CN109652065A - A kind of preparation method of gold doping fluorescent carbon quantum dot - Google Patents
A kind of preparation method of gold doping fluorescent carbon quantum dot Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000010931 gold Substances 0.000 title claims abstract description 72
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 72
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229920001661 Chitosan Polymers 0.000 claims abstract description 53
- 230000004048 modification Effects 0.000 claims abstract description 50
- 238000012986 modification Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 51
- 239000007864 aqueous solution Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002096 quantum dot Substances 0.000 claims 3
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- 244000248349 Citrus limon Species 0.000 claims 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 1
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- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 2
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- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
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- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003260 anti-sepsis Effects 0.000 description 1
- 101150113720 aunc gene Proteins 0.000 description 1
- 229940052223 basic fuchsin Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
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- 239000000090 biomarker Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 150000002243 furanoses Chemical class 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
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- 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
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The present invention provides a kind of preparation method of golden doping fluorescent carbon quantum dot comprising following steps: preparation carries the modification of chitosan compound water solution of gold nanoclusters；After the modification of chitosan compound water solution for carrying gold nanoclusters and aqueous citric acid solution are mixed, hydro-thermal reaction is carried out, the golden doping fluorescent carbon quantum dot is made.Method of the invention is capable of providing the golden doping fluorescent carbon quantum dot for double fluorescence emission wavelengths that hypotoxicity, bio-compatibility are good, good water solubility, fluorescent yield are high, storage stability is good.
Description
Technical field
The invention belongs to medical biochemistry detection fields, and in particular to a kind of golden doping fluorescent carbon amounts of double fluorescence emission wavelengths
Son point and preparation method thereof.
Background technique
In recent years using at most, quanta point material is paid close attention to by researcher, but some researches show that quantum in recent years
For point containing heavy metal chromium and selenium etc., toxicity is big, therefore many scientists are striving to find its new substitute.Carbon quantum dot
(CQD, carbon quantum dot) is a kind of carbon nanomaterial that new development is got up, and is by sp2Hydridization carbon or amorphous carbon
Composition, energy stabilized illumination, size are expected to replace semiconductor amount less than 10nm, the fluorescent nano particle with torispherical structure
Son point is as medical fluorescent material.In recent years, people have developed the carbon source of numerous preparation carbon quantum dots, such as graphite, grape
Sugar, citric acid, anti-sepsis acid, gelatin, sucrose, poly- pyranose sugar derivatives, poly- furanose, poly glucosamine etc..
Single signal fluorescent material has been difficult to meet the needs of each discipline development, and such as single fluorescent material can be complete well
At the detection of molecular ion, label of large biological molecule etc., but enrichment cannot be efficiently separated to effective quantity, to meet
The separation and concentration of target object may be implemented using magnetisable material by existing micro-analysis instrument, someone, not can be carried out but corresponding
Detection, and magnetic carbon quantum dot is the combination of fluorescent material and magnetic material.Dual signal (or even multi signal) fluorescent nano material
Because can by the excitation of different wave length, and then can fluorescence imaging under various circumstances, therefore have a good application prospect,
It has been subjected to the highest attention of the area researches person such as materialogy, analytical chemistry, biology, medicine and pharmacology.
