface that other forms or method obtain simultaneously with the carbon nano dot of electropositivity functional group and electronegativity functional group also in protection scope of the present invention.
Embodiment 1
Composition graphs 1-6 illustrates embodiment 1
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 700nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and urea in mass ratio 1:2 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, react 4h at 160 DEG C, reacted solution ,-40 DEG C of freeze-drying, obtains yellow carbon nano dot powder.
Yellow carbon nano dot powder is placed in beaker, being placed on relative humidity is in the environment of 60% 14 days, carbon nano dot issues in water molecules effect is conigenous assembling, surface becomes black completely, is scattered in deionized water by the black solid obtained and makes strong solution, pour Mw=1000 dialysis tubing into, dialyse 8h at 0 DEG C, again by surplus solution freeze-drying in dialysis tubing, obtain black-and-blue solid, be super carbon nano dot.
Observe the carbon nano dot of embodiment 1 and super carbon nano dot respectively, result as shown in Figure 1, as can be seen from the figure, the carbon nano dot of embodiment 1 is yellow powder, super carbon nano dot is black blue powders, and carbon nano dot and super carbon nano dot all possess good water-soluble, can be dispersed in water.
To carbon nano dot and the super carbon nano dot ultraviolet-visible-infrared absorption spectrum analysis of embodiment 1, result as shown in Figure 2, as can be seen from Figure 2, super carbon nano dot has strong absorption peak, and (absorption region is 470-1000nm in visible near-infrared district, absorption peak at 700nm, peak width at half height 201nm).
Ftir analysis is carried out to the carbon nano dot of embodiment 1 and super carbon nano dot, result as shown in Figure 3, the charateristic avsorption band ν (O-H) in Fig. 3/ν (N-H) (3100-3500cm
-1), ν (C=O)/δ (N-H)/ν (C=N) (1550-1750cm
-1) and δ (C-H)/ν (C-N) (1330-1480cm
-1) demonstrate two kinds of carbon nano dot surfaces all there is the functional groups such as amino, hydroxyl, carboxyl, pyridyl, pyrryl.
In Fig. 3, the atomic force microscopy of the carbon nano dot that (a) is embodiment 1, (b) is the height map of Selected Particles in (a), and (c) is the size distribution plot of carbon nano dot in (a); In Fig. 4, the atomic force microscopy of the super carbon nano dot that (a) is embodiment 1, (b) is the height map of Selected Particles in (a), and (c) is the size distribution plot of carbon nano dot in (a); As can be seen from Fig. 3 and Fig. 4, the distribution of sizes of carbon nano dot is within the scope of 1-5nm, and the size of super carbon nano dot is within the scope of 5-25nm.
In Fig. 5, a () and (b) is respectively the carbon nano dot of embodiment 1 and the high resolution transmission electron microscopy photo of super carbon nano dot, as seen in Figure 5, the small size carbon nano dot of surface charge skewness assembles the super carbon nano dot of formation through self-assembly.
Embodiment 2
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 714nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and urea in mass ratio 1:2 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, react 4h at 160 DEG C, reacted solution ,-40 DEG C of freeze-drying, obtains yellow carbon nano dot powder.
Yellow carbon nano dot powder is placed in the beaker filling ethanol, then beaker is placed in the encloses container that water is housed, places 20 days at 35 DEG C, enter in ethanol after water volatilization, carbon nano dot issues in water molecules effect is conigenous assembling, surface becomes black completely, is scattered in deionized water by the black solid obtained and makes strong solution, pour Mw=1000 dialysis tubing into, dialyse 8h at 0 DEG C, again by surplus solution freeze-drying in dialysis tubing, obtain black-and-blue solid, be super carbon nano dot.
Embodiment 3
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 680nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and urea in mass ratio 1:2 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, react 4h at 160 DEG C, reacted solution ,-40 DEG C of freeze-drying, obtains yellow carbon nano dot powder.
