CN103421495A - Organic functional luminescent carbon quantum dots, preparation method therefor and applications thereof - Google Patents
Organic functional luminescent carbon quantum dots, preparation method therefor and applications thereof Download PDFInfo
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Abstract
The invention relates to nano optical functional materials, especially relates to an organic functional luminescent carbon quantum dots with high luminescent efficiency, a preparation method therefor and applications thereof. The preparation method employs a single-step pyrolysis synthesis method: organic compounds with a low decomposition temperature (150-300 DEG C) is heated at a temperature of 150-350 DEG C (the organic compounds are generally heated for 1-360min and heating methods comprise organic pyrolysis, hydrothermal method and the like) and subjected to a pyrolytic reaction; organic functional luminescent carbon quantum dots are obtained after post-treatment and purification. Surfaces of carbon quantum dots are modified with organosilane or organic high-molecular compounds with acylamino to form the organic functional luminescent carbon quantum dots. The organic functional luminescent carbon quantum dots can be used as luminescent functional materials, optical functional nano hybrid composite materials or used as biological living cell imaging materials.
Description
Technical field
The present invention relates to the nanometer optical function material, particularly a class has luminous carbon quantum dot and the purposes of the organic functional of high-luminous-efficiency, and the preparation method of the luminous carbon quantum dot of this organic functional.
Background technology
Since two thousand six, luminous carbon quantum dot, as a very attracting class in graphite and decolorizing carbon nanoparticle, due to its application tempting at aspects such as opto-electronic device and biomarkers, is subject to scientist's extensive concern (Angew.Chem.Int.Ed.2010,49,6726).With traditional organic dye, with semiconductor-quantum-point, compare, the advantage of luminous carbon quantum dot is unreactiveness, large two-photon excitation cross section, hypotoxicity and excellent biocompatibility (J.Am.Chem.Soc.2007,129,11318; 2009,131,11308; J. Phys.Chem.C2009,113,18110; 2010,114,12062).The biomacromolecules such as the particle size of carbon quantum dot and albumen, nucleic acid are suitable, and less particle size is conducive to organism and by metabolic mode, unnecessary quantum dot is excreted.Therefore, will there is higher using value aspect the tracking of small scale carbon luminescent quantum dot ubcellular process in medical diagnosis, organism inner tissue cell imaging, viable cell.
The method of synthetic carbon quantum dot can be divided into two large classes usually: top-down methods and method from bottom to top.Top-down methods is peeled off based on various larger carbon structures the nano-sized carbon obtained and is carried out aftertreatment, as laser ablation method, electrochemical erosion method (J.Am.Chem.Soc.2006,128,7756; 2007,129,744; 2009,131,4564; J.Phys.Chem.C2008,112,18295; J.Mater.Chem.2009,19,484; ACS Nano 2009,3,2367; Chem.Commun.2008,5116; J.Phys.Chem.B, 2006,110,831; Adv.Mater.2010,22,734).Method comprises thermolysis (Chem.Mater.2008,20,4539 of suitable molecular precursor from bottom to top; 2010,22,4528; Small 2008,4, and 455; Angew.Chem.2007,119,6593; J.Phys.Chem.C 2009,113, and 18546; Chem.Commun.2010,46,3309; 3681; 2009,5118), sulfuric acid dehydration for carbohydrate, hydrothermal synthesis method (Angew.Chem.2009,121,4668; Chem.Mater.2009,21,5563; New J.Chem.2010,34,591) etc.Usually, these methods comprise complicated process and harsh synthesis condition, are difficult to realize the isoparametric relatively independent control of quantum dot size, structure and surface property.The more important thing is, the luminescent quantum productivity ratio obtained lower (<15%), carbon quantum dot macroscopic view block and film almost have no report at present.
Summary of the invention
One of purpose of the present invention is to provide the luminous carbon quantum dot that a class has the organic functional of high-luminous-efficiency.
Two of purpose of the present invention is to provide the preparation method of luminous carbon quantum dot that a class has the organic functional of high-luminous-efficiency.
Three of purpose of the present invention is to provide the purposes of luminous carbon quantum dot that a class has the organic functional of high-luminous-efficiency.
The luminous carbon quantum dot of organic functional of the present invention is obtained by the pyrolysis preparation method: the organic compound that will hang down decomposition temperature (150～300 ℃) is that under 150～350 ℃, heating (is generally heated 1～360 minute in temperature; Type of heating comprises organic pyrolysis, hydro-thermal etc.) carry out pyrolytic reaction, purify and obtain the luminous carbon quantum dot of described organic functional through aftertreatment.