Fluorescent nano material generally includes: semiconductor-quantum-point, rear-earth-doped up-conversion nano material, noble metal nano grain
Sub (such as gold nanoparticle) and carbon quantum dot.But the preparation condition of semiconductor-quantum-point is harsher, and precursor is
The heavy metal ion salt such as Cd, Pb, Hg can all cause greatly to injure to human body and environment, these factors limit to a certain extent
Its application.The raw material for preparing up-conversion is more expensive.Therefore, small toxicity, good biocompatibility gold nanoparticle and
Carbon quantum dot has attracted the concern of more researchers.Huang Hong et al. (Zhejiang Normal University, Master's thesis, 2014) utilizes difference
Carbon source has synthesized various new fluorescent nano material, has studied in detail its fluorescent characteristic and its targets identification performance, and go deep into visiting
Related targets identification mechanism: (1) synthesis of captopril-gold nanoparticle and Hg is begged for2+Targets identification research is general with Kato
Benefit is stabilizer, and tetramethylol chloride is reducing agent, is synthesized by the method for simple, mild, quick (5 minutes), green glimmering
Light gold nanoparticle, utilizes Hg2+The fluorescence of gold nanoparticle specific can be quenched, fluorescence gold nanoparticle can be used for ambient water
Hg in sample2+The quick detection of content；(2) the fluorescence gold nanoparticle of polypeptide Template synthesis Wavelength tunable is adopted with its performance study
It is template with the different polypeptide of sequential structure, sodium borohydride is reducing agent, has synthesized the fluorescence Jenner with different emission
Rice corpuscles, using this gold nanoparticle as probe, it can be achieved that Hg2+High sensitivity and highly selective detection；(3) using strawberry as carbon
Source, hydro-thermal method synthesize the fluorescent carbon quantum dot of N doping, and gained carbon quantum dot good water solubility, stability are high, and can be used as glimmering
Light probe measures Hg2+.It (4) is raw material with grape, one step hydro thermal method synthesizes the higher fluorescent carbon quantum dot of quantum yield, the carbon amounts
Son puts while having many characteristics, such as that small good water solubility, stability height, partial size, size uniformity, cytotoxicity are low, and has preferable thin
Born of the same parents' imaging capability.
When size of nanometer gold grain gradually decreases to suitable with Fermi's wavelength, electronic structure and semiconductor type seemingly, energy
Grade is discontinuous.These extra small gold nano grains have fluorescent characteristic, the gold nanoclusters that are otherwise known as (AuNC).Compared to traditional
Fluorescence probe, gold nanoclusters have the advantages that more.It has higher quantum yield, longer fluorescence lifetime, anti-light bleaching
Ability is strong, and there is emission spectrum wavelength size to rely on adjustability, and Stokes shift is big and bio-toxicity is low.Therefore, Jenner
Rice cluster is expected to be used widely as a kind of novel fluorescence nano material in biomarker, fluorescence imaging field.It revives small clearly etc.
People's (Southeast China University's Master's thesis 2016) is by chemical reduction method, and using gold chloride as precursors, GSH is reducing agent,
The preparation method of fluorescence gold nanoclusters is explored under different condition, and has further investigated mercaptan to the fluorescence intensity of gold nanoclusters
Influence.
Current most of reported carbon quantum dot fluorescence quantum yields are lower, and the reality for limiting it in every field is answered
With some carbon quantum dot surfaces lack effective recognition group, cause it limited to the specific binding capacity of object, select
Property is bad；Biochemical sensor based on carbon quantum dot building is mostly exported using the change of single fluorescent emission intensity as signal single
Member has that fluorescence intensity is interfered vulnerable to factors such as excitation light source intensity, concentration and probe concentrations, the accuracy of detection is caused to need
It improves.Shang Guan Jing virtue et al. (Hunan University's Master's thesis 2017) uses different raw materials, passes through simple hydrothermal synthesis method
It is prepared for a series of carbon quantum dots with unique optical properties.Specifically include that (1) novel high fluorescence nitrogen-doped carbon quantum dot
Preparation and its cell imaging application study, compared to fluorescent dye, most of reported carbon quantum dots there are quantum yield compared with
Low disadvantage strongly limits it in the practical application in biochemical sensitive field；(2) nitrogen, the high fluorescence carbon quantum of phosphor codoping are based on
Point fluorescence probe is prepared and its to Fe in biological sample3+Detection research, in order to realize carbon quantum dot surface functional group it is simple,
It is rapidly introduced into and Heteroatom doping is combined to improve quantum yield, choose atriphos as carbon source, nitrogen source and phosphorus source, pass through
Hydro-thermal method the one-step synthesis nitrogen with high quantum production rate, phosphor codoping carbon quantum dot, the carbon quantum dot have good fluorescence
Stability, hypotoxicity and water solubility, quantum yield is up to 43.2%, to functional group and On Analysis of Chemical Species of Elements it is found that its surface contains
There are the functional groups such as a large amount of carboxyls, phosphate group, such nitrogen, phosphor codoping carbon quantum dot fluorescence probe can be used as Fe3+That detects is new
Method；(3) the Ratiometric fluorescent probe preparation based on label-free carbon quantum dot and its to internal pH Application in Sensing research, in order to
Further solve dyestuff existing for carbon quantum dot binding fluorescent dyes or other fluorescent nano materials building Ratiometric fluorescent probe
The deficiencies of leakage, crosslinking and purification steps troublesome is reaction with citric acid and basic fuchsin by simple hydrothermal synthesis method
Object, a step are prepared for the fluorescent carbon quantum dot of label-free, double transmittings.The carbon quantum dot 380nm exciting light irradiation under, respectively at
There are two fluorescence emission peaks at 475nm and 545nm, and fluorescent emission intensity shows excellent photostability, and experiment shows this
Two fluorescent emission intensities of double transmitting carbon quantum dots have pH responsiveness simultaneously.
