CN109486484A - A kind of carbon dots/Prussian blue composite Nano system preparation and application having both green fluorescence and photothermal conversion efficiency - Google Patents
A kind of carbon dots/Prussian blue composite Nano system preparation and application having both green fluorescence and photothermal conversion efficiency Download PDFInfo
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- CN109486484A CN109486484A CN201710815380.8A CN201710815380A CN109486484A CN 109486484 A CN109486484 A CN 109486484A CN 201710815380 A CN201710815380 A CN 201710815380A CN 109486484 A CN109486484 A CN 109486484A
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- prussian blue
- pbnps
- cds
- conversion efficiency
- photothermal conversion
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 34
- 239000013225 prussian blue Substances 0.000 title claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 6
- 210000004881 tumor cell Anatomy 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 2
- 108010043121 Green Fluorescent Proteins Proteins 0.000 claims 1
- 238000010348 incorporation Methods 0.000 claims 1
- 238000002679 ablation Methods 0.000 abstract description 8
- 230000005284 excitation Effects 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 20
- 235000013339 cereals Nutrition 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000001963 growth medium Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 208000032612 Glial tumor Diseases 0.000 description 2
- 206010018338 Glioma Diseases 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of carbon dots/Prussian blue composite Nano system having both green fluorescence and photothermal conversion efficiency, it is obtained by following methods: preparing prussian blue nano grain first, then carbon dots are generated in prussian blue nano grain surface in situ by microwave method, obtain under 420nm excitation fluoresced green and under 808nm laser irradiation with carbon dots/Prussian blue composite Nano system of photothermal conversion efficiency, which can be used for label and the photo-thermal ablation of tumour cell.
Description
Technical field
The invention belongs to field of nano-luminescent material, and in particular to a kind of carbon for having both green fluorescence and photothermal conversion efficiency
Point/Prussian blue composite Nano system.
The invention further relates to above-mentioned carbon dots/application of the Prussian blue composite Nano system in cell marking.
The invention further relates to application of the above-mentioned carbon dots/Prussian blue composite Nano system in the ablation of cell photo-thermal.
Background technique
Carbon dots have good water solubility, small toxicity, fluorescence intensity high and stablize, system as a kind of novel light-emitting nano material
The advantages that standby easy, be a kind of ideal novel fluorescent material, has important application value in biology and field of medicaments.
Fe in prussian blue nano grain (PBNPs) structure2+And Fe3+ Between charge migration transition cause it near infrared light
There is strong absorption in area, thus has efficient photothermal conversion efficiency.And Prussian blue preparation method is simple, preparation condition temperature
With, it is often more important that, the biological safety of prussian blue nano grain is higher.It therefore, is that one kind has extremely wide research and answers
With the New Generation Optical hot-cast socket agent of prospect.
The high photothermal conversion efficiency of excellent optical performance and prussian blue nano grain based on carbon dots, the present invention pass through microwave
Method generates CDs in PBNPs surface in situ, and preparation has both carbon dots/Prussian blue (CDs/ of optical imagery and photothermal conversion efficiency
PBNPs) composite Nano system, for tumour cell label and photo-thermal ablation.
Summary of the invention
It receives it is an object of that present invention to provide a kind of carbon dots for having both green fluorescence and photothermal conversion efficiency/Prussian blue are compound
Rice system.
To achieve the above object, carbon dots provided by the invention/Prussian blue composite Nano system, is obtained by following methods
It arrives:
A prussian blue nano grain) is prepared: by citric acid and K4[Fe(CN)6] FeCl of the mixed solution addition containing citric acid3 It is molten
In liquid, 1 min is reacted under conditions of 60 DEG C.It is cooled to room temperature.Acetone centrifugation is added, collects precipitating, is freeze-dried get Pu Lu
Scholar's indigo plant nanoparticle.Prussian blue nano grain is added into water；
B) by carbon source citric acid, nitrogen source urea is added in the solution of step A；
C microwave heating) is carried out to the solution of step B；
D the fluoresced green and in 808nm in the case where 420 nm light excite is obtained after) step C products therefrom is dissolved in water, is centrifuged
With the CDs/PBNPs aqueous solution of photothermal conversion efficiency under laser irradiation.
CDs/PBNPs provided by the invention can be applied to cell marking, and the cell addition after culture is contained CDs/
The culture medium of PBNPs carries out total incubation.
The fluoresced green under 420nm excitation of CDs/PBNPs prepared by the present invention, can be directly used for cell mark
Note.
CDs/PBNPs prepared by the present invention has photothermal conversion efficiency under 808nm laser irradiation, can be used for cell
Photo-thermal ablation.
Detailed description of the invention
Fig. 1 is carbon dots prepared by the present invention/Prussian blue composite Nano system under daylight and the irradiation of 420nm exciting light
Photo.
