CN105754592A - Water-soluble fluorescent carbon quantum dot preparation method - Google Patents
Water-soluble fluorescent carbon quantum dot preparation method Download PDFInfo
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- CN105754592A CN105754592A CN201510713466.0A CN201510713466A CN105754592A CN 105754592 A CN105754592 A CN 105754592A CN 201510713466 A CN201510713466 A CN 201510713466A CN 105754592 A CN105754592 A CN 105754592A
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Abstract
The invention belongs to the technical field of nanomaterials and discloses a water-soluble fluorescent carbon quantum dot preparation method.Fresh lemon juice is taken as a carbon source to realize synthesis of water-soluble fluorescent carbon quantum dots by hydrothermal reaction.The method is characterized by including steps: proportionally mixing fresh lemon juice with ethanol to obtain lemon juice water solution serving as a hydrothermal reaction precursor, putting the lemon juice water solution into a reaction kettle, and performing constant-temperature hydrothermal reaction for 2.5-5h at about 120 DEG C; taking out after reaction is finished, adding dichloromethane until the volume of the water solution is increased by 1/3, stirring for 0.5min, standing until uniformity is realized, and taking supernatant liquid; adding acetone until the volume of the supernatant liquid is increased by 1/3, centrifuging the supernatant liquid for 15min at a speed of 10000r/min, and dialyzing supernatant liquid to obtain a fluorescent carbon quantum dot containing water solution.The water-soluble fluorescent carbon quantum dots prepared according to the method is high in fluorescence, low in cost and technically simple, has characteristics of biocompatibility, photobleaching resistance and the like and can be directly applied to fields of living cell marking, bioimaging, photoelectric devices and the like.
Description
Technical field
The present invention relates to a kind of water-solubility fluorescent carbon quantum dot preparation method, belong to technical field of nano material.
Background technology
Carbon quantum dot is the nano material with carbon as framing structure, be a kind of scattered, be smaller in size than the class spherical nanoparticle of 10nm, generally comprise Nano diamond, carbon granule and graphene quantum dot, also referred to as carbon point, carbon nano dot, carbon nano-crystal.Similar with various metal quantum points, carbon quantum dot can send bright fluorescence under light conditions.Carbon quantum dot is most important one in fluorescent carbon nano material, it has the small size property of uniqueness and superior photoluminescent property: carbon quantum dot fluorescence is bright, stable, exciting light spectrum width, emission spectrum is narrow, and transmitting wavelength can be regulated and controled by the size and composition that change material, unglazed bleaching phenomenon, some carbon quantum dot also has up-conversion fluorescence characteristic.Thus extremely useful in biological specimen the most living tissue polychrome imaging, the signal disturbing because sample self is luminous and light scattering causes can be prevented effectively from.In addition, biocompatibility that carbon quantum dot is good and accurate biological target tropism, and hypotoxicity so that it becomes conventional semiconductors quantum dot good replacement in bio-imaging, biomarker etc. are applied, and can be directly used for tumor cell labelling and viable cell labelling.Owing to carbon quantum dot is prone to functionalization and industrialization, preparation technology is simple, low production cost, carbon quantum dot excites in the various fields such as device, fluorescence sense, environment measuring, photocatalysis and photoelectric device show huge application potential at luminescent crystal, film light, brings new development space to the ambits such as biomedicine, luminescent material, photoelectric device, environmental protection.At present the method for synthesis carbon quantum dot is mainly had two kinds: one to be the synthetic method of (Bottom-up) from bottom to top, refers to be directly synthesized fluorescent carbon quantum dot, including combustion method, pyrolysismethod, support synthetic method, microwave method etc. by pyrolysis or the suitable predecessor of carbonization；Two is the synthetic method of (Top-down) from top to bottom, i.e. by smashing the predecessor of carbon, then make it the most luminous by the way of polymer surfaces is passivated, mainly including chemical stripping carbon fiber method, arc discharge, laser ablation, electrochemical oxidation and hydro-thermal method etc., wherein hydro-thermal method is the method that synthesis carbon quantum dot is more commonly used.If divide by the raw material of preparation carbon quantum dot, the method synthesizing carbon quantum dot can be attributed to two classes: inorganic carbon source and organic carbon source.For the carbon quantum dot that the synthesising biological compatibility is good, toxicity is low, fluorescence is strong, to promote that carbon quantum dot is developed at biomedical sector and applies, organic natural biology is selected to make carbon source synthesis carbon quantum dot more desirable.In recent years, many scholars use the natural biologies such as orange juice, pomelo peel, leaves, egg, bean milk, glucose, vitamin to be that carbon source synthesizes carbon quantum dot, but there is the problems such as response time length, productivity is low, power consumption is high, poor repeatability, dispersibility are the best in most carbon quantum dot synthetic methods, thus affects the application of carbon quantum dot.