Summary of the invention
It is an object of the invention to aiming at the above technical problems to be solved, provide a kind of hypotoxicity, bio-compatibility
Well, the golden doping fluorescent carbon quantum dot of the high double fluorescence emission wavelengths of good water solubility, fluorescent yield.
It is a further object to provide the preparation methods of above-mentioned golden doping fluorescent carbon quantum dot.
For this purpose, the present invention provides following technical schemes.
A kind of preparation method of gold doping fluorescent carbon quantum dot comprising following steps:
Step 1. preparation carries the modification of chitosan compound water solution of gold nanoclusters: being 1% by 5~20mL mass concentration
After modification of chitosan aqueous solution is mixed with the aqueous solution of chloraurate that 1~3mL concentration is 4mol/L, adding 3~5mL concentration is
The aqueous citric acid solution of 4mol/L stands 15~60 minutes after mixing；Then the sulfur-bearing of 0.400g and the change of nitrogen are added
Object is closed, the aqueous citric acid solution that 9~14mL concentration is 4mol/L is added after stirring evenly into mixed system, mixes and stands,
The modification of chitosan compound water solution for carrying gold nanoclusters is obtained, wherein the sulfur-bearing and the compound of nitrogen are sulfydryl
Ethamine or any one of thioacetic acid or ethylenediamine；
Step 2. is by the modification of chitosan compound water solution of the load gold nanoclusters of 0.625~5g and contains 1~5g
After the aqueous solution 30mL of citric acid is mixed, 150 DEG C~200 DEG C at a temperature of it is lower carry out hydro-thermal reaction, the gold is made and adulterates
Fluorescent carbon quantum dot.
As a preferred embodiment, the method also includes right after the golden doping fluorescent carbon quantum dot is made
It carries out purification process.
As a preferred embodiment, the purification process includes: to be centrifuged the golden doping fluorescent carbon quantum dot
It dialyses again afterwards.The speed of centrifugation is preferably 5000r/ minutes to 12000r/ minutes, and more preferably 6000r/ minutes extremely
10000r/ minutes.
As a preferred embodiment, the temperature for carrying out hydro-thermal reaction in the step 2 is preferably 160 DEG C~190
℃.More preferably 180 DEG C.
As a preferred embodiment, the time for carrying out hydro-thermal reaction in the step 2 is at least 300 minutes.
As a preferred embodiment, the modification of chitosan graft copolymerization has polymerized monomer N- ethenyl pyrrolidone
The chitosan of ketone and function monomer acrylic acid.
Compared with prior art, golden doping fluorescent carbon quantum dot of the invention has hypotoxicity and good bio-compatible
Property, good water solubility, fluorescent yield is high, and storage stability is good.
Detailed description of the invention
Fig. 1 is total dosage preparation for carrying difference when gold amount is 1% and carrying the modification of chitosan compound water solution of gold nanoclusters
Golden doping fluorescent carbon quantum dot ultraviolet spectrogram.
Fig. 2 is total dosage preparation for carrying difference when gold amount is 1% and carrying the modification of chitosan compound water solution of gold nanoclusters
Golden doping fluorescent carbon quantum dot fluorescence spectra.