Fig. 2 is that carbon dots prepared by the present invention/Prussian blue composite Nano system is glimmering under different wave length excitation
Light shines spectrogram (for excitation wavelength by 340 nm to 480 nm, step-length is 20 nm).
Fig. 3 is that carbon dots prepared by the present invention/Prussian blue composite Nano system marks the laser co-focusing of C6 cell micro-
Mirror figure.
Fig. 4 be carbon dots prepared by the present invention/Prussian blue composite Nano system and water under 808nm laser irradiation when
M- heating curve figure.
Fig. 5 is the light that carbon dots prepared by the present invention/Prussian blue composite Nano system carries out photo-thermal ablation to tumour cell
Learn microscope figure.
Specific embodiment
The present invention provides a kind of conveniently method preparation carbon dots/Prussian blue composite Nano system, by following steps
It obtains:
A prussian blue nano grain) is prepared: by citric acid and K4[Fe(CN)6] FeCl of the mixed solution addition containing citric acid3
In solution, 1 min is reacted under conditions of 60 DEG C.It is cooled to room temperature.Acetone centrifugation is added, collects precipitating, is freeze-dried general
Shandong scholar's indigo plant nanoparticle.Prussian blue nano grain is added into water；
B) by carbon source citric acid, nitrogen source urea is added in the solution of step A；
C microwave heating) is carried out to the solution of step B；
D the fluoresced green and in 808nm in the case where 420 nm light excite is obtained after) step C products therefrom is dissolved in water, is centrifuged
With the CDs/PBNPs aqueous solution of photothermal conversion efficiency under laser irradiation.
Another object of the present invention is prepared CDs/PBNPs being applied to cell marking comprising following steps:
A) by CDs/PBNPs and tumour cell in 37 °C, 5% CO2Under the conditions of be incubated for altogether；
B) CDs/PBNPs described in laser confocal microscope figure observation a is to cell marking situation.
Yet another object of that present invention is to melt prepared CDs/PBNPs applied to cell photo-thermal comprising following step
It is rapid:
A) tumour cell is respectively placed in two culture mediums containing CDs/PBNPs and without containing CDs/PBNPs, at 37 °
C、5% CO2Under the conditions of be incubated for altogether for 24 hours；
B) two culture medium 10min are irradiated respectively with 808nm laser；
C) photo-thermal ablation of the observation CDs/PBNPs to cell.
Technical solution of the present invention is further illustrated combined with specific embodiments below
Embodiment one:
20ml is contained into 107mg citric acid and 5.4mg K4[Fe(CN)6] mixed solution be added to 20ml and contain same matter
Measure the 1mmol/L FeCl of citric acid3 In solution, 1 min is reacted under conditions of 60 DEG C.It is cooled to room temperature.Be added acetone from
The heart collects precipitating, is freeze-dried to obtain prussian blue nano grain.
Embodiment two:
1) using 90mg citric acid as carbon source, 270mg urea mixes 10mg prussian blue nano grain, is dissolved in as nitrogen source
In 10ml water；
2) using household microwave oven as heat source, 5 min of microwave heating is carried out to the solution of step 1,10ml distillation is added after cooling
Water dissolution；
3) solution of step 2 is centrifuged (7000 revs/min, 15 minutes), abandons supernatant, obtains CDs/PBNPs；
4) the luminosity characterization of gained CDs/PBNPs: CDs/PBNPs aqueous solution show it is light blue, in the sharp of 420 nm of wavelength
It shines under excitation, CDs/PBNPs aqueous solution issues obvious green light (Fig. 1)；Different excitation wavelengths are obtained with sepectrophotofluorometer
Fluorescence radiation spectrogram under (340-480nm, 20 nm of step-length) further confirms CDs/PBNPs prepared by the present invention in 420nm
Green fluorescence (Fig. 2) is issued under excitation.
Embodiment three:
1) C6 glioma cell is inoculated in the 6 hole culture dishes for being placed with coverslip, in 37 °C, 5% CO2It is trained in incubator
It supports；
2) after cell is adherent, supernatant is sucked, is added and contains CDs/PBNPs culture medium prepared by the present invention, in 37 °C, 5% CO2
24 h are incubated in incubator altogether；
3) coverslip is taken out, with PBS buffer solution for cleaning, fixed cell；
4) in light microscopic observation CDs/PBNPs to C6 cell marking situation (Fig. 3).The cell of CDs/PBNPs label is mixed in 420nm
Excitation is lower to issue green fluorescence.