Yellow carbon nano dot powder is placed in beaker, being placed on relative humidity is in the environment of 60% 8 days, carbon nano dot issues in water molecules effect is conigenous assembling, surface becomes black completely, is scattered in deionized water by the black solid obtained and makes strong solution, pour Mw=1000 dialysis tubing into, dialyse 8h at 0 DEG C, again by surplus solution freeze-drying in dialysis tubing, obtain black-and-blue solid, be super carbon nano dot.
Embodiment 4
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 660nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and urea in mass ratio 1:1 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, react 6h at 160 DEG C, reacted solution ,-40 DEG C of freeze-drying, obtains yellow carbon nano dot powder.
Yellow carbon nano dot powder is placed in beaker, being placed on relative humidity is in the environment of 60% 8 days, carbon nano dot issues in water molecules effect is conigenous assembling, surface becomes black completely, is scattered in deionized water by the black solid obtained and makes strong solution, pour Mw=1000 dialysis tubing into, dialyse 8h at 0 DEG C, again by surplus solution freeze-drying in dialysis tubing, obtain black-and-blue solid, be super carbon nano dot.
Embodiment 5
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 620nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and urea in mass ratio 1:2 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, react 10h at 200 DEG C, reacted solution ,-40 DEG C of freeze-drying, obtains yellow carbon nano dot powder.
Yellow carbon nano dot powder is placed in beaker, being placed on relative humidity is in the environment of 10% 30 days, carbon nano dot issues in water molecules effect is conigenous assembling, surface becomes black completely, is scattered in deionized water by the black solid obtained and makes strong solution, pour Mw=1000 dialysis tubing into, dialyse 8h at 0 DEG C, again by surplus solution freeze-drying in dialysis tubing, obtain black-and-blue solid, be super carbon nano dot.
Embodiment 6
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 620nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and urea in mass ratio 1:2 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, 4h is reacted at 160 DEG C, reacted solution is-40 DEG C of freeze-drying, obtain yellow carbon nano dot powder, yellow powder is scattered in deionized water, 60 DEG C of oven dry, obtain black solid, be super carbon nano dot.
Embodiment 7
Have the super carbon nano dot of strong near infrared absorption, absorption peak position is 600nm, is assembled formed by carbon nano dot, and this carbon nano dot is surperficial with electropositive groups that is amino and pyrryl, and simultaneously with the electronegativity group of pyridyl, carboxyl and hydroxyl.
The above-mentioned preparation method with the super carbon nano dot of strong near infrared absorption:
By citric acid and ammoniacal liquor in mass ratio 1:2 be dissolved in deionized water, obtain clear solution and be placed in 50ml tetrafluoroethylene autoclave, react 4h at 160 DEG C, reacted solution ,-40 DEG C of freeze-drying, obtains yellow carbon nano dot powder.
Yellow carbon nano dot powder is placed in beaker, being placed on relative humidity is in the environment of 60% 8 days, carbon nano dot issues in water molecules effect is conigenous assembling, surface becomes black completely, is scattered in deionized water by the black solid obtained and makes strong solution, pour Mw=1000 dialysis tubing into, dialyse 8h at 0 DEG C, again by surplus solution freeze-drying in dialysis tubing, obtain black-and-blue solid, be super carbon nano dot.
Embodiment 8
Composition graphs 7 illustrates embodiment 8
There is the application of super carbon nano dot as near infrared photoelectricity changing agent of strong near infrared absorption:
Super carbon nano dot embodiment 1 prepared is scattered in deionized water, and configuration concentration is the dispersion liquid of 25,50,100,200ppm respectively, and the dispersion liquid getting the above-mentioned different concns of 1ml is respectively placed in 1*1*4cm
3in quartz cell, do reference, irradiate dispersion liquid respectively with 732nm laser with the deionized water of same volume (1ml), laser power density is 1W/cm
2, test dispersion liquid temperature every 15s in 10min, when recording 10min, disperse liquid temp to promote 19.8 respectively, 25.6,34,35.2 DEG C, reference deionized water temperature increase 1.1 DEG C.
Fig. 7 is the temperature variation-time curve of the Superstrong carbon nano dot of different concns in embodiment 8.As can be seen from Figure 7, super carbon nano dot of the present invention has stronger photo-thermal conversion efficiency, and photo-thermal conversion efficiency increases along with the increase of concentration.