Fig. 3 is total dosage preparation for carrying difference when gold amount is 2% and carrying the modification of chitosan compound water solution of gold nanoclusters
Golden doping fluorescent carbon quantum dot fluorescence spectra.
Fig. 4 is that the modification of chitosan compound water solution dosage of load gold nanoclusters when always load gold amount is 2% is 0.625g system
Standby golden doping fluorescent carbon quantum dot fluorescence spectra, with two excitation wavelength.
Fig. 5 is TEM (transmission electron microscope) figure of the golden doping fluorescent carbon quantum dot with two excitation wavelength.
Fig. 6 is total dosage preparation for carrying difference when gold amount is 1% and carrying the modification of chitosan compound water solution of gold nanoclusters
Golden doping fluorescent carbon quantum dot fluorescence spectra.
Fig. 7 is total dosage preparation for carrying difference when gold amount is 2% and carrying the modification of chitosan compound water solution of gold nanoclusters
Golden doping fluorescent carbon quantum dot fluorescence spectra.
Fig. 8 is that the modification of chitosan compound water solution dosage of load gold nanoclusters when always load gold amount is 3% is 0.625g system
Standby golden doping fluorescent carbon quantum dot fluorescence spectra, with two excitation wavelength.
Specific embodiment
Combined with specific embodiments below, technical solution of the present invention is described in further detail, but the present invention is not limited to
Following embodiment.
As unspecified, reagent used in the present invention is available reagent, can be obtained by commercial channel.For letter
Syllabus, portion of techniques operation does not specifically describe details, it should be appreciated that these operations are all well known to those skilled in the art
In the range of, it can be achieved according to content documented in this specification.
Modification of chitosan used in the present invention is that graft copolymerization has polymerized monomer n-vinyl pyrrolidone and function list
The chitosan of body acrylic acid.
Preparing modification of chitosan aqueous solution, specific step is as follows:
Be raw material (88 parts) with 1% (wt) shell and sugared acidic aqueous solution (abbreviation CTS), the high cerium of sulfur acid (0.1 part) it is dilute
(20 parts) of nitric acid (0.5%wt) aqueous solution are initiator, under conditions of having nitrogen protection for 45 DEG C, with polymerized monomer N- vinyl
(10 parts) the generation graft copolymerizations of pyrrolidones (10 parts) and function monomer (such as acrylic acid), prepare modification of chitosan (CTS-g-P
(NVP-co-AA))。
Test method is as follows:
(1) test and characterization of golden doping fluorescent carbon quantum dot
Using the pattern and particle size of transmission electron microscope (TEM) observation carbon quantum dot and magnetic carbon quantum dot；
With " modification of chitosan+citric acid+mercaptoethylmaine " system synthesis carbon quantum (modification of chitosan aqueous solution (3mL),
The aqueous solution 30mL of the citric acid containing 3g is added thereto, obtains within hydro-thermal reaction 300 minutes at 180 DEG C in Muffle furnace after mixing
It arrives.) it is blank control, survey ultraviolet spectra；
Using the fluorescent characteristic of sepectrophotofluorometer (excitation wavelength is respectively as follows: 356nm or 425nm) study sample.
(2) measurement of the fluorescent yield of golden doping fluorescent carbon quantum dot
A small amount of reference substance quinine sulfate (QY=0.577) is dissolved in the sulfuric acid solution of 0.05N, in this, as reference substance, is surveyed
Measure the emission peak integral area and ultraviolet suction of determinand and quinine sulfate under Same Wavelength (the maximum excitation wavelength of reference substance)
Luminosity (need to be maintained under 0.05), and the calculation formula of quantum yield is as follows:
YQs=YQr(Fs/Fr)(Ar/As)(ηs/ηr)2
QY is quantum yield, and F is fluorescent emission peak area, and A is the absorbance under excitation wavelength, and η is the refraction of solvent
Rate.Wherein s indicates determinand；R indicates reference substance.
