A kind of preparation method of the fluorescence aqueous two-phase based on carbon quantum dot
Technical field
The present invention relates to a kind of using ionic liquid as the preparation of the carbon quantum dot of presoma, and constructs fluorescence aqueous two-phase, answers
For realizing drug efficiently concentrating and highly sensitive detection simultaneously.
Background technique
Liquid-liquid extraction (LLE) is common isolation technics in chemical industry and analytical chemistry, in biology, medicine, food etc.
It is widely used in the separation in field, preparation and sample pre-treatments.Traditional liquid-liquid extraction system be mainly organic solvent and
The two-phase system that aqueous solution is formed.However, since organic solvent has the shortcomings that volatility, combustibility and toxicity, with the world
Increasingly attention of the society to environmental problem, the use of organic solvent receive different degrees of limitation.In recent years, aqueous two-phase extraction
(ATPE) technology is as a kind of novel isolation technics, and because its is small in size, processing capacity is strong, in the process without using toxic organic
Solvent makes it get more and more people's extensive concerning in Green Chemistry field.Aqueous two-phase system (ATPS) refers between certain organic matters,
Or between organic matter and inorganic salts, in water to form two-phase or multiphase mutual exclusive system after concentration appropriate dissolution.
ATPE is similar to the principle that organic solvent extracts, and is in accordance with substance in two alternate selectivity distribution, when substance enters ATPS
Afterwards, due to the influence of electrostatic interaction, hydrophobic effect and interfacial tension, keep its concentration in upper and lower two-phase different, to reach
The purpose of extraction.
The distinctive skin effect of nano material, small-size effect, macro quanta tunnel effect and quantum confined effect, make it
Light, electricity, thermal and magnetic, machinery, in terms of show unique performance, become the hot spot of material science research.Carbon quantum dot
It is a kind of emerging carbon nanomaterial found recently, general partial size is less than 10nm, but since the difference of synthetic method also has
Exception.This is a kind of fluorescent nano material with conventional semiconductors quantum dot with similar optical performance and nano-scale, poison
The low, good biocompatibility of property is readily synthesized and functional modification, prepares that raw material is easily obtained, preparation cost is cheap, reaction kit
Common and preparation condition is mild etc. be conventional semiconductors quantum dot it is incomparable.The good isotropism of carbon quantum dot surpasses
The features such as thin dimension, synthetic method diversity, makes it have wide application value, and carbon quantum dot can be in numerous applications
Substitute as other carbon nanomaterials (fullerene, nanometer diamond, carbon nanotube).
In terms of synthetic method angle, high-performance and multi-functional carbon quantum dot are further studied, mainly there are following several respects
Work: (1) select green non-poisonous, inexpensive carbon source presoma, streamline operation as far as possible;(2) existing carbon quantum is improved
The optical property of point enables its appearance depressed area to fill and lead up or improve the technique increase table of cladding synthesis by the way that passivator is added
Face luminophore etc.;(3) more novel carbon quantum dots are developed, including expand its fluorescence emission spectral limit as far as possible, prepare quantum
Yield is higher, the better carbon quantum dot of photostability.
In terms of synthetic raw material angle, ionic liquid has good physical and chemical stability, almost without vapour pressure,
Pollution problem of the volatile organic solvent to environment is eliminated, is the ideal substitution of traditional volatile organic solvent
Product have broad application prospects.
This patent, which proposes to react using ionic liquid as presoma with phosphorus pentoxide, prepares carbon quantum dot, and to its fluorescence
The fluorescence aqueous two-phase system of foundation, is then applied to real simultaneously by characteristic and form aqueous two-phase carry out system research at phase condition
The efficient fast enriching of existing drug and highly sensitive detection.
Summary of the invention
Technical problem:
The shortcomings that the technical problem to be solved by the present invention is to for traditional quantum dot, for example, synthetic material is all noble metal
Or heavy metal, synthetic method are complicated, synthetic instrument costly etc., therefore select green solvent --- ionic liquid as presoma and
Phosphorus pentoxide by wet chemistry method prepare carbon quantum dot, preparation flow is simple, at the same have also obtained higher quantum yield and
Preferable photostability.It is then based on the carbon quantum dot and establishes fluorescence aqueous two-phase, influenced by integrated survey into each of phase condition
Kind factor finally obtains optimal fluorescence aqueous two-phase and is applied to the enrichment and detection of drug.
