CN108659814A - A kind of quaternary water-soluble quantum dot and its preparation method and application - Google Patents
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Abstract
The invention discloses a kind of quaternary water-soluble quantum dots comprising the core of AgGaInS and the covering being coated on the core surface of AgGaInS；The invention also discloses the preparation method and application of the quantum dot.The crystallinity for the quantum dot that the present invention is obtained by using substep hydro-thermal method is high, and Size Distribution is uniform, and fluorescence peak adjustable extent is wide and between 450~750nm, and fluorescence quantum yield is up to 25% or more；In addition, the present invention can be advantageously applied in photoelectric device and biomarker by selecting the oligopeptides for containing bioactive macromolecule to be used as surface capping agents.
Description
Technical field
The present invention relates to quanta point material fields, and in particular to a kind of quaternary water-soluble quantum dot and preparation method thereof and answers
With.
Background technology
Semiconductor nano (Nanocrystals, NCs) is also referred to as quantum dot (Quantum dots, QDs), is
A kind of semi-conducting material being all restricted in the dimension of three, space；Quantum dot is studied so far, multiple types structure occurs
And material；It is divided from structure, there is nucleocapsid, alloy structure, heterojunction structure etc.；For material category, there is II-VI group (such as
CdS), iii-v (such as InP)；The quantum dot Course of development of these types is more long, therefore synthesis technology is very ripe, but contains
There are A class heavy metal elements, such as Cd, Hg, therefore huge damage is produced to biotic environment.
AgInS was successfully synthesized from 20072Quantum dot starts, and thus opens grinding for I-III-V races ternary quantum dots
Study carefully；Ternary quantum dots have the higher absorption coefficient of light, preferable biocompatibility and stronger defect tolerance, therefore obtain
The concern of people；However the ternary I-III-V races quantum dot synthesized at present is mostly organic synthesis, and quantum yield is universal
It is relatively low, strongly limit their applications in luminescent material and biomarker field.
Invention content
In view of this, the main purpose of the present invention is to provide a kind of quaternary water-soluble quantum dot, solves the prior art
The problem that the quantum yield of middle quantum dot is low and biocompatibility is bad.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：A kind of quaternary water-soluble quantum dot, packet
Include the core of AgGaInS and the covering being coated on the core surface of AgGaInS.
Preferably, the covering is made of glutathione analogs and sodium citrate.
What another technical solution of the present invention was realized in：A kind of preparation method of quaternary water-soluble quantum dot, should
Method is achieved by the steps of：
Step 1, to containing silver salt, indium salts, gallium salt mixed aqueous solution in the aqueous solution containing covering and stirring is added
Uniformly, precursor solution is obtained；
Step 2, the pH value for the precursor solution that the step 1 obtains is adjusted to 8~10.5, and it is molten to obtain alkaline presoma
Liquid；
Step 3, the aqueous solution containing sulphur source is added in the alkaline precursor solution obtained to the step 2 to stir evenly,
Obtain the mixed aqueous solution containing alkaline presoma and sulphur source；
Step 4, substep hydro-thermal method is carried out to the mixed aqueous solution containing alkaline presoma and sulphur source that the step 3 obtains
Processing obtains quaternary water-soluble quantum dot (the AgGaInS quantum dots of surface capping agents cladding).
Preferably, in the step 1, it is described containing silver salt, indium salts, gallium salt mixed aqueous solution in indium ion, gallium ion
The ratio between the sum of mole and the mole of silver ion be 1:(0.05~1)；The mixing water containing silver salt, indium salts, gallium salt
The mole of the sum of mole of indium ion, gallium ion, silver ion and the covering in the aqueous solution containing covering in solution
The ratio between be 1:(6~15).
Preferably, in the step 1, it is described containing silver salt, indium salts, gallium salt mixed aqueous solution in silver ion substance
A concentration of 0.01~0.15mol/L is measured, the substance withdrawl syndrome of indium ion is 0.01~0.15mol/L, the substance of gallium ion
Measure a concentration of 0.01~0.15mol/L；In the aqueous solution containing covering the substance withdrawl syndrome of covering be 0.01~
0.6mol/L。
Preferably, in the step 1, the silver salt is at least one of silver nitrate, silver acetate；The indium salts are nitric acid
At least one of indium, indium acetate, inidum chloride；The gallium salt is at least one of gallium nitrate, gallium sulfate, gallium chloride.
Preferably, in the step 3, indium ion in the alkalinity presoma, gallium ion, silver ion the sum of mole with
It is 1 containing the ratio between mole of element sulphur in sulphur source aqueous solution:(1~20)；The substance of element sulphur in the sulphur source aqueous solution
Measure a concentration of 0.01~0.15mol/L；The sulphur source is at least one of thioacetamide, thiocarbamide, vulcanized sodium.
Preferably, specific method is in the step 4：The mixed aqueous solution containing alkaline presoma and sulphur source is added
Heat is heated to 110~120 DEG C, 120~240min of constant temperature to 60~80 DEG C, 30~50min of constant temperature, and cooling centrifuges,
Obtain quaternary water-soluble quantum dot.
Quaternary water-soluble quantum dot of the present invention is mostly as the purposes of fluorescence probe；The fluorescence probe is mainly used for photoelectricity, life
Object and medical domain.
Compared with prior art, the crystallinity for the quantum dot that the present invention is obtained by using substep hydro-thermal method is very high, ruler
Very little distribution is very uniform, and fluorescence peak adjustable extent is wide and between 450~750nm, and fluorescence quantum yield is up to 25% or more；This
Outside, the present invention can be advantageously applied to photoelectricity by selecting the oligopeptides for containing bioactive macromolecule to be used as surface capping agents
In device and biomarker.