Summary of the invention
The purpose of the present invention is to propose to the preparation method of a kind of water-solubility fluorescent carbon quantum dot, particularly a kind of with Fresh Lemon juice as carbon source, the method of one-step synthesis water-solubility fluorescent carbon quantum dot, the method can solve prior art synthesis fluorescent carbon quantum dot exist response time length, highly energy-consuming, yield poorly, the problem of poor repeatability.
The technical scheme is that with Fresh Lemon juice as carbon source, by hydro-thermal reaction synthesizing water-solubility fluorescent carbon quantum dot.Its composition principle is the vitamin in Fresh Lemon juice and citric acid molecule thermal dehydration is initially formed the carbon quantum dot basic framework unit being made up of C=C, then remaining cellulose C and citric acid molecule arrive the surface of this core and are dehydrated and produce new C=C, and the most constantly grow.Along with the prolongation of heat time heating time, gradually form the carbon quantum dot of the most a few nanometer.Meanwhile, cellulose C and citric acid hydro-thermal carbonized product carbon quantum dot surface in Fructus Citri Limoniae juice there are the oxygen-containing functional groups such as many hydroxyls (-OH), carboxyl (-COOH) and carbonyl (-C=O), H and O in these functional groups can be dehydrated removing in thermal and hydric environment, remaining functional group is connected to the C=C skeleton surface of carbon quantum dot and edge plays passivation, makes carbon quantum dot have good water solublity and photoluminescent property.The water-soluble liquid of heating-up temperature in this synthetic method, heat time heating time, Fructus Citri Limoniae juice is long-pending and the growth of carbon quantum dot all can be had a direct impact by concentration.Therefore, can be by controlling these because of the fluorescent carbon quantum dot usually preparing different colours.
The technical process being technically characterized in that synthesis fluorescent carbon quantum dot of the present invention comprises the steps of
1. lemon is cleaned peeling go seed to put into juice extractor to be squeezed into juice, take lemon juice and mix in the ratio of 4:3 with ethanol, make the Fructus Citri Limoniae juice aqueous solution presoma as hydro-thermal reaction；
2. described Fructus Citri Limoniae juice aqueous solution is put in the reactor polytetrafluoroethyllining lining with oil bath pan heating, react 2.5 ~ 5 hours at about 120 DEG C of incubation water heatings；
3. after Fructus Citri Limoniae juice reactant aqueous solution terminates, allow hydro-thermal reaction thing naturally cool to room temperature further take out, add methylene chloride reagent to this supernatant volume the most wherein increase by 1/3 and stir 0.5 min, take the supernatant after being allowed to settle uniformly, repeatable 2 ~ 3 times of this step；
4. in the supernatant, add methylene chloride reagent to this supernatant volume increase by 1/3 and stir 0.5 min, after standing uniformly, take again the supernatant；Add acetone the most wherein and increase by 1/3 to this supernatant volume, then this clear liquid is centrifuged 15 min with the rotating speed of 10000 r/min, then takes the supernatant, the aqueous solution containing fluorescent carbon quantum dot after dialysis, can be obtained.
