CN102719248B - Aqueous phase silicon carbide quantum dot and preparation method and application thereof - Google Patents
Aqueous phase silicon carbide quantum dot and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of biological application of quantum dots, in particular to a non-cytotoxicity aqueous phase silicon carbide quantum dot and a preparation method thereof, and application of the quantum dot as a fluorescent material. The preparation method comprises the following steps: firstly, corroding homogeneous nano beta-SiC particles synthesized by auto-combustion into a mesh structure with corrosive liquid prepared by mixing nitric acid and hydrofluoric acid; secondly, smashing the structure by the cavitation effect of an ultrasonic wave to form silicon carbide nano particles of different sizes; and finally, centrifuging the silicon carbide nano particles at a high speed to obtain quantum dots with controllable sizes, and applying the quantum dots to the fluorescent labeling and imaging of living cells successfully for the first time. The process is simple, the cost is low and the process parameters are easy to control; besides, the prepared quantum dots are non-toxic, excellent in biocompatibility, and obvious in photoluminescence effect, and can be applied to the fluorescent labeling of living cells for a long time.
Description
Technical field
The present invention relates to the biologic applications technical field of quantum dot, be specifically related to a kind of no cytotoxicity water silicon carbide quantum dot and preparation method thereof, and this quantum dot is in the application in active somatic cell fluorescent mark.
Background technology
Follow the development of the nano-carbon materials such as C60, CNT (carbon nano-tube) and Graphene, quantum dot is due to its remarkable fluorescence property with in the widespread use of biomedical sector, become gradually the focus of people's research, its synthetic method is mainly divided into organic synthesis and water-based is synthetic.The quantum dot of organic synthesis, owing to not possessing wetting ability, therefore can not directly apply to living things system, must carry out finishing and biological functional processing to it, operating process complexity, and conditional request is higher; The method of the synthetic quantum dot of water, due to green, inexpensive, more and more comes into one's own, about the research work of this respect makes fast progress.
Up-to-date result of study shows, there is the poisonous element such as Cd, Se in the quantum dot generally adopting at present, although there are some researches show through the quantum dot toxicity of surface parcel and can greatly reduce, the murder by poisoning enrichment on life entity and active somatic cell, the physiological impact of the long-time section growth of tissue still be can not be ignored.Meanwhile, the toxicant in quantum dot raw material and preparation process all has detrimentally affect to environment and operator.In addition, to be difficult to Effective Regulation be also the important factor that further develops of this Bio-Nano-Materials of restriction to quantum dot size structure.Therefore, utilize water method to prepare the controlled quanta point material of no cytotoxicity, surface tissue and size and become the common recognition of biology at present and material educational circles.
Summary of the invention
In order to overcome the above problems, the invention provides a kind of water silicon carbide quantum dot and preparation method thereof, and by its successful first Application in active somatic cell fluorescent dye.
In water silicon carbide quanta point material of the present invention, silicon carbide quantum dot concentration is 0.03-0.06mol/L, and it is closely spherical that quantum dot is, and diameter is 2-5nm.In order to adapt to the application of this material of later stage on active somatic cell, the pH value of this water silicon carbide quanta point material is 6.4-6.8.
Its concrete steps of preparing are:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stirring reaction, β-SiC grain diameter is 50-100nm;
C. by the mixture standing and reacting in step B;
D. after said mixture is centrifugal, extract corrosive fluid out, add high purity water, the SiC particle after utilizing high purity water to corrosion carries out eccentric cleaning;
E. the aqueous solution after eccentric cleaning is carried out to supersound process;
F. the aqueous solution through supersound process is carried out to centrifugal treating, get supernatant liquor and be silicon carbide Quantum Dot Labeling material, centrifugal speed is 2800-3000rpm.
First, the present invention is diluted to suitable concentration by commercial concentrated nitric acid and hydrofluoric acid with high purity water, and is configured to corrosive fluid.Contriver passes through many experiments and proves, the hydrofluoric acid after dilution and the optimum proportion of salpeter solution are 3:1, because the corrosion process in later stage is exothermic process, if the proportioning of two kinds of acidic solutions exceedes this ratio, react very violent, the more difficult control of experimentation; If lower than this ratio, react comparatively slow, the quantum dot finally obtaining is less.