Embodiment 1:
Measuring when total load gold is 1%, changes the modification of chitosan compound water solution dosage of load gold nanoclusters, " citric acid+
Golden doping fluorescent carbon quantum dot is prepared in mercaptoethylmaine " system
(1) after taking the aqueous solution of chloraurate of (wt) modification of chitosan of 10mL 1% aqueous solution, 1mL 4mol/L to mix, add
The aqueous citric acid solution of 3mL4mol/L stands 30 minutes (15 to 60 minutes) after mixing；Again plus 0.400g mercaptoethylmaine, it stirs
The aqueous citric acid solution for adding 12mL 4mol/L in uniformly backward mixed system is mixed, at least 3h is mixed and stand, obtains carrying gold nano
The modification of chitosan compound water solution of cluster.
(2) take respectively with upload gold amount for 1% load gold nanoclusters modification of chitosan compound water solution 1.25g,
The aqueous solution 30mL of the citric acid containing 2.5g is added in 2.5g, 5g thereto, after mixing in Muffle furnace at 180 DEG C hydro-thermal reaction
At least 300 minutes, prepare crude product.
(3) (extremely with 5000r/ minutes to 12000r/ minutes, more preferably 6000r/ minutes through appropriate purification process
10000r/ minutes, most preferably 8000r/ minutes speed is packed into the bag filter pure water dialysis 72h of 2000Da after being centrifuged 30 minutes,
Freeze-dried back；Or directly refrigerator is stored refrigerated.), obtain golden doping fluorescent carbon quantum dot.
TEM figure shows that the golden doping fluorescent carbon quantum dot that the present embodiment obtains is almost spherical, average diameter about 7.5nm.
Obtained golden doping fluorescent carbon quantum dot sample is diluted 15000 times, is tested.The results show that with addition
Load gold nanoclusters modification of chitosan compound water solution amount it is different, product appearance color is also different, and 1.25g dosage is brown
Color, 2.5g dosage are yellow, and 5g dosage is brown.Ultraviolet spectrogram as shown in Figure 1, fluorescence spectra as shown in Fig. 2, in Fig. 2
Numerical value " 14000 " indicate same concentrations sample dilute 14000 times before testing.
By test result as it can be seen that with golden doping fluorescent carbon quantum dot aqueous solution prepared by " citric acid+mercaptoethylmaine " system,
As the peak value about 450nm of the emission spectrum under the excitation light action in 365nm；Transmitting under the excitation light action in 425nm
The peak value of spectrum about 500nm；It can be seen that golden doping fluorescent carbon quantum dot makes " response " to the exciting light of dual wavelength.
Embodiment 2:
Measuring when total load gold is 1%, changes the modification of chitosan compound water solution dosage of load gold nanoclusters, " citric acid+
Golden doping fluorescent carbon quantum dot in the preparation of thioacetic acid " system
(1) after taking the aqueous solution of chloraurate of (wt) modification of chitosan of 20mL 1% aqueous solution, 1mL 4mol/L to mix, add
The aqueous citric acid solution of 3mL4mol/L stands 30 minutes (15 to 60 minutes) after mixing；Again plus 0.400g thioacetic acid, it stirs
The aqueous citric acid solution for adding 14mL 4mol/L in uniformly backward mixed system is mixed, at least 3h is mixed and stand, obtains carrying gold nano
The modification of chitosan compound water solution of cluster.
(2) take respectively with upload gold amount for 1% load gold nanoclusters modification of chitosan compound water solution 0.625g,
The aqueous solution 30mL of the citric acid containing 1.5g is added thereto, is lauched in Muffle furnace at 160 DEG C after mixing by 1.25g, 2.5g, 5g
Thermal response at least 300 minutes, prepare crude product.
(3) (extremely with 5000r/ minutes to 12000r/ minutes, more preferably 6000r/ minutes through appropriate purification process
10000r/ minutes, most preferably 8000r/ minutes speed is packed into the bag filter pure water dialysis 72h of 2000Da after being centrifuged 30 minutes,
Freeze-dried back；Or directly refrigerator is stored refrigerated.), obtain golden doping fluorescent carbon quantum dot.