The luminous carbon quantum dot of organic functional of the present invention is a kind of ultra-fine carbon nano-particles of amorphous structure, and its particle diameter is 1～10 nanometer; The luminous carbon quantum dot of described organic functional is that the finishing at the carbon quantum dot has organosilane or with the organic high molecular compound of amide group.
The luminous carbon quantum dot of described organic functional can send blue light or green glow (as shown in Figure 1) under illumination, and wherein the wavelength of illumination is 300～1064nm, and corresponding luminescence center wavelength is 400～550nm; The luminous quantum efficiency of the luminous carbon quantum dot of described organic functional is up to 10～60%, and the luminous carbon quantum dot of described organic functional is for a long time repeatedly luminous after illumination; The luminous carbon quantum dot of described organic functional is very soluble in water and common are in the machine solvent.
Described pyrolytic reaction can complete the soonest in 1 minute.Wherein the luminous carbon quantum dot of organosilane functionalization can conveniently be combined into the nano-hybrid material of several functions, as the luminous carbon quantum dot/silicon dioxide hybrid materials (CDs/Silica, lower same) obtained after the coated silica layer can be for the active somatic cell video picture.But that this is a class formation is novel, easy to prepare, luminous efficiency is high, stable Reusability, nontoxic, "dead", produce and use the luminous carbon quanta point material of safe height.Interestingly, due to the low-cost of organosilane with the several functions group, this brand-new convenience and the synthetic route easily repeated will provide the new way of a kind of synthesized semiconductor, metal/nanometer crystalline substance and nano composite material thereof.
Described organosilane is organo silane coupling agent; Described organo silane coupling agent includes but not limited to a kind of with in the amino silicane coupling agent of the silica-based group of two to three alcoxyls, imino-silane coupling agent, epoxy silane coupling and mercaptosilane coupling agents etc.
The described organic high molecular compound with amide group is selected from the derivative of derivative, amide group titanate coupling agent, the amide group titanate coupling agent of the derivative of organic alkyl amide compound, organic alkyl amide compound, polynary amide compound, aromatic amides, aromatic amides, with the polymkeric substance of amide group with one or more in the derivative of the polymkeric substance of amide group.
Described organic alkyl amide compound is selected from one or more in the hydrocarbyl amide of carbonatoms≤18.
Described polynary amide compound is selected from one or more in the amido derivatives of the amido derivatives of amido derivatives, triethylene tetramine of the alkyl diamine of carbonatoms≤18 and tetraethylene pentamine.
Described aromatic amides is dodecanoyl amido aniline, phenyl stearylamide or their mixture etc.
The described polymkeric substance with amide group is amide group silicone oil, amide group polyoxyethylene glycol or their mixture etc.
The preparation method of the luminous carbon quantum dot of organic functional of the present invention includes but not limited to a step pyrolysis synthesis method:
By organosilane or degassed with nitrogen with amino organic high molecular compound after be warmed up to 150～350 ℃ (preferably 200～300 ℃) by room temperature, at this temperature, the organic compound that is 150～300 ℃ by decomposition temperature join above-mentioned with nitrogen the organosilane after degassed or with in amino organic high molecular compound, carry out organic pyrolytic reaction (time of general organic pyrolytic reaction is 1～120 minute), after completing, organic pyrolytic reaction purified, obtain that finishing at the carbon quantum dot has organosilane or with the luminous carbon quantum dot of the organic functional of the organic high molecular compound of amide group,
Wherein, organic compound and organosilane or the organic compound that is 0.1～3 gram with the ratio of amino organic high molecular compound: the organosilane of 10 milliliters or with amino organic high molecular compound;
Or
The mixing solutions of the second alcohol and water of the organic compound that will to contain decomposition temperature be 150～300 ℃ is to carry out hydrothermal treatment consists (time of generally carrying out hydrothermal treatment consists is 1～6 hour) under 150～250 ℃ in temperature, then extracted after dialysis or acidifying are purified and obtained the carbon quantum dot, the carbon quantum dot obtained reacts with the organic high molecular compound with amino and carries out organic surface-functionalizedly, and obtaining finishing at the carbon quantum dot has the luminous carbon quantum dot with the organic functional of the organic high molecular compound of amide group;
The concentration of the organic compound in described mixing solutions is 0.01～0.55 grams per milliliter (being preferably 0.055 grams per milliliter), and the ethanol in described mixing solutions and the volume ratio of water are 1: 1;
Described carbon quantum dot is 1: 0.5～2 with the mass ratio with amino organic high molecular compound.