The raw material that the present invention adopts is the synthetic homogeneous nano β-SiC particle (Physical Chemistry Technology Inst., Chinese Academy of Sciences provides) of self-propagating combustion, why select the synthetic β-SiC particle of self-propagating combustion, because cooling rapidly in its self-propagating combustion reaction process, thereby form non-equilibrium crystallization condition, make β-SiC particle surface form more defect (lattice distortion etc.), activity is higher, corrosion intensity of activation is lower, very easily in hydrofluoric acid solution, corrosion forms fenestral fabric, this structure is the later stage to obtain tiny nearly spherical quantum dot by ultrasonic cavitation to have established condition.In addition, the nitric acid in corrosive fluid of the present invention has oxidisability, has further strengthened the corrosive nature of corrosive fluid, has reached better corrosive effect.The method has been abandoned SiC prepared by chemical synthesis and must have been adopted the galvanic corrosion could to form the tradition of quantum dot nano-particle.
β-SiC grain diameter is less, the fenestral fabric of more perishable one-tenth open type, and the quantum dot quantity of acquisition is more, and quantum yield is approximately high; If particle diameter is too large, can not be etched into fenestral fabric, the quantum dot of formation is less.In order to obtain quantum dot more and that particle diameter is controlled, β-SiC grain diameter is 50-100nm.
In experimentation, find, in the time that β-SiC particle is placed in corrosive fluid, can emit large calorimetric, also produce certain gas, because β-SiC particle is very little, be attached to bubble surface, can form larger bubble and be difficult for breaking, so, just start the first at room temperature stirring reaction of β-SiC particle and corrosive fluid, when making bubble breaking, discharged as early as possible heat, guaranteed reacting balance, general reaction 10 minutes, the reaction that this process occurs is:
SiC+2HNO
3+2H
2O→2HNO
2+4OH
-+SiC
4+（1）
4OH
-+SiC
4+→SiO
2+CO
2+2H
2 （2）
After question response tends to be steady, in order to guarantee corrosion speed and control reaction preferably faster, be placed on 60-80 ℃ of reaction.The blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 60g-80g β-SiC particle.This process reaction chemical equation is:
SiO
2+6HF→H
2SiF
6+2H
2O （3）
In whole corrosion process, the oxygenizement of the dissociation of hydrofluoric acid to C-Si key and nitric acid makes β-SiC particle surface form the close organism active groups such as hydroxyl and oxygen base, and β-SiC particle is etched into porous web trellis.
Because whole system after corrosion is strongly-acid, pH value can reach 1.0 left and right, in the time being applied to active somatic cell fluorescent mark, grows totally unfavorable for active somatic cell, therefore, must carry out deacidification treatment to it.
Because β-SiC particle after corrosion is suspension in whole system, so the present invention adopts centrifugal treating, after making to corrode, there is latticed β-SiC particle and separate with corrosive fluid is rapid.By after said mixture centrifugation, extract upper strata corrosive fluid out, add high purity water 200-400ml, stir 5 minutes, again it is carried out to aforesaid operations, repeatedly carry out 4 to 5 times, make finally to obtain solution system pH value and be adapted to adopted active somatic cell, generally solution system pH value is at 6.4-6.8.
Silicon-carbide particle suspension after deacidification treatment is imported to glass cylinder, in ultrasonic wave separating apparatus, aqueous phase solution is carried out to supersound process 20 minutes, ultrasonic wave separating apparatus output rating is 1kW, and frequency is 15kHz.This is mainly to utilize the cavatition of the aqueous solution in ultrasonic wave, break into less nano-scale particle and become quantum dot and fall into the aqueous solution thering is latticed β-SiC particle, and quantum dot surface can form the close organism active groups such as O base and COO base, can be combined with the material such as protein, ion thus, single stage method of the present invention has realized quantum dot synthesizes and surface biological functional modification, has improved preparation efficiency.
For the nanoparticle of different size, adopt centrifugal treating then to cut out by chromatography, can obtain size mono-dispersed nano particle, therefore the present invention adopts high speed centrifugation to make different-grain diameter quantum dot size distribution in supernatant liquor different sites, thereby it is controlled to reach quantum dot size.Centrifugal speed has determined centrifugal force size, and rotating speed is too little, and the powder granule of corrosion is suspended in solution, and the quantum dot particle dia obtaining is larger; Rotating speed is too large, be suspended in the quantum dot number of particles of supernatant liquor very little, concentration is lower, centrifugal rotational speed of the present invention adopts 2800-3000rpm more suitable, in the solution system finally obtaining, silicon carbide quantum dot concentration is 0.03-0.06mol/L, under visible ray, be pistac, it is closely spherical that quantum dot is, and diameter is 2-5nm.In order to adapt to the application of later stage on active somatic cell, the pH value of water silicon carbide quanta point material is 6.4-6.8.
