CN104709894B - Preparation method and applications of fluorescent carbon quantum dots - Google Patents
Preparation method and applications of fluorescent carbon quantum dots Download PDFInfo
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- CN104709894B CN104709894B CN201310690195.2A CN201310690195A CN104709894B CN 104709894 B CN104709894 B CN 104709894B CN 201310690195 A CN201310690195 A CN 201310690195A CN 104709894 B CN104709894 B CN 104709894B
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Abstract
The present invention discloses a preparation method and applications of fluorescent carbon quantum dots (Carbon dots, short for CDs). According to the preparation method, formic acid and bovine serum albumin (BSA) are adopted as raw materials, a molar ratio of the amino of the BSA to the aldehyde of the formic acid is 1:1, hydrothermal synthesis is performed, the aldehyde of the formic acid and the amino of the BSA are subjected to condensation to generate carbon nitrogen double bond, the generated polymer having the carbon nitrogen double bond self-reacts to generate carbon quantum dots, and a water-based membrane and a dextran G-25 gel column are used to separate and purify. According to the present invention, the carbon quantum dots prepared through the method have characteristics of small particle size, good light stability, wide excitation and emission spectrum range, high fluorescence quantum yield, low toxicity, and environmental protection, and can be successfully used in biological cell imaging, wherein the yield of the carbon quantum dots is generally low in the prior art is solved with the preparation method of the present invention.
Description
Technical field
The present invention relates to fluorescent nano material, specifically a kind of preparation of fluorescent carbon quantum dot and application.
Background technology
In recent years, developing rapidly with nanotechnology, nano material (such as: nano magnetic material, nano ceramic material,
Nano-sensor, nanometer FUNCTIONALLY GRADIENT MATERIAL, nano semiconductor material and nano catalytic material) extensively recognized by people and should
With.In biological, field of medicaments, the preparation of nano material and application also gradually become finely, for the quantum of biomarker
Point is one kind therein.Quantum dot, can be described as nanocrystalline again, is a kind of nanometer elementary composition by ii-vi race or iii-v race
Granule.Particle diameter is typically in the range of between 1～10nm, and because electronics and hole are by quantum confinement, continuous band structure becomes and has
The discrete energy level structure of molecular characterization, by launching fluorescence after excitation.The research of quantum dot is 90 years 20th century
In generation, starts from cdse quantum dot earliest, and as fluorescent probe, it has much excellent property: one, emission spectrum can pass through
The size changing quantum dot is controlling；2nd, good light stability；3rd, excitation spectrum, emission spectrum are narrow；4th, stokes displacement
Greatly；5th, good biocompatibility；6th, fluorescence lifetime is long.The quantum dot with above 6 points of properties is almost a kind of preferable fluorescence
Probe, but quantum dot is made up of poisonous heavy metal element, and toxicity limits its application in terms of biological medicine, low toxicity
Carbon point (carbon dots) arises at the historic moment as a kind of new fluorescent probe, and carbon point is except possessing the excitation spectrum of quantum dot
Wide1, particle diameter little2, good light stability3, stokes displacement is big, outside good biocompatibility, the advantageous property of fluorescence lifetime length, also have
Have hypotoxic feature, thus be seen as in terms of biomarker quantum dot succedaneum (document 1:hu shengliang,
Bai peikang, sun jing, cao shirui, progress in chem istry, 2010,22:345-351.).
Carbon point be the discovery that first 2004 by xiaoyou xu etc. purify arc process preparation CNT when accidental
The carbon nano-particles with photoluminescent property finding, fluorescence quantum yield at that time is very low.2006, the section of Clemson University
Scholar sun and his colleagues prepared with laser ablation (document 2:sheila n.baker, gary a.baker,
Angew.chem.int.ed.2010,49,6,726 6744), and using organic reagent passivation, the method has synthesized fluorescence property
Preferably product, is referred to as carbon point first.2008, Wuhan University pang etc., with graphite as carbon source, was closed with electrochemical oxidation process
Become carbon quantum dot, subsequently occur in that hydro-thermal method and microwave method.With the appearance of new preparation method, the fluorescence property of carbon point also by
Being enhanced gradually, also becomes extensively in the application of medical science and biological field.But the quantum yield of carbon point is still very low, also
Do not reach the level of quantum dot, under such situation background, the preparation of the carbon point of high-fluorescence quantum yield seems particularly necessary.