The organic compound that described low decomposition temperature is 150～300 ℃ includes but not limited to be selected from one or more in the derivative of organic multicomponent acid, amino acid, carbohydrate and carbohydrate.
Described organic multicomponent acid includes but not limited to be selected from one or more in gluconic acid, lactic acid, citric acid and phthalic acid.
Described amino acid includes but not limited to be selected from one or more in Methionin, glycine and aspartic acid.
Described carbohydrate is carbohydrate (fructose, glucose, sucrose etc.) compound.
Described organosilane is organo silane coupling agent; Described organo silane coupling agent includes but not limited to a kind of with in the amino silicane coupling agent of the silica-based group of two to three alcoxyls, imino-silane coupling agent, epoxy silane coupling and mercaptosilane coupling agents etc.
Described with amino organic high molecular compound include but not limited to be selected from the derivative of derivative, polyamine compound, the aromatic amine compound of organic hydrocarbon ylamine compounds, organic hydrocarbon ylamine compounds, the derivative of aromatic amine compound, amino titanate coupling agent, amino titanate coupling agent, with amino polymkeric substance with one or more in the derivative of amino polymkeric substance.
Described organic hydrocarbon ylamine compounds includes but not limited to be selected from one or more in the alkylamine of carbonatoms≤18.
Described polyamine compound includes but not limited to be selected from one or more in alkyl diamine, triethylene tetramine and the tetraethylene pentamine of carbonatoms≤18.
Described aromatic amine compound includes but not limited to it is ten diamino aniline, phenyl stearylamine or their mixture.
Describedly with amino polymkeric substance, include but not limited to it is amido silicon oil or amino polyoxyethylene glycol or their mixture.
The luminous carbon quantum dot of organic functional of the present invention can be as the lighting function materials'use, as the use of light function nano hybrid composite material or as living organisms cell imaging materials'use.
The luminous carbon quantum dot of organic functional of the present invention can be under illumination (wavelength 300～1064nm) excites, can show bright blue light or green emission light wave (wavelength 400～550nm) according to the kind of different exciting lights and carbon quantum dot, keep luminous at least two years under indoor conditions.The organosilane functionalization that wherein the luminous carbon quantum dot of organosilane functionalization obtains after the coated silica layer again luminous carbon quantum dot/silica dioxide composite particles hybrid material (CDs/Silica) can be for the living organisms cell imaging.Under ultraviolet excitation, the carbon quantum dot of preparation or its film, block show bright blue emission, and can under indoor conditions, keep luminous at least two years.
The luminous carbon quantum dot of organic functional of the present invention can be used as the object of light function nano hybrid material.Under ultraviolet excitation, the luminous carbon quantum dot of prepared organosilane functionalization or the luminous carbon quantum dot/silica dioxide composite particles of organosilane functionalization show bright blue emission (Fig. 1-2), under indoor conditions, keep luminous at least two years.Comparing advantage with dyestuff or semiconductor-quantum-point also has: the chemical stability that preparation process is simple, high, more homogeneous and hypotoxicity.Therefore, the luminous carbon quantum dot the present invention relates to is very potential to be become the luminous embedded material that a class is new and prepares luminescent device.When biological assessment, the concentration of CDs/Silica, apparently higher than the required concentration of the biological video picture of active somatic cell, therefore has the longer time shutter.This shows the unreactiveness of CDs/Silica, even also do not discharge the chemical substance of any toxicity under harsh and unforgiving environments, particularly with the Cytotoxic CdSe based quantum dot of the typical participation of having reported, compares and has advance.
The luminous carbon quantum dot of organic functional of the present invention can be used as light function nano hybrid material, can use as the living organisms cell imaging, although (with reference to the Tsang method, (Small 2005 for the CDs/Silica composite particles of preparation, 1,949) luminous quantum efficiency preparation) descends to some extent, but the absorption emmission spectrum of CDs/Silica is identical with carbon quantum dot pure before the coated silica layer, prove that structure and the stability of luminescent properties in this process of the luminous carbon quantum dot of organic functional of the present invention keeps fine.The about 12nm of the particle diameter of this CDs/Silica, wherein most particles are pellet shapes, are the ideal dimensions of clinical application.