The water silicon carbide quanta point material no cytotoxicity making due to the present invention, and much smaller than exciton bohr (Bohr) radius of silicon carbide body material, so fluorescent effect is obvious, therefore this material is used as fluorescence labeling material by contriver, directly added in the nutrient solution of active somatic cell or substratum and can be realized fluorescent mark, imaging for a long time, is convenient for people to the pattern at fluorescence microscopy Microscopic observation active somatic cell.Active somatic cell of the present invention is plant or microorganism active somatic cell.
In sum, the present invention has the following advantages:
1) the standby silicon carbide quantum dot no cytotoxicity of this water legal system, and surface has the close organism active groups such as oxygen base, carboxyl, can not affect active somatic cell growth physiological function, can realize the imaging of long time-histories fluorescent mark to it.
2) preparation technology is simple, and what abandoned available technology adopting is electrochemical etching method, and adopts the method for directly etching, processing parameter to be easy to control, with low cost, can single stage method realize quantum dot synthetic with surface biological functional modification.
3) after processing by ultrasonic dispersion and high speed centrifugation, can realize the Effective Regulation to quantum dot size, the quanta point material of preparing is much smaller than exciton bohr (Bohr) radius of silicon carbide body material, and its photoluminescence effect is remarkable, transmitting light intensity is stronger, and fluorescent effect is more obvious.
Accompanying drawing explanation
Fig. 1 is latticed microstructure morphology after spreading synthetic β-SiC particle erosion, and this pattern has been established condition for next step obtains tiny nearly spherical quantum dot by ultrasonic cavitation.
Fig. 2 is the TEM photo of color and microtexture under water silicon carbide quanta point material visible ray, and quantum dot is closely spherical, the about 2nm of (110) spacing, and this quantum dot can have stronger photoluminescence effect.
Fig. 3 is 2 days and the 4 days fluorescent mark imaging gray-scale map that water silicon carbide quanta point material is applied to aureobasidium pullulans (Aureobasidium pulluans948) active somatic cell;
Fig. 4 is that water silicon carbide quanta point material is applied to optics and the fluorescent mark imaging gray-scale map after Arabidopis thaliana root active somatic cell.
Embodiment
Embodiment 1-5 water silicon carbide of the present invention quanta point material and preparation method thereof; Embodiment 6-7 is the application of the water silicon carbide quanta point material that makes of the present invention in active somatic cell fluorescent mark.The synthetic homogeneous nano β-SiC particle of self-propagating combustion used is provided by Physical Chemistry Technology Inst., Chinese Academy of Sciences.Embodiment 1
A kind of water silicon carbide quanta point material, its pH value is 6.4, and silicon carbide quantum dot concentration is 0.03mol/L, and it is closely spherical that quantum dot is, and diameter is 5nm.
Its concrete preparation process is:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stir 10 minutes, wherein, β-SiC grain diameter is 70nm, and the blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 80g β-SiC particle;
C. the mixture in step B is corroded 1 hour in 75 ℃;
D. by said mixture after 600rpm low-speed centrifugal, extract out corrosive fluid, add high purity water 200ml, stir 5min, after centrifugation, again it is carried out to aforesaid operations, repeatedly eccentric cleaning to solution system pH value 6.4.
E. the aqueous solution after eccentric cleaning is carried out to supersound process, ultrasonic power is 1kW, and frequency is 15kHz, ultrasonic time 20min;
F. to through the aqueous solution of supersound process in the processing of 2800rpm high speed centrifugation, get supernatant liquor and be silicon carbide Quantum Dot Labeling material.
Embodiment 2
A kind of water silicon carbide quanta point material, its pH value is 6.5, and silicon carbide quantum dot concentration is 0.06mol/L, and it is closely spherical that quantum dot is, and diameter is 2nm.
Its concrete preparation process is:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stir 10 minutes, wherein, β-SiC grain diameter is 50nm, and the blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 70g β-SiC particle;
C. the mixture in step B is corroded 1 hour in 65 ℃;
D. by said mixture after 800rpm low-speed centrifugal, extract out corrosive fluid, add high purity water 300ml, stir 5min, after centrifugation, again it is carried out to aforesaid operations, repeatedly eccentric cleaning to solution system pH value 6.5.