Obtained golden doping fluorescent carbon quantum dot sample is diluted 10000 times, is tested.As a result as shown in fig. 6, result
It has been shown that, fluorescence intensity ratio Fig. 2 counter sample of the present embodiment products obtained therefrom are lower (the curve A in such as Fig. 2).
TEM figure shows that the golden doping fluorescent carbon quantum dot that the present embodiment obtains is almost spherical, average diameter about 7.5nm.
By test result as it can be seen that with golden doping fluorescent carbon quantum dot aqueous solution prepared by " citric acid+thioacetic acid " system,
As the peak value about 450nm of the emission spectrum under the excitation light action in 365nm；Transmitting under the excitation light action in 425nm
The peak value of spectrum about 500nm；It can be seen that golden doping fluorescent carbon quantum dot makes " response " to the exciting light of dual wavelength.
Embodiment 3:
Measuring when total load gold is 2%, changes the modification of chitosan compound water solution dosage of load gold nanoclusters, " citric acid+
Golden doping fluorescent carbon quantum dot in the preparation of mercaptoethylmaine " system
(1) after taking the aqueous solution of chloraurate of (wt) modification of chitosan of 10mL 1% aqueous solution, 2mL 4mol/L to mix, add
The aqueous citric acid solution of 3mL4mol/L stands 30 minutes (15 to 60 minutes) after mixing；Again plus 0.400g mercaptoethylmaine, it stirs
The aqueous citric acid solution for adding 12mL 4mol/L in uniformly backward mixed system is mixed, at least 3h is mixed and stand, obtains carrying gold nano
The modification of chitosan compound water solution of cluster.
(2) take respectively with upload gold amount for 1% load gold nanoclusters modification of chitosan compound water solution 0.625g,
The aqueous solution 30mL of the citric acid containing 2.5g is added thereto, is lauched in Muffle furnace at 190 DEG C after mixing by 1.25g, 2.5g, 5g
Thermal response at least 300 minutes, prepare crude product.
(3) (extremely with 5000r/ minutes to 12000r/ minutes, more preferably 6000r/ minutes through appropriate purification process
10000r/ minutes, most preferably 8000r/ minutes speed is packed into the bag filter pure water dialysis 72h of 2000Da after being centrifuged 30 minutes,
Freeze-dried back；Or directly refrigerator is stored refrigerated.), obtain golden doping fluorescent carbon quantum dot.
TEM figure shows that the golden doping fluorescent carbon quantum dot that the present embodiment obtains is almost spherical, average diameter about 7.5nm.
Obtained golden doping fluorescent carbon quantum dot sample is diluted 15000 times, is tested.The results show that product appearance
Color is brown.Fluorescence spectra is as shown in Figure 3.
By test result as it can be seen that with golden doping fluorescent carbon quantum dot aqueous solution prepared by " citric acid+mercaptoethylmaine " system,
As the peak value about 450nm of the emission spectrum under the excitation light action in 365nm；Transmitting under the excitation light action in 425nm
The peak value of spectrum about 500nm；It can be seen that golden doping fluorescent carbon quantum dot makes " response " to the exciting light of dual wavelength.
Embodiment 4:
Measuring when total load gold is 2%, changes the modification of chitosan compound water solution dosage of load gold nanoclusters, " citric acid+
Golden doping fluorescent carbon quantum dot in the preparation of ethylenediamine " system
(1) after taking the aqueous solution of chloraurate of (wt) modification of chitosan of 5mL 1% aqueous solution, 2mL 4mol/L to mix, add
The aqueous citric acid solution of 3mL4mol/L stands 30 minutes (15 to 60 minutes) after mixing；Again plus 0.400g ethylenediamine, stirring
The aqueous citric acid solution for uniformly adding 14mL 4mol/L in backward mixed system, mixes and stands at least 3h, obtain carrying gold nanoclusters
Modification of chitosan compound water solution.
(2) take with upload gold amount for 2% load gold nanoclusters modification of chitosan compound water solution 0.625g, 1.25g,
2.5g, 5g (sample for adding additional a 10g), are added the aqueous solution 30mL of the citric acid containing 1.0g, in horse after mixing thereto
Not in furnace at 150 DEG C hydro-thermal reaction at least 300 minutes, prepare crude product (with a large amount of black solids precipitate generate).