Described CDs/Silica can be for the experiment of biological video picture, and the BGC823 cell is cultivated according to the rule of having set up.Exciting and bright field image of 360nm laser, CDs/Silica can observe strong optical signalling.MMT method bio-toxicity and the detection of CDs/Silica show, CDs/Silica is unreactiveness, even also do not discharge any poisonous chemical substance under harsh and unforgiving environments, particularly with what reported, has the typical case to participate in Cytotoxic CdSe based quantum dot to compare.Can be observed the optical signalling that CDs/Silica is strong in biological video picture experiment, do not observe the cellular form damage, further confirm its low cytotoxicity.In addition, phosphor dot only arrives at the tenuigenin area observation of cell, nucleus fluorescence intensity corresponding to central region very a little less than, show that CDs/Silica passes cell but do not enter nucleus.This interactional result of study with active cells and nano material is consistent, heredity does not occur and destroy (seeing Fig. 3～4).
The luminous carbon quantum dot of the organic functional of high-luminous-efficiency of the present invention has been compared following advantage with existing other carbon quantum dot:
One, the characteristics of luminescence: the luminous carbon quantum dot of organic functional of the present invention can send blue light or green glow (centre wavelength 400～550nm) under rayed, luminous quantum efficiency is 10～60%, and for a long time repeatedly luminous after illumination, soluble in water and common are the machine solvent, this be a kind of easy to prepare, luminous efficiency is high, stablize repeatedly used luminous carbon CdS quantum dots.
Two, novel structure: the carbon quantum dot of the ultra-fine amorphous structure that the luminous carbon quantum dot of organic functional of the present invention is a kind of organic coupling, surface band has the organic functional group of functionalization, its particle diameter is 1～10 nanometer, than current bibliographical information to pass through the carbon quantum dot that burning/pyrolytic process obtains little a lot.This should be owing to the accelerated surface passivation reaction, also causes the high luminous quantum efficiency of luminous carbon quantum dot of the organic functional that obtains simultaneously.Under ultraviolet excitation, the luminous carbon quantum dot of organic functional prepared by the present invention and the luminous carbon quantum dot/silica dioxide composite particles of organic functional show bright blue emission, and can under indoor conditions, keep luminous at least two years.
Three, preparation method's novelty, with low cost, with the method for having reported, compares, and the liquid phase method for pyrolysis that the present invention uses is more easily realized size, structure and the morphology control of particle by the adjustment of parameter etc.The present invention adopts the organic compound of low decomposition temperature (150～300 ℃) as main raw material, prepares the carbon quantum dot with other and compares, and material cost is cheaper to be easy to get.Synthetic route belongs to one-step synthesis, except heating installation, does not need to use other complicated exacting terms and equipment.
Four, workability energy: the luminous carbon quantum dot of the organic functional that the present invention obtains, all there is good solvability in common organic solvent, water and organosilane, the carbon quantum dot that wherein organosilane and polyamine functional obtain is the carbon quantum dot of mobility, can be miscible with above-mentioned solvent and silane, there is good processability.
Five, biologically inert and video picture characteristic: nontoxic, "dead", produce and use safety, the luminous carbon quantum dot of organic functional of the present invention is highly stable in a large amount of non-aqueous solution, by silane group be hydrolyzed and with silicon-dioxide performed polymer cocondensation, can further make the luminescent nanoparticle of coated with silica for biomarker and video picture.The particle diameter of the luminescent quantum dot of this coated with silica is 12 nanometers approximately, highly stable, can water-dispersion, and can carry out the biomaterial functionalization by silicon dioxide layer.The result proof CDs/Silica of biological assessment is nontoxic really, and can carry out biological video picture by fluorescent microscope, these all illustrate that CDs/Silica has competition comparability (Adv.Mater.2006,18,1953) with developing now good CdSe/ZnS quantum dot.
Six, hybridization compounding performance: with multiple organic functional group, easily can covalent linkage be connected to surface or the interface of organic polymer material due to the luminous carbon quantum dot of organic functional of the present invention, form multiple hybrid composite material.For example embodiment 1 by silane group, be hydrolyzed and with silicon-dioxide performed polymer cocondensation, can further make the luminescent nanoparticle of coated with silica, thus for the biomass cells video picture.