Example IV:
1) using 90mg citric acid as carbon source, 360mg urea mixes 10mg prussian blue nano grain, is dissolved in as nitrogen source
In 10ml water；
2) using household microwave oven as heat source, 5 min of microwave heating is carried out to the solution of step 1,10ml distillation is added after cooling
Water dissolution；
3) (7000 revs/min, 15 minutes) are centrifuged to the solution of step 2, obtain CDs/PBNPs；
Embodiment five:
1) compound concentration is the CDs/PBNPs solution of 0.8 mg/mL；
2) with 808 nm laser irradiation, 10 min, every 15 seconds record temperature；
3) CDs/PBNPs is obtained using the temperature (°C) of CDs/PBNPs solution as ordinate using the time (s) as abscissa
The temperature changing curve diagram (Fig. 4) of solution.Photothermal conversion the experimental results showed that, temperature is kept not water substantially upon laser irradiation
Become, and temperature has obvious rising to CDs/PBNPs solution upon laser irradiation, has been more than the temperature threshold that photo-thermal kills tumour cell
It is worth (42 °C), shows that CDs/PBNPs has excellent photothermal conversion performance, can be used for photo-thermal ablation.
Embodiment six:
1) in the 96 hole culture dishes for being inoculated in C6 glioma cell, in 37 °C, 5% CO2It is cultivated in incubator；
2) after cell is adherent, supernatant is sucked, is separately added into 2 holes containing CDs/PBNPs culture medium prepared by the present invention
With do not contain CDs/PBNPs culture medium prepared by the present invention, in 37 °C, 5% CO224 h are incubated in incubator altogether；
3) 10min is irradiated respectively with 808 nm laser；
4) in light, comparison CDs/PBNPs melts situation (Fig. 5) to C6 cell photo-thermal under the microscope.Wherein left figure is C6 tumour cell
Optical microscope after CDs/PBNPs is added；Right figure is that the C6 tumour cell of CDs/PBNPs is added in 808nm laser photograph
Optical microscope after penetrating.It can be seen that the C6 cell being added after CDs/PBNPs is substantially dead under 808nm laser irradiation, therefore
CDs/PBNPs has photo-thermal toxicity to tumour cell, can be used for the ablation of tumour cell photo-thermal.
Claims (5)
1. a kind of carbon dots/Prussian blue composite Nano system (CDs/PBNPs) for having both green fluorescence and photothermal conversion efficiency is led to
Following methods are crossed to obtain:
A prussian blue nano grain) is prepared, prussian blue nano grain is added into water；
B) by carbon source citric acid, nitrogen source urea is added in the solution of step A；
C microwave heating) is carried out to the solution of step B；
D the fluoresced green and in 808nm in the case where 420 nm light excite is obtained after) step C products therefrom is dissolved in water, is centrifuged
With the CDs/PBNPs aqueous solution of photothermal conversion efficiency under infrared laser.
2. the green fluorescence and the CDs/PBNPs of photothermal conversion efficiency according to claim 1 of having both is existed by microwave method
Prussian blue nano grain Surface Creation green fluorescent carbon dots and obtain.
3. the CDs/PBNPs according to claim 1 for having both green fluorescence and photothermal conversion efficiency, wherein citric acid with
The quality of urea is 1:3 to 1:5 than range, and incorporation prussian blue nano grain quality is 5mg-15mg, and the microwave time is 3-5 points
Clock.
4. the label that CDs/PBNPs prepared by claim 1 is used for tumour cell.
5. the photo-thermal of CDs/PBNPs prepared by claim 1 for tumour cell melts.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710815380.8A CN109486484A (en) | 2017-09-12 | 2017-09-12 | A kind of carbon dots/Prussian blue composite Nano system preparation and application having both green fluorescence and photothermal conversion efficiency |
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|---|---|---|---|
| CN201710815380.8A CN109486484A (en) | 2017-09-12 | 2017-09-12 | A kind of carbon dots/Prussian blue composite Nano system preparation and application having both green fluorescence and photothermal conversion efficiency |
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| CN109486484A true CN109486484A (en) | 2019-03-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152021A (en) * | 2019-06-26 | 2019-08-23 | 湖北大学 | A kind of medicament carrier system and preparation method thereof having target administration ability in cancer cell |
| CN112919496A (en) * | 2021-01-28 | 2021-06-08 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN113150778A (en) * | 2021-05-07 | 2021-07-23 | 澳门大学 | Aluminum functionalized fluorescent carbon dot and preparation method and application thereof |
-
2017
- 2017-09-12 CN CN201710815380.8A patent/CN109486484A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152021A (en) * | 2019-06-26 | 2019-08-23 | 湖北大学 | A kind of medicament carrier system and preparation method thereof having target administration ability in cancer cell |
| CN110152021B (en) * | 2019-06-26 | 2021-07-06 | 湖北大学 | Drug carrier system with cancer cell internal target administration capability and preparation method thereof |
| CN112919496A (en) * | 2021-01-28 | 2021-06-08 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN112919496B (en) * | 2021-01-28 | 2022-03-29 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN113150778A (en) * | 2021-05-07 | 2021-07-23 | 澳门大学 | Aluminum functionalized fluorescent carbon dot and preparation method and application thereof |
| CN113150778B (en) * | 2021-05-07 | 2023-03-07 | 澳门大学 | Aluminum functionalized fluorescent carbon dot and preparation method and application thereof |
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Application publication date: 20190319 |