CN103864047A - Functional carbon nanoparticles and application thereof - Google Patents
Functional carbon nanoparticles and application thereof Download PDFInfo
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- CN103864047A CN103864047A CN201210555354.3A CN201210555354A CN103864047A CN 103864047 A CN103864047 A CN 103864047A CN 201210555354 A CN201210555354 A CN 201210555354A CN 103864047 A CN103864047 A CN 103864047A
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Abstract
The invention discloses a preparation and characteristic of functional fluorescent carbon nanoparticles (referred to as CNPs) and an application thereof in bio-detection techniques. The preparation is characterized in that 1g of sodium alginate and 0.1g of NaOH are mixed and slowly added to 30ml of deionized water and thoroughly stirred and then placed in an autoclave and reacted for 4h at 160 DEG C. The carbon nanoparticles obtained by the reaction are subjected to acid-base neutralization. The nanoparticles have rich source of raw materials, cheap and easily available raw materials, and simple preparation method; synthesized carbon nanoparticles have good fluorescence properties including fluorescent stability, no light flashes, controllable excitation and emission wavelength, good biocompatibility, low toxicity, very small molecular weight and particle size, and have rapid development in biological detection, sensing, angiography, and many other application fields.
Description
Technical field
The present invention relates to nano-luminescent material, specifically a kind of preparation of carbon nano-particle, characterize and application.
Background technology
2004, the investigator of Clemson University was with chancing on carbon nano-particle in electrophoretic separation multi-walled carbon nano-tubes process.Its chief component element is carbon, is one of the abundantest element of nature, is also one of most important component of life entity.Due to nontoxic and possess good fluorescent characteristic, enjoy favor, in various fields, be widely used.Be mainly used in mark and the living imaging of microorganism, zooblast.The technology of now having reported and the problem of existence thereof comprise following several aspect:
(1) emitting semiconductor quantum dot (claiming again quantum dot) technology (document 1:Warren C.W.Chan and ShumingNie, Science, 1998,281,2016-2018).The invention of quantum dot, has started the frontier of nanoparticle as fluorescent marker application.But the unstable easy flicker of quantum dot light emitting, there is the shortcomings such as certain toxicity, can affect the activity of cell or biomacromolecule, limit to a certain extent its use.Overcome its various defects and fluorescent carbon nano particle is environmentally friendly biomarker, cause the great interest of people.
(2) the fluorescent carbon nano-particles technology of inorganics carbonization (document 2:Xiao-You Xu, Robert Ray, et al..J.Am Chem.Soc.2004,126,12736-1273; Document 3:M Bottini, C Balasubramanian, Ml Dawson, A Bergamaschi, S Bellueei, TMustelin.J.Phys.Chem.B, 2006,110,831-836.; Document 4:Sun Y.P., Zhou B., Lin Y., et a1..J.Am.Chem.Soc, 2006,128,7756-7757.).The carbon nano-particle that inorganic carbide obtains is with low cost, but luminously mainly concentrates in visible region, so limited its further application in living imaging.The main raw material of use has Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, graphite target, business gac at present.The carbon nano-particle obtaining can send multicolor visible light, has good biocompatibility, but the step separating is more loaded down with trivial details.
(3) the fluorescent carbon nanotechnology of organic carbon: the particle diameter of organic carbon gained carbon nano-particle is large, but luminous quantum efficiency is higher and have a characteristic of up-conversion fluorescence and near infrared emission.Main raw material has the polysaccharose substances such as sucrose, starch, glucose.There is special photoluminescent property using starch and sucrose as carbon source synthesize nano carbon particle according to the literature, under the lasing of near-infrared wavelength, can send near infrared light.Because near infrared energy penetrate tissue carries out deep tissues imaging and autofluorescence background is low, be expected to be introduced in tumour cell body in living imaging research, overcome the defect such as high toxicity and high cost of semiconductor-quantum-point.(document 5:Peng H, Travas-SejdicJ, ChemMater, 2009,21 (23), 5563-5; Document 6:Zhao QL, Zhang ZL, Huang BH, Peng J, Zhang M, Pang DW.ChemCommun, 2008,41,5116-8; Document 7:Ray S C, Saha A, Jana NR, Sarkar R.PhysChem, 2009,113 (43), 18546-51.).In the practice of medical science and life science and research, bringing into play more and more important effect.The great advantage of carbon nano-particle is to possess good fluorescence characteristic, so have certain advantage aspect biological detection.But preparation technology's more complicated of carbon nano-particle at present, carbon source source is explored extensive not enough, and the problems such as the more difficult separation of gained carbon nano-particle wait further solution.