The accompanying drawing explanation
Fig. 1. the luminous photo of luminous carbon quantum dot SCQD1 ethanolic soln under UV-irradiation of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Fig. 2. the photo of silicon/carbon dioxide quantum dot composite particles under visible ray and UV-irradiation prepared by the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Fig. 3. the silicon/carbon dioxide quantum dot composite particles that the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1 makes, with the toxicity variation diagram (after processing in 48 hours) of three kinds of different clones of MMT method detection.
Fig. 4 (a), (b). the silicon/carbon dioxide quantum dot composite particles that the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1 makes is the biological video picture photo after 24 hours for the BGC823 cell cultures: (a) bright field photo; (b) fluorescence photo after the laser excitation of 360nm wavelength.
Fig. 5. Fourier transform infrared spectroscopy (FTIR) figure of luminous carbon quantum dot SCQD1, the AEAPMS of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Fig. 6. the luminous carbon quantum dot SCQD1's of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1
13The C-NMR nuclear magnetic spectrogram.
Fig. 7. luminous carbon quantum dot SCQD1 uv-visible absorption spectra figure and the fluorescence spectrum figure under different excitation wavelengths of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Fig. 8. the distribution of sizes histogram of dynamic light scattering (DLS) test of the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Fig. 9. the Raman spectrogram of the luminous carbon quantum dot SCQD1 of the AEAPMS of the embodiment of the present invention 1 and the organic functional of high-luminous-efficiency.
Figure 10. X-ray diffraction (XRD) collection of illustrative plates of the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Figure 11. silicon/carbon dioxide quantum dot composite particles prepared by the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1 is in the aqueous solution, and uv-absorbing and fluorescence spectrum under the exciting of the light of 340～480nm wavelength, increasing degree is 20cm.
Figure 12. the transmission electron microscope photo of silicon/carbon dioxide quantum dot composite particles prepared by the luminous carbon quantum dot SCQD1 of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 1.
Figure 13. the transmission electron microscope photo of the luminous carbon quantum dot of the organic functional of the high-luminous-efficiency of the embodiment of the present invention 5.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but be not to concrete restriction of the present invention.
The preparation of the luminous carbon quantum dot SCQD 1 of organic functional: under room temperature, add 10 milliliters of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (AEAPMS) in the 100ml there-necked flask, degassed 5 minutes of nitrogen; At logical nitrogen with under stirring, be warmed up to 270 ℃, add fast 0.1g lactic acid in system, at this temperature, keep 1 minute, the product obtained naturally cools to room temperature, and recrystallization separates after (normal hexane: the volume ratio of methylene dichloride is 2: 1) purifies the luminous carbon quantum dot SCQD1 that obtains the organic functional of high-luminous-efficiency with post.
The luminous carbon quantum dot of described organic functional is that surface at the carbon quantum dot is with N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
Ultimate analysis measured value: C, 45.81; H, 8.87; N, 13.65.Infrared spectrum and
13The C-NMR nuclear magnetic spectrogram is respectively shown in Fig. 5 and Fig. 6.Fourier transform infrared spectroscopy (FTIR) shows that C=ONR is at 1654cm
-1The generation (as Fig. 5) of characteristic feature peak proof acylation reaction.Further evidence can from
13Chemical shift 171ppm on C-NMR is attributed to the C=ONR key and proves.Uv-visible absorption spectra (as Fig. 7) shows, at 360nm, obvious charateristic avsorption band is arranged, when the optical excitation with in 340～400nm wavelength region, this luminous carbon quantum dot demonstrates strong blue-fluorescence (as Fig. 1), the centre wavelength of fluorescence spectrum is 450nm, peak width at half height (FWHM) is low to moderate 60nm, further improve excitation wavelength, the emission displacement of SCQD1 in different solvents is from 450nm to 530nm, and luminous quantum efficiency is that 60%(is as Fig. 7).The distribution of sizes of this luminous carbon quantum dot also can characterize by dynamic light scattering (DLS), and Fig. 8 shows that the size of particles of SCQD1 is about 1.4nm in ethanol.Raman spectrum (Fig. 9) shows, this luminous carbon quantum dot has weak G band, shows that it is metamict.In addition, XRD test (Figure 10) provides the wide reflection of Liao Yige center at 4.3A, and the state of disarray of carbon is described, the result of this and Raman spectrum and front meets fully.