Beneficial effects of the present invention: use the nanocrystal that water-solubility fluorescent carbon quantum dot is 3 ~ 6 nm sizes of the preparation method synthesis of the present invention, even size distribution, productivity is high, repeatability and good dispersion, fluorescence is strong, good stability, Wavelength tunable, and prepared carbon quantum dot toxicity is low, good biocompatibility, the application containing aspects such as group, beneficially cell marking and bio-imaging, fluorescent probe, pharmaceutical carrier such as abundant hydroxyl, carboxyls and modification.Carbon source of the present invention is Fresh Lemon juice, and raw material is easy to get, nontoxic, and without special protection in its production process, synthesis technique is simple, and process is easy to control, with low cost, and the response time is short, energy-and time-economizing, be suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is the photo (a) under sun exposure of the carbon quantum dot aqueous sample (1,2,3,4) prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4 and carbon quantum dot sample (1) excite with the monochromatic light of 405 nm wavelength before the photo of (A) (B) afterwards；
Fig. 2 is carbon quantum dot surface topography (a) of the embodiment of the present invention 1 synthesis, transmission electron microscope (TEM) figure of lattice fringe (b) and corresponding fourier transform (FFT) figure (c) thereof；
Fig. 3 is the carbon quantum dot particle diameter distribution statistics figure of the embodiment of the present invention 1 synthesis；
Fig. 4 is excitation spectrum and the fluorescence Spectra (PL) of the carbon quantum dot of the embodiment of the present invention 1 synthesis；
Fig. 5 is excitation spectrum (PLE) and the fluorescence Spectra (PL) of the carbon quantum dot of the embodiment of the present invention 4 synthesis；
Fig. 6 is the fluorescence microscope images (a) contrast with corresponding optical microscopic image (b) of the fluorescent carbon quantum dot labelling lung carcinoma cell of the embodiment of the present invention 1 synthesis.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, technical scheme is described in detail.
Embodiment
1
Lemon is cleaned peeling go seed to put into juice extractor to be squeezed into juice, take 80 ml lemon juice and 60 ml ethanol in the ratio mixing and stirring of 4:3, obtain 140 ml Fructus Citri Limoniae juice aqueous solutions；This aqueous solution is transferred in the teflon-lined reactor oil bath pan that volume is 200 ml, after 120 DEG C of incubation water heatings react 2.5 hours, naturally cool to room temperature and take out product；Add methylene chloride reagent to this supernatant volume wherein increase by 1/3 and stir 0.5 min, take the supernatant after being allowed to settle uniformly, repeatable 2 ~ 3 times of this step；Add acetone the most wherein and increase by 1/3 to this supernatant volume, this clear liquid is centrifuged 15 min with the rotating speed of 10000 r/min, takes again the supernatant, the aqueous solution containing fluorescent carbon quantum dot can be obtained.
Fig. 2 provides carbon quantum dot surface topography (a) of the embodiment of the present invention 1 synthesis, the TEM figure of lattice fringe (b) and corresponding FFT figure (c) thereof.Fig. 2 (a) shows the torispherical nanocrystal that water-solubility fluorescent carbon quantum dot is 3 ~ 6 nm sizes of the preparation method synthesis using the present invention, even size distribution, and productivity is high, good dispersion；Carbon quantum degree of crystallinity prepared by Fig. 2 (b) display present invention is high, and lattice fringe is clear, and interplanar distance is 0.215 nm, and corresponding to (0-110) crystal face, this coincide with the carbon quantum lattice fourier transform FFT figure of display in Fig. 2 (c).
According to Fig. 2 (a) available carbon quantum dot particle diameter distribution statistics figure, as shown in Figure 3.As seen from Figure 3, the carbon quantum dot uniform particle sizes of present invention synthesis, distribution of sizes is in the range of 3-6 nm, and mean diameter is 4.266 nm.