E. the aqueous solution after eccentric cleaning is carried out to supersound process, ultrasonic power is 1kW, and frequency is 15kHz, ultrasonic time 20min;
F. to through the aqueous solution of supersound process in the processing of 3000rpm high speed centrifugation, get supernatant liquor and be silicon carbide Quantum Dot Labeling material.
Embodiment 3
A kind of water silicon carbide quanta point material, its pH value is 6.6, and silicon carbide quantum dot concentration is 0.04mol/L, and it is closely spherical that quantum dot is, and diameter is 3nm.
Its concrete preparation process is:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stir 10 minutes, wherein, β-SiC grain diameter is 100nm, and the blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 60g β-SiC particle;
C. the mixture in step B is corroded 1 hour in 70 ℃;
D. by said mixture after 500rpm low-speed centrifugal, extract out corrosive fluid, add high purity water 400ml, stir 5min, after centrifugation, again it is carried out to aforesaid operations, repeatedly eccentric cleaning to solution system pH value 6.6.
E. the aqueous solution after eccentric cleaning is carried out to supersound process, ultrasonic power is 1kW, and frequency is 15kHz, ultrasonic time 20min;
F. to through the aqueous solution of supersound process in the processing of 2900rpm high speed centrifugation, get supernatant liquor and be silicon carbide Quantum Dot Labeling material.
Embodiment 4
A kind of water silicon carbide quanta point material, its pH value is 6.7, and silicon carbide quantum dot concentration is 0.05mol/L, and it is closely spherical that quantum dot is, and diameter is 4nm.
Its concrete preparation process is:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stir 10 minutes, wherein, β-SiC grain diameter is 60nm, and the blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 65g β-SiC particle;
C. the mixture in step B is corroded 1 hour in 60 ℃;
D. by said mixture after 700rpm low-speed centrifugal, extract out corrosive fluid, add high purity water 220ml, stir 5min, after centrifugation, again it is carried out to aforesaid operations, repeatedly eccentric cleaning to solution system pH value 6.7.
E. the aqueous solution after eccentric cleaning is carried out to supersound process, ultrasonic power is 1kW, and frequency is 15kHz, ultrasonic time 20min;
F. to through the aqueous solution of supersound process in the processing of 2800rpm high speed centrifugation, get supernatant liquor and be silicon carbide Quantum Dot Labeling material.
Embodiment 5
A kind of water silicon carbide quanta point material, its pH value is 6.8, and silicon carbide quantum dot concentration is 0.03mol/L, and it is closely spherical that quantum dot is, and diameter is 2nm.
Its concrete preparation process is:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stir 10 minutes, wherein, β-SiC grain diameter is 80nm, and the blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 75g β-SiC particle;
C. the mixture in step B is corroded 1 hour in 80 ℃;
D. by said mixture after 650rpm low-speed centrifugal, extract out corrosive fluid, add high purity water 330ml, stir 5min, after centrifugation, again it is carried out to aforesaid operations, repeatedly eccentric cleaning to solution system pH value 6.8.
E. the aqueous solution after eccentric cleaning is carried out to supersound process, ultrasonic power is 1kW, and frequency is 15kHz, ultrasonic time 20min;
F. to through the aqueous solution of supersound process in the processing of 3000rpm high speed centrifugation, get supernatant liquor and be silicon carbide Quantum Dot Labeling material.
Embodiment 6
1, aureobasidium pullulans (Aureobasidium pulluans 948) culture condition
Slant medium (W/V): peptone 2%, yeast extract paste 1%, glucose 2%, agar 2%, 6.0121 ℃ of sterilizing 20min of pH.
Seed liquor substratum (W/V): 2% glucose, 2% yeast extract paste, 0.5%K
2hPO
4, 0.1%NaCl, 0.02%MgSO
47H
2o, 0.06% (NH
4)
2sO
4, initial 6.5,8 pounds of sterilizings of pH (121 ℃) 20min;
Fermention medium: 4% glucose, 2% yeast extract paste, 0.5%K
2hPO
4, 0.1%NaCl, 0.02%MgSO
47H
2o, 0.06% (NH
4)
2sO
4, initial 6.5,8 pounds of sterilizings of pH (121 ℃) 20min; Be made into 60ml solution, to the water silicon carbide quanta point material that adds 5ml embodiment 1 to make in solution.