The preparation of luminous carbon quantum dot SCQD1/ silica dioxide composite particles CDs/Silica: the above-mentioned luminous carbon quantum dot SCQD1 prepared of 0.2mL is under agitation joined in 200mL ethanol, then the sodium silicate aqueous solution (1.5wt%) and the 0.2mL tetraethoxy (mass concentration 98%) that add 3mL, finally little by little add the ammoniacal liquor (aqueous solution that mass concentration is 27%) of 0.5mL to obtain mixture; Mixture under agitation reacts and within three days, obtains product C Ds/Silica.Under ultraviolet excitation, the CDs/Silica of preparation shows bright blue emission, and can under indoor conditions, keep luminous at least two years (as Fig. 2).The uv-absorbing of product C Ds/Silica and fluorescence spectrum are as Figure 11, although the luminous efficiency of CDs/Silica descends to some extent, but it is identical that absorption emmission spectrum and the silicon-dioxide of CDs/Silica do not coat front pure luminous carbon quantum dot SCQD1, prove that the structure of luminescent quantum dot of described organic functional and the stability of luminescent properties in this process keep fine.The transmission electron microscope photo of CDs/Silica as shown in figure 12, can find out that most particles are little and spherical.The particle diameter of the luminous carbon quantum dot of this coated with silica is 12 nanometers approximately, are the ideal dimensions of clinical application, show in a particle to have wrapped up several carbon quantum dots.Its dynamic light scattering test shows that the aqueous solution announcement of CDs/Silica is mainly about 15nm, meets with the TEM observed result.Further EDX shows that the weight ratio of C/Si is 2.45, slightly lower than the weight ratio of pure SCQD1, confirms the hydrolyzing/condensing process of SCQD1 and silicon precursor.Forming another evidence of silicon dioxide layer is specific Si-O-Si asymmetric stretch peak (1090cm in FTIR spectrum
-1).
The test of mtt assay bio-toxicity and biological video picture experiment adopt universal method to carry out.In order to estimate the physiology toxicity of the above-mentioned CDs/Silica prepared, use the MMT method to detect three kinds of different clones: people's cancer of the stomach BGC823 cell, rat liver cancer H22 cell, rat brain glioma C6 cell.As shown in Figure 3: all cells are to change the CDs/Silica amount (never be added to and add 100 μ g/mL) added, and do not add up difference significantly.It is worthy of note that the concentration of when biological assessment CDs/Silica, apparently higher than the required concentration of the biological video picture of active somatic cell, therefore has the longer time shutter.This shows that CDs/Silica is unreactiveness, even also do not discharge the chemical substance of any toxicity under harsh and unforgiving environments, with the CdSe based quantum dot, compares especially, has reported typical participation cytotoxicity.
Experiment at CDs/Silica for biological video picture, the BGC823 cell is cultivated according to the rule of having set up.As bright field, (Fig. 4 is a) and as shown in the image photograph of the laser excitation (Fig. 4 b) of 360nm wavelength, and CDs/Silica can observe strong optical signalling.Especially, do not observe the cellular form damage, further confirm its low cytotoxicity.In addition, phosphor dot only arrives at the tenuigenin area observation of cell, nucleus fluorescence intensity corresponding to central region be very a little less than, show that CDs/Silica passes cell but do not enter nucleus.This is also consistent with the interaction result of the research active cells of bibliographical information and nano material, heredity occurs and destroy.
Embodiment 2.
The preparation of the luminous carbon quantum dot SCQD2 of organic functional: under room temperature, add 50 milliliters of aminopropyl triethoxysilanes in the 500ml there-necked flask, degassed 15 minutes of nitrogen; At logical nitrogen with under stirring, be warmed up to 350 ℃, add fast the 8g gluconic acid in system, at this temperature, keep 30 minutes, the product obtained naturally cools to room temperature, and recrystallization separates after (normal hexane: the volume ratio of ethyl acetate is 2: 1) purifies the luminous carbon quantum dot SCQD2 that obtains the organic functional of high-luminous-efficiency with post.The surface of SCQD2 is with aminopropyl triethoxysilane, and particle diameter is 4.5 nanometers.When the optical excitation with the 360nm wavelength, SCQD2 demonstrates strong blue-fluorescence, and the centre wavelength of fluorescence spectrum is 450nm, and peak width at half height (FWHM) is low to moderate 60nm, and luminous quantum efficiency is 45%.
Embodiment 3.