Summary of the invention
In order to address the above problem, the object of the invention is taking cheap carbon source as raw material, adopt easy synthetic method to obtain the carbon nano-particle (Carbon Nanoparticles) with good fluorescence characteristic, then the carbon nano-particle of gained is carried out the research of phenetic analysis and application aspect.
To achieve these goals, technical scheme of the present invention is as follows:
Taking sodium alginate as raw material, adopt hydrothermal synthesis method to obtain having the carbon nano-particle of good fluorescence characteristic.
Its preparation method is: adopt hydrothermal synthesis method to be prepared from, carbon source and highly basic are placed in to autoclave reactor, then add after a certain amount of deionized water, single step reaction obtains carbon nano-particle.Then use the changing conditions of the quantum yield of sodium borohydride Treatment Analysis gained carbon nano-particle.
Specific experiment operating process: take in the deionized water that the sodium alginate of 1g and the sodium hydroxide of 0.1g slowly joins 30ml and fully stir simultaneously.Then be placed in encloses container (autoclave) reaction 4h, temperature is 160 DEG C.After having reacted, with HCl neutralizing treatment (mass concentration 1～30%), with 2 days (changing water one time every 2h) of dialysis tubing (molecular weight cut-off 300 ~ 3000, in this case MWCO500) dialysis.Obtained solution is used respectively to 0.45 μ m, and macromole impurity is removed in 0.22 μ m microfiltration membrane processing.Then with the centrifugal 20min of high speed tabletop refrigerated centrifuge (10000rpm), remove relatively little impurity, obtain fluorescent carbon nano particle Alg-CNPs.
Sodium borohydride is processed carbon nano-particle: the carbon nano-particle of every milliliter adds after the sodium borohydride of 0.1g, stirs and makes it abundant dissolving, then its quantum yield is analyzed.
The sign of carbon nano-particle: (1) analyzes the fluorescent characteristic of carbon nano-particle by fluorescence spectrophotometer.(2) by the absorption value under full wavelength absorption situation and the concrete exciting light effect of ultraviolet spectrophotometer analysis carbon nano-particle.(3) analyze the structure of functional groups of carbon nano-particle with Fourier infrared spectrograph.(4) quantum yield (QYs) of analysis carbon nano-particle after sodium borohydride is processed.(5) impact (pH=3,5,7,9,11,13) of different pH values on carbon nano-particle fluorescent characteristic.
Carbon nano-particle is used for bio-imaging: utilize carbon nano-particle for probe, carry out blend be prepared into fluorescence fish food with fish food, fish is carried out, after the nursing of fluorescence fish food, utilizing fluorescence imaging system to carry out bio-imaging.
Tool of the present invention has the following advantages:
(1) utilize sodium alginate for carbon source, only need simple single step reaction method can prepare carbon nano-particle, simplified the complicated building-up process of carbon nano-particle
(2) expand the range of choice of carbon nano-particle carbon source, do not needed through loaded down with trivial details synthesis step and equipment is prepared and separation and purification, be applicable to carrying out scale operation
(3) the carbon nano-particle photoluminescent property obtaining is stable, has certain advantage in the application of fluorescent microscope context of detection
(4) carbon nano-particle obtaining good dispersity in water, fluorescence emission spectrum is adjustable, is expected to be applied to biological detection and living animal imaging as biomarker
Brief description of the drawings:
Fig. 1 is the transmission electron microscope photo of Alg-CNPs after reduction;
Fig. 2 is Alg-CNPs ultra-violet absorption spectrum and fluorescence spectrum after reduction, insertion be Alg-CNPs fluorescence spectrum before reduction;
Fig. 3 is the Fourier transform infrared spectroscopy of Alg-CNPs after reduction;
Fig. 4 is the light stability of Alg-CNPs after reduction;
Fig. 5 is different pH values on reducing the impact of fluorescent characteristic of rear Alg-CNPs;
Fig. 6 is that after reduction, Alg-CNPs carbon nano-particle is for Poecilia living body fluorescent imaging photo, and the upper left corner is Poecilia living body fluorescent imaging photo, and lower right is the fish imaging photo of contrast.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1: carbon nano-particle preparation and separation and purification
(1) preparation of Alg-CNPs:
The NaOH that takes 1g sodium alginate and 0.1g is placed in beaker, adds the deionized water of 30ml.Then reactant is placed in to autoclave and reacts 4h, temperature is 160 degrees Celsius.After placement room temperature is cooling, reaction product is transferred to 7 with the HCl of 1M by pH.