(3) (extremely with 5000r/ minutes to 12000r/ minutes, more preferably 6000r/ minutes through appropriate purification process
10000r/ minutes, most preferably 8000r/ minutes speed is packed into the bag filter pure water dialysis 72h of 2000Da after being centrifuged 30 minutes,
Freeze-dried back；Or directly refrigerator is stored refrigerated.), obtain golden doping fluorescent carbon quantum dot.
TEM figure shows that the golden doping fluorescent carbon quantum dot that the present embodiment obtains is almost spherical, and base average diameter is about
7.5nm。
Obtained golden doping fluorescent carbon quantum dot sample is diluted 1000 times, is tested.
It is by test result (Fig. 7) as it can be seen that water-soluble with the golden doping fluorescent carbon quantum dot of " citric acid+ethylenediamine " system preparation
Liquid, by taking " sample of modification of chitosan compound water solution additive amount 0.625g " as an example (only 10 times of dilution), when swashing in 365nm
The peak value of emission spectrum under luminous function about 450nm；When 425nm excitation light action under emission spectrum peak value about
500nm；It can be seen that golden doping fluorescent carbon quantum dot makes " response " to the exciting light of dual wavelength.
Embodiment 5:
Total gold amount that carries is 2%, and the modification of chitosan compound water solution dosage for carrying gold nanoclusters is 0.625g, in " lemon
Golden doping fluorescent carbon quantum dot in the preparation of acid+mercaptoethylmaine " system
(1) after taking the aqueous solution of chloraurate of (wt) modification of chitosan of 10mL 1% aqueous solution, 2mL 4mol/L to mix, add
The aqueous citric acid solution of 3mL4mol/L stands 30 minutes (15 to 60 minutes) after mixing；Again plus 0.400g mercaptoethylmaine, it stirs
The aqueous citric acid solution for adding 12mL 4mol/L in uniformly backward mixed system is mixed, at least 3h is mixed and stand, obtains carrying gold nano
The modification of chitosan compound water solution of cluster.
(2) it takes to upload gold amount for the 2% modification of chitosan compound water solution 0.625g for carrying gold nanoclusters, thereto
The aqueous solution 30mL of the citric acid containing 2.5g is added, hydro-thermal reaction 300 minutes, preparation are thick at 180 DEG C in Muffle furnace after mixing
Product.
(3) (extremely with 5000r/ minutes to 12000r/ minutes, more preferably 6000r/ minutes through appropriate purification process
10000r/ minutes, most preferably 8000r/ minutes speed is packed into the bag filter pure water dialysis 72h of 2000Da after being centrifuged 30 minutes,
Freeze-dried back；Or directly refrigerator is stored refrigerated.), obtain golden doping fluorescent carbon quantum dot.
TEM figure (Fig. 5) shows that the golden doping fluorescent carbon quantum dot that the present embodiment obtains is almost spherical, and average diameter is about
7.5nm。
Obtained golden doping fluorescent carbon quantum dot sample is diluted 45000 times, is tested.The experimental result of corresponding test
As shown in Figure 4.From fig. 4, it can be seen that with golden doping fluorescent carbon quantum dot aqueous solution prepared by " citric acid+mercaptoethylmaine " system, when
The peak value about 450nm of emission spectrum under the excitation light action of 365nm；Transmitting light under the excitation light action in 425nm
The peak value of spectrum about 510nm；It can be seen that golden doping fluorescent carbon quantum dot makes " response " to the exciting light of dual wavelength.
Embodiment 6:
Total gold amount that carries is 3%, and the modification of chitosan compound water solution dosage for carrying gold nanoclusters is 0.625g, in " lemon
Golden doping fluorescent carbon quantum dot in the preparation of acid+mercaptoethylmaine " system
(1) after taking the aqueous solution of chloraurate of (wt) modification of chitosan of 10mL 1% aqueous solution, 3mL 4mol/L to mix, add
The aqueous citric acid solution of 5mL4mol/L stands 30 minutes (15 to 60 minutes) after mixing；Again plus 0.400g mercaptoethylmaine, it stirs
The aqueous citric acid solution for adding 9mL 4mol/L in uniformly backward mixed system is mixed, at least 3h is mixed and stand, obtains carrying gold nano
The modification of chitosan compound water solution of cluster.