Embodiment 9
Composition graphs 8 illustrates embodiment 9
There is the application of super carbon nano dot as near infrared photoelectricity changing agent of strong near infrared absorption:
Super carbon nano dot embodiment 1 prepared is scattered in deionized water, and configuration concentration is 100ppm dispersion liquid, gets 1ml respectively and is placed in three 1*1*4cm
3in quartz cell, with 732nm laser radiation dispersion liquid, laser power density is set to 0.5,1,2W/cm respectively
2, test dispersion liquid temperature every 15s in 10min, during 10min, disperse liquid temp to promote 16.1 respectively, 34,55.5 DEG C.
Fig. 8 is the temperature variation-time curve of Superstrong carbon nano dot under different capacity density laser irradiates in embodiment 9.As can be seen from Figure 8, super carbon nano dot of the present invention has stronger photo-thermal conversion efficiency, and photo-thermal conversion efficiency increases with the increase of the power density of the laser irradiated.
Embodiment 10
Composition graphs 9 illustrates embodiment 10
There is the application of super carbon nano dot as near infrared photoelectricity changing agent of strong near infrared absorption:
Super carbon nano dot embodiment 1 prepared is scattered in deionized water, and configuration concentration is the dispersion liquid of 25,50,100,200ppm respectively, and the dispersion liquid getting the above-mentioned different concns of 1ml is respectively placed in 1*1*4cm
3in quartz cell, do reference with the deionized water of same volume (1ml), irradiate dispersion liquid respectively with 808nm laser, laser power density is preferably 1W/cm
2, test dispersion liquid temperature every 15s in 10min, during 10min, disperse liquid temp to promote 9.6 respectively, 18.9,26.5,35.2 DEG C, the temperature increase of reference deionized water 1.1 DEG C.
Fig. 9 is the temperature variation-time curve of the Superstrong carbon nano dot of different concns in embodiment 10.As can be seen from Figure 9, super carbon nano dot of the present invention has stronger photo-thermal conversion efficiency, and photo-thermal conversion efficiency increases along with the increase of concentration.
Embodiment 11
In conjunction with Figure 10, embodiment 11 is described
There is the application of super carbon nano dot as near infrared photoelectricity changing agent of strong near infrared absorption:
By the super carbon nano dot aqueous dispersions of 100ppm, 808nm laser radiation 12min, to reaching balance with external environment heat exchange, then stops irradiating, records intensification section and temperature descending section dispersion liquid temperature every 15s.
In Figure 10, the super carbon nano dot dispersion liquid that (a) is embodiment 11 is down to the temperature variation-time curve in the process of room temperature after laser radiation to temperature, and (b) bears logarithmic curve for m-cooling motivating force during temperature descending section in this process; Excess of export carbon nano dot photo-thermal conversion efficiency is calculated by the temperature-time curve of intensification section and temperature descending section, method of calculation refer to document (MicroscaleHeatTransferTransducedbySurfacePlasmonResonant GoldNanoparticles, D.K.Roper, W.Ahn, M.Hoepfner, J.Phys.Chem.C, 2007,111,3636), as shown in Figure 10 (b), timeconstantτ
s=345.56s, photo-thermal conversion efficiency is 53.2%.
Embodiment 12
In conjunction with Figure 11, embodiment 12 is described
(1) in 96 orifice plates, by HeLa cell (8*10
3/ hole) in cell culture medium (DMEM), hatch 24h, cell incubation, at 37 DEG C, is incubated in 5%CO
2carry out in incubator;
(2) with the super carbon nano dot dispersion liquid of deionized water configuration, concentration is respectively 0,25,50,100,200,400ppm, and be scattered in respectively in substratum, the HeLa cell in (1) is continued to hatch 24h in the substratum of above-mentioned concentration, after 24h, measures cell survival rate with mtt assay.
Figure 11 is HeLa cell survival rate histogram in the super carbon nano dot of different concns in embodiment 12, can find out, after testing, when super carbon nano dot concentration is increased to 400ppm, HeLa cell survival rate still remains on more than 85%, prove the low bio-toxicity of super carbon nano dot, have further in the potentiality of biologic medical field application.