Technical solution:
1, technical solution of the invention are as follows:
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: a certain amount of distilled water is added in a certain amount of ionic liquid
In, it stirs evenly, mixed solution is put into the round-bottomed flask for have phosphorus pentoxide and heats a period of time, solution is by no discoloration
It for yellow, is cooled to room temperature, obtains carbon quantum dot;
B, the foundation of fluorescence aqueous two-phase: the carbon quantum dot prepared in a certain amount of a is added in a certain amount of distilled water, then
A certain amount of sodium dihydrogen phosphate is added, low speed is stood after shaking a period of time under the conditions of certain temperature, obtains fluorescence aqueous two-phase.
2, preparation method according to claim 1, it is characterised in that: in the step a, the amount of ionic liquid used
For 0.08~0.4g, the amount of phosphorus pentoxide is 1.0~10.0g, and the amount of distilled water is 1~10mL, the reaction time is 1~
10min。
3, preparation method according to claim 1, it is characterised in that: in the step b, the amount of carbon quantum dot is 10
~200 μ L, the additional amount of distilled water are 1~10mL, and the amount of sodium dihydrogen phosphate is 0.4~4g, stand or the shaking time be 5~
60min is 0~50 DEG C at phase temperature.
4, preparation method according to claim 1, it is characterised in that: in the step a, ionic liquid is 1- fourth
Base -3- methyl imidazolium tetrafluoroborate ([Bmim] BF4), 1- ethyl-3-methylimidazole trifluoromethyl sulfonic acid ([Emim]
OTF), 1- hexyl -3- methylimidazole villaumite ([Hmim] Cl), 1- butyl-pyridinium tetrafluoroborate ([BPy] BF4), 1- dodecane
Base -3- methylimidazole bromide ([C12Mim] Br), 1- butyl -1- methyl piperidine villaumite ([BMPi] Cl), N- ethylpyridine tetrafluoro boron
Hydrochlorate
([EPy]BF4), 1- cetyl -3- methyl imidazolium tetrafluoroborate ([C16mim]BF4)。
5, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in-quantitatively distillation using above-mentioned carbon quantum dot
Then the side that a certain amount of sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test is added in water
Method through the following steps that carry out: at a certain temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add a certain amount of preparation
Carbon quantum dot, a certain amount of distilled water and a certain amount of sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration, with pH
2.0 B-R buffer solution is diluted to scale, and then low speed is stood after shaking a period of time, finally takes the upper phase of fluorescence aqueous two-phase
The fluorescence intensity after the Quercetin solution of various concentration is added in measurement at certain excitation wavelength (λ ex=370nm), finally utilizes
The additional amount of fluorescent quenching degree characterization Quercetin is to achieve the purpose that detect Quercetin.
Detailed description of the invention
Fig. 1 is the synthetic route schematic diagram of phosphorus pentoxide wet chemistry method preparation carbon quantum dot of the present invention.
Fig. 2 is the infared spectrum of carbon quantum dot produced by the present invention.
Fig. 3 is fluorescence aqueous two-phase phasor produced by the present invention.
Fig. 4 is the upper and lower phase fluorescence intensity comparison diagram of fluorescence aqueous two-phase produced by the present invention.
Fig. 5 be fluorescence aqueous two-phase prepared by the present invention and various concentration Quercetin effect after the upper phase fluorogram that measures
Spectrum, λ ex=370nm;The volume of carbon quantum dot is 120 μ L;Distilled water volume is 5mL;B-R buffer solution is 4mL;Biphosphate
Sodium is 0.95g;The concentration of Quercetin: 10-9, 10-8, 10-7, 5 × 10-6, 10-6, 7 × 10-5, 10-5, 6 × 10-4, 10-4, 10-3mol
L-1。
Specific embodiment
Preparating example
Following embodiment is some citings of the invention, should not be seen as limitation of the invention.