(2) separation and purification of Alg-CNPs:
The product solution of gained is used respectively to 0.45 μ m, and macromole impurity is removed in 0.22 μ m microfiltration membrane processing.Then with the centrifugal 20min of high speed tabletop refrigerated centrifuge (10000rpm), then use dialysis tubing (500Da) to process except the small-molecule substance such as desalting, dialysis time is 2 days (changing water one time every 2h).
Embodiment 2: carbon nano-particle property representation
(1) transmission electron microscope of carbon nano-particle characterizes:
As seen from Figure 1, the particle diameter of sodium alginate carbon nano-particle is in 100nm left and right, and size distribution is more even, and monodispersity is better.
(2) ultra-violet absorption spectrum of carbon nano-particle and fluorescence spectrum figure
Fig. 2 is ultra-violet absorption spectrum and the fluorescence spectrum figure of alg-CNPs after reduction, and as can be seen from the figure carbon nano-particle has absorption peak at 260nm place, and this peak is C=C typical peaks.Carbon nano-particle is under the effect of different wave length (320nm-420nm) exciting light, and radiative wavelength is different, mainly concentrates in visible-range.Along with the increase of excitation wavelength, emission wavelength generation red shift.
(3) the Fourier infrared spectrum figure of carbon nano-particle
Fig. 3 is the infrared spectrogram of alg-CNPs, and the carbon nano-particle of synthetic gained is at 3391cm
-1there is O-H stretching vibration absorption peak left and right, at 2925cm
-1have-CH of left and right
2stretching vibration absorption peak, 1599cm
-1for the stretching vibration absorption peak of C=O, 1399cm
-1for-CH
2flexural vibration absorption peak.
(4) the light stability experimental result picture of carbon nano-particle
Carbon nano-particle, rhodamine B and the fluorescein light stability in the aqueous solution as shown in Figure 4, light source used is 30W incandescent light, sample is 10cm apart from incandescent light, surveys its maximum fluorescence intensity respectively at maximum excitation wavelength 360nm, fluorescein maximum excitation wavelength 319nm, the rhodamine B maximum excitation wavelength 552nm of carbon point.Experimental result shows: along with the prolongation of time, the fluorescence intensity of fluorescein and rhodamine constantly weakens.Wherein, fluorescein in front 10min and poly-rapid drawdown, decays to 27% of initial intensity fluorescence after 50min, and the strength retrogression of fluorescein is to initial 82%.And the fluorescence intensity of carbon nano-particle is more stable, substantially remain unchanged.
Embodiment 3: sodium borohydride is processed and improved carbon nano-particle fluorescence quantum yield
(1) sodium borohydride processing
The carbon nano-particle of getting 15ml is placed in beaker, fully mixes after adding the sodium borohydride of 1.5g, then removes unnecessary sodium borohydride (500Da) with dialysis process, and dialysis time is 2 days (changing water one time every 2h).
(2) sodium borohydride is processed rear carbon nano-particle fluorescence quantum yield
The conclusion that can draw from table 1 is that synthetic carbon nano-particle quantum yield after sodium borohydride reduction improves greatly.
(3) impact of pH value on carbon nano-particle photoluminescent property
Get respectively the alg-CNPs sample of 0.5ml, add the deionized water of 4.5ml, then adjust pH to 3,5,7,9,11,13 to do three groups of parallel laboratory tests with the HCl of 5M and 5MNaOH.Fig. 5 is the impact of pH value on carbon nano-particle fluorescent characteristic, and the conclusion that can draw in figure is, carbon nano-particle fluorescence intensity is affected by pH, and in the time of pH meta-acid, carbon nano-particle fluorescence intensity is corresponding stronger; In the time of pH partial neutral or alkalescence, its fluorescence intensity dies down.
Embodiment 4: carbon nano-particle is for bio-imaging
Be that 1:1 is mixed in beaker by fish food with the mass ratio of carbon quantum dot, add a small amount of water, blended.Be placed in little centrifuge tube, 24h is processed in lyophilize, obtains powdery substance and is fish food.Bio-imaging adopts commercially available Poecilia, within every 24 hours, feeds once, and each nursing all outwelled water, and then the tap water renewing adds fish food.Feeding amount is 20mg/ time.After 36 hours, utilize the imaging of small animal living body imager, excitation light source 455 nanometers, emmission spectrum 500-720 nanometer, time shutter 460ms.