Embodiment 13
In conjunction with Figure 12, embodiment 13 is described
(1) in 96 orifice plates, by HeLa cell (8*10
3/ hole) in cell culture medium (DMEM), hatch 24h, cell incubation, at 37 DEG C, is incubated in 5%CO
2carry out in incubator;
(2) use 808nm laser at 1W/cm
2power density under irradiate HeLa cell 10min in (1), measure cell survival rate with mtt assay after irradiation;
(3) again with the super carbon nano dot dispersion liquid that deionized water configuration concentration is 100ppm, and be scattered in substratum, HeLa cell in (1) is placed in the substratum of super carbon nano dot dispersion liquid, under the existence of super carbon nano dot, uses 808nm laser at 1W/cm
2power density under irradiate HeLa cell 10min, measure cell survival rate with mtt assay after irradiation.
Figure 12 is that embodiment 13 does not exist with under existent condition at super carbon nano dot, the survival rate of cell after laser radiation, as can be seen from Figure 12, and 1W/cm
2808nm laser radiation ten minutes survival rates on HeLa cell without impact, when super carbon nano dot exists, due to the photo-thermal effect of super carbon nano dot, cancer cells is almost all killed.
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. there is the super carbon nano dot of strong near infrared absorption, it is characterized in that, formed with the carbon nano dot self-assembly of electropositivity functional group and electronegativity functional group by surface simultaneously, in the spectral range of 470-1000nm, there is absorption peak, and the photo-thermal conversion efficiency in this spectral range is 30%-65%.
2. the super carbon nano dot with strong near infrared absorption according to claim 1, is characterized in that, described electropositivity functional group is amino and/or pyrryl, and described electronegativity functional group is one or more in pyridyl, carboxyl, hydroxyl.
3. the super carbon nano dot with strong near infrared absorption according to claim 1, is characterized in that, the absorption peak position of described super carbon nano dot is in the spectral range of 640-715nm, and peak width at half height is distributed in the spectral range of 170-250nm.
4. the super carbon nano dot with strong near infrared absorption according to claim 1, is characterized in that, described surface is prepared with the carbon nano dot of electropositivity and electronegativity functional group simultaneously by the following method:
Step one, by carbon source and urea in mass ratio 2:1-1:4 be dissolved in deionized water, obtain clear solution;
Or, by carbon source and ammoniacal liquor in mass ratio 2:1-1:4 be dissolved in deionized water, obtain clear solution;
Step 2, the clear solution of step one gained is placed in reaction unit, react 4-10h at 160-200 DEG C, reacted solution, after freeze-drying, obtains yellow carbon nano dot powder, is surface simultaneously with the carbon nano dot of electropositivity and electronegativity functional group.
5. the super carbon nano dot with strong near infrared absorption according to claim 4, it is characterized in that, described carbon source is citric acid.
6. the preparation method with the super carbon nano dot of strong near infrared absorption of claim 1-5 described in any one, it is characterized in that, that surface is placed in Aquo System with the carbon nano dot of electropositivity functional group and electronegativity functional group simultaneously, color to carbon nano dot becomes black, the black solid obtained, is super carbon nano dot.
7. the preparation method with the super carbon nano dot of strong near infrared absorption according to claim 6, it is characterized in that, the method also comprises, and by the black solid redispersion that obtains in water, successively after dialysis, freeze-drying, obtains super carbon nano dot.
8. the preparation method with the super carbon nano dot of strong near infrared absorption according to claim 6, it is characterized in that, described Aquo System is the one in the mixing solutions of damp atmosphere, neutral aqueous solution, water and organic solvent.
9. the super carbon nano dot with strong near infrared absorption of claim 1-5 described in any one is as photothermal deformation applications to nanostructures.
10. the application with the super carbon nano dot of strong near infrared absorption according to claim 9, is characterized in that, described super carbon nano dot can as photoacoustic imaging(PAI) contrast medium, photothermal deformation agent or paint additive.
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