Embodiment 1
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.08g 1- butyl -3- methyl imidazolium tetrafluoroborate
([Bmim]BF4) be added in 4mL distilled water, it stirs evenly, mixed solution is put into the round-bottomed flask for having 5g phosphorus pentoxide
Middle heating 5min, solution become yellow from colourless, are cooled to room temperature, and obtain carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 5mL amount using above-mentioned 120 μ L carbon quantum dot
Then 1.5g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 120 μ L preparation carbon amounts
Sub- point, 5mL distilled water and 1.5g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 10min after the shaking 30min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 2
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.40g 1- ethyl-3-methylimidazole trifluoromethyl sulphur
Hydrochlorate ([Emim] OTF) is added in 6mL distilled water, stirs evenly, mixed solution is put into the circle for having 4.5g phosphorus pentoxide
6min is heated in the flask of bottom, solution becomes yellow from colourless, is cooled to room temperature, and obtains carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 4mL amount using above-mentioned 180 μ L carbon quantum dot
Then 3.6g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 180 μ L preparation carbon amounts
Sub- point, 4mL distilled water and 3.6g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 20min after the shaking 40min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 3
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.30g 1- hexyl -3- methylimidazole villaumite ([Hmim]
Cl it) is added in 1mL distilled water, stirs evenly, mixed solution is put into the round-bottomed flask for having 5.5g phosphorus pentoxide and is heated
5min, solution become yellow from colourless, are cooled to room temperature, and obtain carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 8mL amount using above-mentioned 140 μ L carbon quantum dot
Then 3.8g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 140 μ L preparation carbon amounts
Sub- point, 8mL distilled water and 3.8g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 30min after the shaking 30min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 4
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.25g 1- butyl-pyridinium tetrafluoroborate ([BPy]
BF4 it) is added in 3mL distilled water, stirs evenly, mixed solution is put into the round-bottomed flask for having 4.5g phosphorus pentoxide and is heated
2min, solution become yellow from colourless, are cooled to room temperature, and obtain carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 6mL amount using above-mentioned 100 μ L carbon quantum dot
Then 4.6g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 100 μ L preparation carbon amounts
Sub- point, 6mL distilled water and 4.6g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 10min after the shaking 50min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 5
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.35g 1- dodecyl -3- methylimidazole bromide
([C12Mim] Br) it is added in 4mL distilled water, it stirs evenly, mixed solution is put into the round bottom for having 3.5g phosphorus pentoxide and is burnt
4min is heated in bottle, solution becomes yellow from colourless, is cooled to room temperature, and obtains carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 6mL amount using above-mentioned 190 μ L carbon quantum dot
Then 5.9g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 190 μ L preparation carbon amounts
Sub- point, 6mL distilled water and 5.9g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 40min after the shaking 30min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 6
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.38g 1- butyl -1- methyl piperidine villaumite ([BMPi]
Cl it) is added in 5mL distilled water, stirs evenly, mixed solution is put into the round-bottomed flask for having 5.5g phosphorus pentoxide and is heated
6min, solution become yellow from colourless, are cooled to room temperature, and obtain carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 5mL amount using above-mentioned 180 μ L carbon quantum dot
Then 6.9g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 180 μ L preparation carbon amounts
Sub- point, 5mL distilled water and 6.9g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 40min after the shaking 20min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 7
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.30g N- ethylpyridine tetrafluoroborate ([EPy]
BF4) be added in 4mL distilled water, it stirs evenly, mixed solution is put into the round-bottomed flask for having 6.5g phosphorus pentoxide and is heated
6min, solution become yellow from colourless, are cooled to room temperature, and obtain carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 6mL amount using above-mentioned 150 μ L carbon quantum dot
Then 5.7g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 150 μ L preparation carbon amounts
Sub- point, 6mL distilled water and 5.7g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 5min after the shaking 50min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to excite
The fluorescence intensity of the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).
Embodiment 8
A, phosphorus pentoxide wet chemistry method prepares carbon quantum dot: by 0.40g 1- cetyl -3- methylimidazole tetrafluoro boron
Hydrochlorate ([C16mim]BF4) be added in 5mL distilled water, it stirs evenly, mixed solution is put into the circle for having 3.5g phosphorus pentoxide
3min is heated in the flask of bottom, solution becomes yellow from colourless, is cooled to room temperature, and obtains carbon quantum dot;
B, the application of fluorescence aqueous two-phase of the invention in drug test is dissolved in 5mL amount using above-mentioned 120 μ L carbon quantum dot
Then 5.8g is added in distilled water sodium dihydrogen phosphate establishes fluorescence aqueous two-phase and the fluorescence aqueous two-phase is applied to drug test
Method through the following steps that carry out: at room temperature, in Yu Ruogan 10mL colorimetric cylinder, sequentially add 120 μ L preparation carbon amounts
Sub- point, 5mL distilled water and 5.8g sodium dihydrogen phosphate, the flavonoids drug Quercetin of various concentration are molten with the B-R buffering of pH 2.0
Liquid is diluted to scale, and then low speed stands 30min after the shaking 40min time, and the upper phase of fluorescence aqueous two-phase is finally taken centainly to swash
Send out the fluorescence intensity that the flavonoids drug Quercetin of various concentration is added in measurement under wavelength (λ ex=370nm).