Content of the invention
For above problem, it is an object of the invention to provide a kind of preparation of fluorescent carbon quantum dot (carbon dots)
Methods and applications.
To achieve these goals, the technical solution used in the present invention is:
Using hydro-thermal method one-step synthesis fluorescent carbon quantum dot, preparation method is as follows: with bovine serum albumin (bsa) and formic acid
For raw material, the amino of bsa is 1:1 with the mol ratio of the aldehyde radical of formic acid, and the aldehyde radical of formic acid and the amino condensation of bsa first generates carbon
Nitrogen double bond, the polymer autoreactivity with carbon-to-nitrogen double bon of generation generates fluorescent carbon quantum dot.
Introduce carbon-to-nitrogen double bon in the carbon point structure of fluorescent carbon quantum dot, increase the conjugation between double bond, there is carbon
The polymer autoreactivity of nitrogen double bond generates the carbon nanoparticle with photoluminescent property, i.e. fluorescent carbon quantum dot.
Bsa is dissolved in deionized water, dropwise instills formic acid then in mixture in the deionized water dissolved with bsa, soon
Speed stirring, the solution mixing formic acid is put in hydrothermal reaction kettle, using heating device, temperature programming 1h, reaction temperature 200
DEG C, response time 10h, the solution that product is clarified for yellow.
Described product glucosan g-25 gel detached dowel separating-purifying, removes unreacted formic acid, gained carbon after purification
Point aqueous solution is golden yellow liquid.
Described fluorescent carbon quantum dot is applied in biomarker.
With bsa and formic acid as raw material, under the conditions of 200 DEG C of temperature programmings, the amino of bsa is condensed with the aldehyde radical of formic acid
Reaction, generate carbon-to-nitrogen double bon (this reaction purpose be in carbon point structure introduction carbon-to-nitrogen double bon, strengthen polymer architecture in double bond it
Between conjugation so that improve carbon point fluorescence quantum yield), the polymer with carbon-to-nitrogen double bon of generation, this structure
Polymer autoreactivity generates the carbon nanoparticle with photoluminescent property.Product glucosan g-25 gel column separation post separation carries
Pure, the carbon point fluorescence quantum yield of gained is 17%.
The following advantage having of the carbon point of present invention preparation:
(1), simply it is not necessary to loaded down with trivial details separation application, the carbon nano-particles particle diameter of synthesis is little, toxicity for preparation method
Low, good biocompatibility.
(2) fluorescence quantum yield is high, has up-conversion fluorescence.
(3), there is not photobleaching phenomenon in good light stability.
(4) fluorescence quantum yield of this carbon point is higher, can be used for living animal fluorescence imaging, carries out real-time, dynamic detection.
Brief description
Fig. 1 is photo under ultraviolet light for the carbon point；
Fig. 2 is the electron micrograph of carbon point；
Fig. 3 is the xps figure of carbon point；
Fig. 4 is carbon swarming spectrogram in carbon point；
Fig. 5 is the infrared spectrogram of carbon point；
Fig. 6 is the ultraviolet spectrogram of carbon point；
Fig. 7 is the fluorescence spectra of carbon point；
Fig. 8 is the cell imaging picture of carbon point.
Specific embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
The preparation of carbon point and sign:
(1) preparation of carbon point and separating-purifying:
Take bsa 0.9g first, be dissolved in 20ml deionized water, then dropwise instill 88% formic acid 0.318g, adjoint
Stirring, makes mixture mix homogeneously, the solution of mix homogeneously is transferred in hydrothermal reaction kettle, Muffle stove heat, using program
Intensification 1h, is warming up to 200 DEG C, and the response time is 10h, products obtained therefrom is removed not anti-with glucosan g-25 gel column separating purification
The formic acid answered, gained carbon point aqueous solution is golden yellow liquid, afterwards by product lyophilization.
(2) measurement of the quantum yield of carbon point:
Choose quinine sulfate solution as reference sample, from formula be:
In formulaFor quantum yield qy%, a is ultraviolet absorption value, and i is fluorescence integrated emission intensity,Refraction for solvent refers to
Number, s is reference, and x is testing sample,
(3) property representation of carbon point property
The surface texture of (a) carbon point and size dimension
Fig. 2 is the electron micrograph of carbon point, uniform in size from the visible carbon dots being obtained with this method of photo,
Carbon point grain size is 2nm.
Fig. 3 is the xps figure of carbon point.It can be seen that substantial amounts of c, o, n element are contained in the surface of carbon point.