The carbon quantum dot fluorescent characteristic of the embodiment of the present invention 1 synthesis can carbon quantum dot excitation spectrum as shown in Figure 4 and fluorescence Spectra characterize.PLE and PL curve in Fig. 4 shows, the carbon quantum dot exciting light peak position of the embodiment of the present invention 1 preparation is near 396 nm, for purple light；Fluorescent peal is at 477 nm, for light green color fluorescence.
The carbon quantum dot of the embodiment of the present invention 1 synthesis can be directly used for the fields such as tumor cell labelling and bio-imaging, as shown in Fig. 6 (a).With the optical microphotograph of lung carcinoma cell as compared with Fig. 6 (b), the fluorescence microscopy of fluorescent carbon quantum dot labelling lung carcinoma cell has third dimension as Fig. 6 (a), and the level of cell tissue becomes apparent from.
Embodiment
2
Lemon is cleaned peeling go seed to put into juice extractor to be squeezed into juice, take 80 ml lemon juice and 60 ml ethanol and mix in the ratio of 4:3, stir, obtain 140 ml Fructus Citri Limoniae juice aqueous solutions；This aqueous solution is transferred in the teflon-lined reactor oil bath pan that volume is 200 ml, after 120 DEG C of incubation water heatings react 5 hours, naturally cool to room temperature and take out product；Adding methylene chloride reagent to this supernatant volume wherein increase by 1/3 and stir 0.5 min, take the supernatant after being allowed to settle uniformly, this step can repeat 2 ~ 3 times；Add acetone the most wherein and increase by 1/3 to this supernatant volume, this clear liquid is centrifuged 15 min with the rotating speed of 10000 r/min, takes again the supernatant, the aqueous solution containing fluorescent carbon quantum dot can be obtained.
The fluorescent characteristic of the carbon quantum dot of the 2-in-1 one-tenth of the embodiment of the present invention can excitation spectrum as shown in Figure 5 and fluorescence Spectra characterize.PLE and PL curve in Fig. 5 shows, the carbon quantum dot exciting light peak position of the embodiment of the present invention 2 preparation is near 407 nm, for purple light；Fluorescent peal, at 487 nm, is green fluorescence.
Embodiment
3
Lemon is cleaned peeling go seed to put into juice extractor to be squeezed into juice, take 24 ml lemon juice and 12 ml ethanol and mix in the ratio of 2:1, stir, make the 36 ml Fructus Citri Limoniae juice aqueous solutions presoma as hydro-thermal reaction；This aqueous solution is transferred in the teflon-lined reactor oil bath pan that volume is 200 ml, after 120 DEG C of incubation water heatings react 2.5 hours, naturally cool to room temperature and take out product；Adding methylene chloride reagent to this supernatant volume wherein increase by 1/3 and stir 0.5 min, take the supernatant after being allowed to settle uniformly, this step can repeat 2 ~ 3 times；Add acetone the most wherein and increase by 1/3 to this supernatant volume, this clear liquid is centrifuged 15 min with the rotating speed of 10000 r/min, takes the supernatant, the aqueous solution containing fluorescent carbon quantum dot can be obtained.
Embodiment
4
Lemon is cleaned peeling go seed to put into juice extractor to be squeezed into juice, take 20 ml lemon juice and 20 ml ethanol and mix in the ratio of 1:1, stir, make the 40 ml Fructus Citri Limoniae juice aqueous solutions presoma as hydro-thermal reaction；This aqueous solution is transferred in the teflon-lined reactor oil bath pan that volume is 50 ml, after 120 DEG C of incubation water heatings react 2.5 hours, naturally cool to room temperature and take out product；Adding methylene chloride reagent to this supernatant volume wherein increase by 1/3 and stir 0.5 min, take the supernatant after being allowed to settle uniformly, this step can repeat 2 ~ 3 times；Add acetone the most wherein and increase by 1/3 to this supernatant volume, this clear liquid is centrifuged 15 min with the rotating speed of 10000 r/min, takes again the supernatant, the aqueous solution containing fluorescent carbon quantum dot can be obtained.