(2) it takes to upload gold amount for the 3% modification of chitosan compound water solution 0.625g for carrying gold nanoclusters, thereto
The aqueous solution 30mL of the citric acid containing 5.0g is added, hydro-thermal reaction 300 minutes, preparation are thick at 200 DEG C in Muffle furnace after mixing
Product.
(3) (extremely with 5000r/ minutes to 12000r/ minutes, more preferably 6000r/ minutes through appropriate purification process
10000r/ minutes, most preferably 8000r/ minutes speed is packed into the bag filter pure water dialysis 72h of 2000Da after being centrifuged 30 minutes,
Freeze-dried back；Or directly refrigerator is stored refrigerated.), obtain golden doping fluorescent carbon quantum dot.
TEM figure shows that the golden doping fluorescent carbon quantum dot that the present embodiment obtains is almost spherical, average diameter about 7.5nm.
Obtained golden doping fluorescent carbon quantum dot sample is diluted 50000 times, is tested.Corresponding test experiments result
Counter sample is suitable (the curve A in such as Fig. 3) in (Fig. 8) and Fig. 3.
By test result as it can be seen that with golden doping fluorescent carbon quantum dot aqueous solution prepared by " citric acid+mercaptoethylmaine " system,
As the peak value about 450nm of the emission spectrum under the excitation light action in 365nm；Transmitting under the excitation light action in 425nm
The peak value of spectrum about 500nm；It can be seen that golden doping fluorescent carbon quantum dot makes " response " to the exciting light of dual wavelength.
Claims (8)
1. a kind of preparation method of gold doping fluorescent carbon quantum dot comprising following steps:
Step 1. preparation carries the modification of chitosan compound water solution of gold nanoclusters: the modification for being 1% by 5~20mL mass concentration
After chitosan aqueous solution is mixed with the aqueous solution of chloraurate that 1~3mL concentration is 4mol/L, adding 3~5mL concentration is 4mol/L
Aqueous citric acid solution, stand 15~60 minutes after mixing；Then the sulfur-bearing of 0.400g and the compound of nitrogen are added, is stirred
It mixes in uniformly backward mixed system and the aqueous citric acid solution that 9~14mL concentration is 4mol/L is added, mix and stand, obtain described
The modification of chitosan compound water solution of gold nanoclusters is carried, wherein the sulfur-bearing and the compound of nitrogen are mercaptoethylmaine or mercapto
Any one of guanidine-acetic acid or ethylenediamine；
Step 2. is by the modification of chitosan compound water solution of the load gold nanoclusters of 0.625~5g and contains 1~5g lemon
After the aqueous solution 30mL of acid is mixed, 150 DEG C~200 DEG C at a temperature of carry out hydro-thermal reaction, the golden doping fluorescent carbon is made
Quantum dot.
2. the method according to claim 1, wherein the method also includes the golden doping fluorescent carbon is being made
Purification process is carried out to it after quantum dot.
3. according to the method described in claim 2, it is characterized in that, the purification process includes: by the golden doping fluorescent carbon
It dialyses again after quantum dot centrifugation.
4. according to the method described in claim 3, it is characterized in that, the speed of centrifugation is 5000r/ minutes to 12000r/ minutes.
5. according to the method described in claim 3, it is characterized in that, the speed of centrifugation is 6000r/ minutes to 10000r/ minutes.
6. the method according to claim 1, wherein the temperature for carrying out hydro-thermal reaction in the step 2 is 160 DEG C
~190 DEG C.
7. the method according to claim 1, wherein the time for carrying out hydro-thermal reaction in the step 2 is at least
300 minutes.
8. the method according to claim 1, wherein the modification of chitosan is that graft copolymerization has polymerized monomer N-
The chitosan of vinyl pyrrolidone and function monomer acrylic acid.
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