Fig. 4 is the xps carbon swarming spectrogram of carbon point.It can be seen that containing at 284.06ev in carbon point structure
There is c=c structure, at 286.8ev, contain c-n structure, contain c=o structure at 288.05ev.
Fig. 5 is the infrared spectrogram of carbon point.It can be seen that in 3411cm-1And 2971cm-1N-h and c- is contained at place
The stretching vibration absworption peak of h, in 1750cm-1To 1650cm-1In the range of the stretching vibration absworption peak containing c=o and c=n and n-h
Bending vibration absworption peak, in 1346cm-1There is the stretching vibration absworption peak of c-n at place, in 1200cm-1Stretching vibration containing c-o
Characteristic absorption peak.
The spectral characteristic of (b) carbon point
Fig. 6 is the ultraviolet spectrogram of carbon point.In figure is visible to occur in that n → π at 270nm*The characteristic absorption peak of transition.
Fig. 7 is the fluorescence spectra of carbon point, the visible increase with excitation wavelength of in figure, and emission spectrum occurs red shift,
It is transmitted in greatly at 330nm, excites scope width.
(5) biologic applications of carbon point property
Fig. 8 is the cell dyeing photo of carbon point.Carbon dots solution labelling tca-8113 Dendritic cell from 1mg/ml concentration is thin
Born of the same parents, in figure can be seen that carbon point and successfully dyeed tca-8113 Tca8113 cells, and fluorescence intensity be significantly stronger than blank right
According to group.
Claims (4)
1. a kind of preparation method of fluorescent carbon quantum dot it is characterised in that:
Using hydro-thermal method one-step synthesis fluorescent carbon quantum dot, preparation method is as follows: is former with bovine serum albumin (bsa) and formic acid
The mol ratio of material, the amino of bsa and the aldehyde radical of formic acid is 1:1, and the aldehyde radical of formic acid and the amino condensation of bsa first generates carbon nitrogen pair
Key, the polymer autoreactivity with carbon-to-nitrogen double bon of generation generates fluorescent carbon quantum dot.
2. according to claim 1 fluorescent carbon quantum dot preparation method it is characterised in that:
Introduce carbon-to-nitrogen double bon in the carbon point structure of fluorescent carbon quantum dot, increase the conjugation between double bond, there is carbon nitrogen double
The polymer autoreactivity of key generates the carbon nanoparticle with photoluminescent property, i.e. fluorescent carbon quantum dot.
3. according to claim 2 fluorescent carbon quantum dot preparation method it is characterised in that:
Bsa is dissolved in deionized water, dropwise instills formic acid then in mixture in the deionized water dissolved with bsa, quickly stir
Mix, the solution mixing formic acid is put in hydrothermal reaction kettle, using heating device, temperature programming 1h, 200 DEG C of reaction temperature,
Response time 10h, the solution that product is clarified for yellow.
4. according to claim 3 fluorescent carbon quantum dot preparation method it is characterised in that:
Described product glucosan g-25 gel detached dowel separating-purifying, removes unreacted formic acid, gained carbon water after purification
Solution is golden yellow liquid.
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| CN105403547A (en) * | 2015-11-26 | 2016-03-16 | 青岛康原药业有限公司 | Cu<2+> measurement adopting Lys (lysine) enhanced BSA (bovine serum albumin) modified CDs (carbon dots) fluorescent probe |
| CN106853964A (en) * | 2015-12-08 | 2017-06-16 | 湖南华腾制药有限公司 | A kind of preparation method of nano-luminescent material |
| CN106147761A (en) * | 2016-02-29 | 2016-11-23 | 安徽工业大学 | The activation of a kind of carbon quantum dot, separation and bovine serum albumin molecule is carried out fluorescently-labeled method |
| CN105907391A (en) * | 2016-04-21 | 2016-08-31 | 安徽建筑大学 | Method for preparing carbon quantum dots by aldehyde precursor |
| CN106904592B (en) * | 2017-02-27 | 2018-08-31 | 西南大学 | A kind of preparation method of fluorescent orange carbon quantum dot |
| CN112978709A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Carbon quantum dot precursor composition, carbon quantum dot and preparation method thereof |
| CN114477140B (en) * | 2022-03-02 | 2024-03-19 | 澳门大学 | Red light-emitting carbon nano dot, and preparation method and application thereof |
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| CN103160279A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院大连化学物理研究所 | Functional carbon dots, and preparation and application thereof |
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