Claims (4)
1. a water-solubility fluorescent carbon quantum dot preparation method, the method is with Fresh Lemon juice as carbon source, by hydro-thermal reaction synthesizing water-solubility fluorescent carbon quantum dot, it is characterised in that the method includes the steps of:
Lemon is cleaned peeling go seed to put into juice extractor to be squeezed into juice, take lemon juice and be mixed in proportion with ethanol, make Fructus Citri Limoniae juice aqueous solution as hydro-thermal reaction presoma；
Described Fructus Citri Limoniae juice aqueous solution is put in the reactor polytetrafluoroethyllining lining with oil bath pan heating, react 2.5-5 hour at about 120 DEG C of incubation water heatings；
After Fructus Citri Limoniae juice reactant aqueous solution terminates, allow hydro-thermal reaction product naturally cool to room temperature further take out, adding methylene chloride reagent to this supernatant volume the most wherein increase by 1/3 and stir 0.5 min, wait it to take the supernatant after standing uniformly, this step can repeat 2-3 time；
In the supernatant, add methylene chloride reagent to this supernatant volume increase by 1/3 and stir 0.5 min, after standing uniformly, take again the supernatant；Add acetone the most wherein and increase by 1/3 to this supernatant volume, then this clear liquid is centrifuged 15 min with the rotating speed of 10000 r/min, then takes the supernatant, the aqueous solution containing fluorescent carbon quantum dot after dialysis, can be obtained.
2. water-solubility fluorescent carbon quantum dot preparation method as claimed in claim 1, it is characterised in that described hydro-thermal reaction presoma desirable lemon juice is mixed in the ratio of 4:3 with ethanol.
3. water-solubility fluorescent carbon quantum dot preparation method as claimed in claim 1, it is characterised in that described hydro-thermal reaction presoma desirable lemon juice is mixed in the ratio of 2:1 with ethanol.
4. water-solubility fluorescent carbon quantum dot preparation method as claimed in claim 1, it is characterised in that described hydro-thermal reaction presoma desirable lemon juice is mixed in the ratio of 1:1 with ethanol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698393A (en) * | 2016-12-05 | 2017-05-24 | 广西师范学院 | Method for synthesizing water-soluble carbon quantum dots from orange peels |
| CN107601456A (en) * | 2017-09-21 | 2018-01-19 | 安康德美（中山）纳米科技有限公司 | A kind of high-performance fluorescent carbon quantum dot and preparation method thereof |
| CN114229808A (en) * | 2021-11-22 | 2022-03-25 | 苏州科技大学 | g-C3N4Synthetic method of CQDs material |
| RU2804088C1 (en) * | 2022-12-29 | 2023-09-26 | Федеральное государственное автономное образовательное учреждение высшего образования "Северо-Восточный федеральный университет имени М.К. Аммосова" | Method for making solution of carbon points from berry juices |
-
2015
- 2015-10-29 CN CN201510713466.0A patent/CN105754592A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SWAGATIKA SAHU ET AL.: "Simple one-step synthesis of highly luminescent carbon dots from orange juice: application as excellent bio-imaging agents", 《CHEM. COMMUN.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698393A (en) * | 2016-12-05 | 2017-05-24 | 广西师范学院 | Method for synthesizing water-soluble carbon quantum dots from orange peels |
| CN107601456A (en) * | 2017-09-21 | 2018-01-19 | 安康德美（中山）纳米科技有限公司 | A kind of high-performance fluorescent carbon quantum dot and preparation method thereof |
| CN107601456B (en) * | 2017-09-21 | 2019-08-09 | 安康德美（中山）纳米科技有限公司 | A kind of high-performance fluorescent carbon quantum dot and preparation method thereof |
| CN114229808A (en) * | 2021-11-22 | 2022-03-25 | 苏州科技大学 | g-C3N4Synthetic method of CQDs material |
| RU2804088C1 (en) * | 2022-12-29 | 2023-09-26 | Федеральное государственное автономное образовательное учреждение высшего образования "Северо-Восточный федеральный университет имени М.К. Аммосова" | Method for making solution of carbon points from berry juices |
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