The preparation of the luminous carbon quantum dot SCQD3 of organic functional: under room temperature, add 50 milliliters of γ-glycidyl ether oxygen propyl trimethoxy silicanes in the 500ml there-necked flask, degassed 15 minutes of nitrogen; At logical nitrogen with under stirring, be warmed up to 300 ℃, add fast the 8g phthalic acid in system, at this temperature, keep 30 minutes, the product obtained naturally cools to room temperature, and recrystallization separates after (normal hexane: the volume ratio of ethyl acetate is 3: 1) purifies the luminous carbon quantum dot SCQD3 that obtains the organic functional of high-luminous-efficiency with post.The surface of SCQD3 is with aminopropyl triethoxysilane, and particle diameter is 1.5 nanometers.When the optical excitation with in 340～400nm wavelength region, SCQD3 demonstrates strong blue-fluorescence, and luminous quantum efficiency is 15%.
Embodiment 4.
The preparation of the luminous carbon quantum dot CQD4 of organic functional: under room temperature, add 10 milliliters of triethylene tetramines in the 100ml there-necked flask, degassed 5 minutes of nitrogen; At logical nitrogen with under stirring, be warmed up to 260 ℃, add fast 3g glucose in system, at this temperature, keep 10 minutes, the product obtained naturally cools to room temperature, and recrystallization separates after (normal hexane: the volume ratio of ethyl acetate is 3: 1) purifies the luminous carbon quantum dot CQD 4 that obtains the organic functional of high-luminous-efficiency with post.The surface of CQD 4 is with triethylene tetramine, and particle diameter is 10 nanometers.When the optical excitation with in 340～400nm wavelength region, CQD 4 demonstrates strong blue-fluorescence, and luminous quantum efficiency is 28%.
The preparation of the luminous carbon quantum dot CQD5 of organic functional: under room temperature, get 1.1g glucose and dissolve in the 10ml deionized water, add 10ml ethanol to stir and form the bubble-free solution of homogeneous, in the water heating kettle of 40ml, under 150 ℃, reaction is 4 hours, then naturally cools to room temperature.Extract 3～4 times, in water, dialysis obtains containing the yellow carbon quantum dot aqueous solution in two days, the polyoxyethylene glycol that is 2 by the mass ratio of gained carbon quantum dot and polyoxyethylene glycol again carries out organic surface-functionalized in room temperature reaction, obtain the luminous carbon quantum dot CQD 5 of organic functional.The surface of CQD 5 is with polyoxyethylene glycol, and particle diameter is about 2.0～2.5nm; Transmission electron microscope photo as shown in figure 13.When the optical excitation with in 300～400nm wavelength region, CQD 5 demonstrates strong blue-fluorescence, and luminous efficiency is 10.1%.
Embodiment 6.
The preparation of the luminous carbon quantum dot CQD6 of organic functional: get 1.1g glucose and dissolve in the 10ml deionized water, add 10ml ethanol to stir and form the bubble-free solution of homogeneous, utilize hydrothermal method, in 150～250 ℃ of high-temperature water thermal treatment glucose 6 hours, forming particle diameter is the carbon ball particle of 1 μ m left and right, then gained carbon ball particle is placed in to the concentrated nitric acid that mass concentration is 98% and carries out acidifying under 80 ℃, form the aqueous solution that contains yellow carbon quantum dot.The polyoxyethylene glycol that is 0.5 by the mass ratio of gained carbon quantum dot and polyoxyethylene glycol again carries out organic surface-functionalized in room temperature reaction, obtain the luminous carbon quantum dot CQD 6 of the organic functional of high-luminous-efficiency, and particle diameter is the 10nm left and right; The surface of CQD 6 is with polyoxyethylene glycol, and when the optical excitation with in 300～400nm wavelength region, CQD 6 demonstrates strong blue-fluorescence, and luminous efficiency is 15%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (10)
1. the luminous carbon quantum dot of an organic functional, it is a kind of carbon nano-particles of amorphous structure, it is characterized in that: the luminous carbon quantum dot of described organic functional is that the finishing at the carbon quantum dot has organosilane or with the organic high molecular compound of amide group.
2. the luminous carbon quantum dot of organic functional according to claim 1, it is characterized in that: the luminous carbon quantum dot of described organic functional sends blue light or green glow under illumination; Wherein the wavelength of illumination is 300～1064nm.
3. the luminous carbon quantum dot of organic functional according to claim 1 and 2, it is characterized in that: the particle diameter of the luminous carbon quantum dot of described organic functional is 1～10 nanometer.
4. the luminous carbon quantum dot of organic functional according to claim 1, it is characterized in that: described organosilane is organo silane coupling agent;
The described organic high molecular compound with amide group is selected from the derivative of derivative, amide group titanate coupling agent, the amide group titanate coupling agent of the derivative of organic alkyl amide compound, organic alkyl amide compound, polynary amide compound, aromatic amides, aromatic amides, with the polymkeric substance of amide group with one or more in the derivative of the polymkeric substance of amide group.