Table 1: quantum yield (QY) value before carbon nano-particle reduction and after reduction
Claims (8)
1. functional carbon nano-particle, is characterized in that: taking sodium alginate as raw material, adopt hydrothermal synthesis method to obtain the carbon nano-particle with good fluorescence characteristic.
2. functional carbon nano-particle according to claim 1, is characterized in that: the sodium alginate of 0.1～5g is mixed with 0.01～10g NaOH in the deionized water that slowly joins 10～40ml and fully stir simultaneously; Then be placed in encloses container or autoclave reacts 1～40h, temperature is 140～280 DEG C; After having reacted, by HCl(mass concentration 1～30%) neutralizing treatment is to PH=5～9, packs in dialysis tubing (molecular weight cut-off 300 ~ 3000) and in water, dialyses 1～4 day, and dialysis procedure is changed one time water for every 1～8 hour; Solution in obtained dialysis tubing is removed to macromole impurity with the processing of 0.1～0.8um microfiltration membrane, and obtaining supernatant liquor is fluorescent carbon nano particle Alg-CNPs.
3. functional carbon nano-particle according to claim 2, it is characterized in that: get 1～50ml fluorescent carbon nano particle Alg-CNPs and be placed in beaker, add the abundant stirring reduction overnight of 0.1～5g sodium borohydride, then pack in dialysis tubing (molecular weight cut-off 300 ~ 3000) and in water, dialyse 1～4 day, dialysis procedure is changed one time water for every 1～8 hour; Through reduction after dialysis tubing in solution, the quantum yield of carbon nano-particle improves greatly.
4. the application of the arbitrary described carbon nano-particle of a claim 1-3 in biomarker.
5. according to application claimed in claim 4, it is characterized in that: described biomarker refers to the mark of carbon nano-particle for antibody, antigen, albumen or nucleic acid molecule.
6. according to application claimed in claim 4, it is characterized in that: described biomarker refers to drinking-water, food or the medicine of carbon nano-particle for animal, and drinking-water, food or the medicament mixed of carbon nano-particle and animal, for animal imaging.
7. the arbitrary described carbon nano-particle of a claim 1-3 is for the detection of blood and fruit juice glucose content.
8. the arbitrary described carbon nano-particle of claim 1-3 strengthens surface-enhanced raman scattering for after combining with gold and silver or copper heavy metal ion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673288A (en) * | 2015-02-06 | 2015-06-03 | 广西师范大学 | Preparation method of water-soluble graphene quantum dot for emitting white fluorescence |
| CN106118645A (en) * | 2016-06-27 | 2016-11-16 | 青岛大学 | A kind of method that Direct Hydrothermal carbonization Thallus Laminariae (Thallus Eckloniae) prepares fluorescent carbon nano-particle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267684A (en) * | 2010-06-03 | 2011-12-07 | 中国科学院化学研究所 | Metallic nano particle/ carbon composite material and preparation method and application thereof |
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| CN102267684A (en) * | 2010-06-03 | 2011-12-07 | 中国科学院化学研究所 | Metallic nano particle/ carbon composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAODIE HE ET AL.: "Water soluble carbon nanoparticles: Hydrothermal synthesis and excellent photoluminescence properties", 《COLLOIDS AND SURFACES B: BIOINTERFACES》, no. 87, 27 May 2011 (2011-05-27), pages 326 - 332, XP028248616, DOI: 10.1016/j.colsurfb.2011.05.036 * |
| 田磊: "发光碳纳米颗粒和CdS量子点的合成表征及应用", 《中国博士学位论文全文数据库》, 31 December 2011 (2011-12-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673288A (en) * | 2015-02-06 | 2015-06-03 | 广西师范大学 | Preparation method of water-soluble graphene quantum dot for emitting white fluorescence |
| CN106118645A (en) * | 2016-06-27 | 2016-11-16 | 青岛大学 | A kind of method that Direct Hydrothermal carbonization Thallus Laminariae (Thallus Eckloniae) prepares fluorescent carbon nano-particle |
| CN106118645B (en) * | 2016-06-27 | 2018-07-06 | 青岛大学 | A kind of method that Direct Hydrothermal carbonization kelp prepares fluorescence carbon nano-particle |
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Application publication date: 20140618 |