2, experimental technique
The slant strains scraping two of preservation in biochemical cultivation case is encircled in the seed culture medium preparing and activated, and 28 ℃, 200r/min, cultivates 2 days.Again the bacterial classification of activation is inoculated into fermention medium with 7% inoculum size by seed liquor bacterial classification, cultivates after 2-4 days, at fluorescence microscopy Microscopic observation active somatic cell pattern.
Known by embodiment 6 and Fig. 3: the SiC fluorescent material no cytotoxicity that 1, prepared by this patent, for the impact of active somatic cell growth nothing, can show the pattern (when beginning be granular, spherical, long-time growth after become silk palpus shape) of aureobasidium pullulans in different time sections; 2, Aureobasidium pullulans mycetocyte can fluoresce for a long time, illustrates that SiC fluorescent material is difficult for being quenched; 3, in nutrient solution, add SiC fluorescent material and can realize fluorescent dye, method is simple and effective.
Embodiment 7
Arabidopis thaliana (Arobidopsis thaliana L.) (environmental for Columbia) seed is dispersed on GM minimum medium after sterilizing, wherein adds the water silicon carbide quanta point material that the embodiment 3 of volume ratio 40% makes.Place for 4 ℃ and move to growth room after 4 days and cultivate, temperature is 20-22 ℃, and illumination condition is illumination in 16 hours, 8 hours dark, growth of seedling after 10 days for observing root section observation of cell structure under fluorescent microscope.
Known by embodiment 7 and Fig. 4:
1, the SiC fluorescent material no cytotoxicity that prepared by this patent, for the impact of active somatic cell growth nothing, can demonstrate the pattern of Arabidopis thaliana root, and root different sites fluorescence power difference to some extent, eugonic position (root teat position) fluorescence is stronger; 2, Arabidopis thaliana root cell can fluoresce for a long time, illustrates that SiC fluorescent material is difficult for being quenched; 3, in nutrient solution, add SiC fluorescent material and can realize fluorescent dye, method is simple and effective.
Claims (9)
1. a water silicon carbide quanta point material, is characterized in that: silicon carbide quantum dot concentration is 0.03-0.06mol/L, and it is closely spherical that quantum dot is, and diameter is 2-5nm.
2. water silicon carbide quanta point material according to claim 1, is characterized in that: the pH value of water silicon carbide quanta point material is 6.4-6.8.
3. the method for preparation water silicon carbide quanta point material as claimed in claim 1 or 2, is characterized in that: its concrete steps are:
A. the hydrofluoric acid that is 40% by mass concentration and mass concentration are that 65% nitric acid is mixed with corrosive fluid according to volume ratio 3:1, and stir;
B. homogeneous nano β-SiC powder synthetic self-propagating combustion is placed in to the corrosive fluid of steps A configuration, stirring reaction, β-SiC grain diameter is 50-100nm
C. by the mixture standing and reacting in step B;
D. after said mixture is centrifugal, extract corrosive fluid out, add high purity water, the SiC particle after utilizing high purity water to corrosion carries out eccentric cleaning;
E. the aqueous solution after eccentric cleaning is carried out to supersound process;
F. the aqueous solution through supersound process is carried out to centrifugal treating, get supernatant liquor and be silicon carbide Quantum Dot Labeling material, centrifugal speed is 2800-3000rpm.
4. the preparation method of water silicon carbide quanta point material according to claim 3, is characterized in that: in step B, the blending ratio of β-SiC particle and corrosive fluid is in every 100ml corrosive fluid, to add 60g-80g β-SiC particle.
5. the preparation method of water silicon carbide quanta point material according to claim 3, is characterized in that: in step C, temperature of reaction is 60 ℃-80 ℃, and the reaction times is 1 hour.
6. the preparation method of water silicon carbide quanta point material according to claim 3, is characterized in that: in step D, centrifugal speed is 500-800rpm.
7. the preparation method of water silicon carbide quanta point material according to claim 3, is characterized in that: in step D, after eccentric cleaning, solution system pH value is 6.4-6.8.
8. the preparation method of water silicon carbide quanta point material according to claim 3, is characterized in that: in step e, ultrasonic power is 1kW, and frequency is 15kHz, and ultrasonic time is 20min.
9. the water silicon carbide quanta point material described in a claim 1 or 2 is for the purposes of fluorescence labeling material.
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| 范吉阳等.3C-SiC纳米颗粒量子限制效应的实验证据.《研究快讯》.2005,第34卷(第8期),570-572页. |
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