5. the luminous carbon quantum dot of organic functional according to claim 4 is characterized in that: described organo silane coupling agent is selected from a kind of in amino silicane coupling agent, imino-silane coupling agent, epoxy silane coupling and mercaptosilane coupling agents;
Described organic alkyl amide compound is selected from one or more in the hydrocarbyl amide of carbonatoms≤18;
Described polynary amide compound is selected from one or more in the amido derivatives of the amido derivatives of amido derivatives, triethylene tetramine of the alkyl diamine of carbonatoms≤18 and tetraethylene pentamine;
Described aromatic amides is dodecanoyl amido aniline, phenyl stearylamide or their mixture;
The described polymkeric substance with amide group is amide group silicone oil, amide group polyoxyethylene glycol or their mixture.
6. the preparation method according to the luminous carbon quantum dot of the described organic functional of claim 1～5 any one is characterized in that:
By organosilane or degassed with nitrogen with amino organic high molecular compound after be warmed up to 150～350 ℃ by room temperature, at this temperature, the organic compound that is 150～300 ℃ by decomposition temperature join above-mentioned with nitrogen the organosilane after degassed or with in amino organic high molecular compound, carry out organic pyrolytic reaction, purified after organic pyrolytic reaction completes, obtained that finishing at the carbon quantum dot has organosilane or with the luminous carbon quantum dot of the organic functional of the organic high molecular compound of amide group;
Wherein, organic compound and organosilane or the organic compound that is 0.1～3 gram with the ratio of amino organic high molecular compound: the organosilane of 10 milliliters or with amino organic high molecular compound;
Or
The mixing solutions of the second alcohol and water of the organic compound that will to contain decomposition temperature be 150～300 ℃ is to carry out hydrothermal treatment consists under 150～250 ℃ in temperature, then extracted after dialysis or acidifying are purified and obtained the carbon quantum dot, the carbon quantum dot obtained reacts with the organic high molecular compound with amino and carries out organic surface-functionalizedly, and obtaining finishing at the carbon quantum dot has the luminous carbon quantum dot with the organic functional of the organic high molecular compound of amide group;
The concentration of the organic compound in described mixing solutions is 0.01～0.55 grams per milliliter, and the ethanol in described mixing solutions and the volume ratio of water are 1: 1;
Described carbon quantum dot is 1: 0.5～2 with the mass ratio with amino organic high molecular compound.
The organic compound that described decomposition temperature is 150～300 ℃ is selected from one or more in the derivative of organic multicomponent acid, amino acid, carbohydrate and carbohydrate.
7. preparation method according to claim 6, it is characterized in that: described organic multicomponent acid is selected from one or more in gluconic acid, lactic acid, citric acid and phthalic acid;
Described amino acid is selected from one or more in Methionin, glycine and aspartic acid;
Described carbohydrate is sugar compounds.
8. preparation method according to claim 6, it is characterized in that: described organosilane is organo silane coupling agent;
Described with amino organic high molecular compound be selected from the derivative of derivative, polyamine compound, the aromatic amine compound of organic hydrocarbon ylamine compounds, organic hydrocarbon ylamine compounds, the derivative of aromatic amine compound, amino titanate coupling agent, amino titanate coupling agent, with amino polymkeric substance with one or more in the derivative of amino polymkeric substance.
9. preparation method according to claim 8 is characterized in that: described organo silane coupling agent is selected from a kind of in amino silicane coupling agent, imino-silane coupling agent, epoxy silane coupling and mercaptosilane coupling agents;
Described organic hydrocarbon ylamine compounds is selected from one or more in the alkylamine of carbonatoms≤18;
Described polyamine compound is selected from one or more in alkyl diamine, triethylene tetramine and the tetraethylene pentamine of carbonatoms≤18;
Described aromatic amine compound is ten diamino aniline, phenyl stearylamine or their mixture;
Described is amido silicon oil or amino polyoxyethylene glycol or their mixture with amino polymkeric substance.
10. the purposes according to the luminous carbon quantum dot of the described organic functional of claim 1～5 any one is characterized in that: the luminous carbon quantum dot of described organic functional is as the lighting function materials'use, used or as living organisms cell imaging materials'use as light function nano hybrid composite material.
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