Description of the drawings
Fig. 1 is the synthesis schematic diagram of quaternary water-soluble quantum dot provided in an embodiment of the present invention；
Fig. 2 is the high-resolution-ration transmission electric-lens figure of quaternary water-soluble quantum dot provided in an embodiment of the present invention；
Fig. 3 is the fluorescence spectra of quaternary water-soluble quantum dot provided in an embodiment of the present invention；
Fig. 4 is the fluorescence quantum yield schematic diagram of quaternary water-soluble quantum dot provided in an embodiment of the present invention；
Fig. 5 is that quaternary water-soluble quantum dot provided in an embodiment of the present invention carries out cytotoxicity testing result schematic diagram.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The symbol and formula used in the present invention has meaning well known to this field.Specifically, AgGaInS indicate by silver,
The alloy of indium, gallium and element sulphur composition；Glu-Cys-Pro oligopeptides is i.e. glutamate-cysteine-proline tripeptides；It is coated on
Glu-Cys-Pro oligopeptides on quantum dot surface is the biocompatibility ligand to surface modification, with the metal on surface from
Son cooperation.Although it should be understood that being referred to as surface capping agents herein, them are not intended to limit in the present invention
Method in only play the role of it is surface coated.
The present invention provides embodiments to provide a kind of quaternary water-soluble quantum dot comprising the core and cladding of AgGaInS
Covering on the surface；Wherein, surface capping agents are made of glutathione analogs and sodium citrate, glutathione analogs
For Glu-Cys-Pro oligopeptides.
The present invention also provides a kind of preparation method of quaternary water-soluble quantum dot, this method is achieved by the steps of：
Step 1, to containing silver salt, indium salts, gallium salt mixed aqueous solution in be added containing substance withdrawl syndrome be 0.01~
The aqueous solution of the covering of 0.6mol/L simultaneously stirs evenly, and obtains precursor solution；
Wherein, containing silver salt, indium salts, gallium salt mixed aqueous solution in indium ion, gallium ion the sum of mole and silver from
The ratio between mole of son is 1:(0.05~1)；Containing silver salt, indium salts, gallium salt mixed aqueous solution in indium ion, gallium ion, silver
The sum of mole of ion is 1 with the ratio between the mole of covering in the aqueous solution containing covering:(6~15)；Contain silver
Salt, indium salts, gallium salt mixed aqueous solution in silver ion substance withdrawl syndrome be 0.01~0.15mol/L, the substance of indium ion
A concentration of 0.01~0.15mol/L of amount, the substance withdrawl syndrome of gallium ion is 0.01~0.15mol/L；Contain covering water
The substance withdrawl syndrome of covering is 0.01~0.6mol/L in solution；Silver salt is at least one of silver nitrate, silver acetate；Indium
Salt is at least one of indium nitrate, indium acetate, inidum chloride；Gallium salt is at least one of gallium nitrate, gallium sulfate, gallium chloride.
Step 2, sodium hydroxide solution is added in the precursor solution obtained to step 1 and adjusts pH value to 8~10.5, obtains
Alkaline precursor solution；
Step 3, it is added in the alkaline precursor solution obtained to the step 2 and contains a concentration of 0.01~0.15mol/L
The aqueous solution of sulphur source stir evenly, obtain the mixed aqueous solution containing alkaline presoma and sulphur source；Wherein, in alkaline presoma
The sum of mole of indium ion, gallium ion, silver ion with containing the ratio between mole of element sulphur in sulphur source solution be 1:(1~
20)；Substance withdrawl syndrome containing element sulphur in sulphur source solution is 0.01~0.15mol/L；Sulphur source is thioacetamide, sulphur
At least one of urea, vulcanized sodium.
Step 4, substep hydro-thermal method is carried out to the mixed aqueous solution containing alkaline presoma and sulphur source that the step 3 obtains
Processing obtains quaternary water-soluble quantum dot (the AgGaInS quantum dots of surface capping agents cladding)；Wherein, the specific side of the step
Method is：The mixed aqueous solution of alkaline presoma and sulphur source is heated to 60~80 DEG C, 30~50min of constant temperature, it is heated to 110~
120 DEG C, 120~240min of constant temperature, cooling, centrifugation, obtaining quaternary water-soluble quantum dot, (surface capping agents coat
AgGaInS quantum dots).
The quaternary water-soluble quantum dot that the embodiment of the present invention obtains is mostly as the purposes of fluorescence probe；The fluorescence probe is main
For photoelectricity, biological and medical field.
The quantum dot that the present invention is obtained by using substep hydro-thermal method compared with the quantum dot that existing one step hydro thermal method obtains,
The crystallinity for the quantum dot that the present invention obtains is very high, and Size Distribution is very uniform, and fluorescence peak adjustable extent is wide and between 450~
750nm, fluorescence quantum yield are up to 25% or more；In addition, the present invention is by selecting the oligopeptides containing bioactive macromolecule to make
For surface capping agents, can be advantageously applied in photoelectric device and biomarker.
Embodiment 1
A kind of preparation method of quaternary water-soluble quantum dot, this method are achieved by the steps of：
Step 1, respectively by the silver nitrate aqueous solution of 5ml 0.02mol/L, 1mL 0.05mol/L, indium nitrate aqueous solution,
The gallium nitrate aqueous solution of 6mL 0.02mol/L is mixed evenly, and adds the Glu-Cys-Pro oligopeptides of 1.5mL0.2mol/L
Covering aqueous solution that aqueous solution and the sodium citrate aqueous solution of 4.5mL 0.1mol/L are mixed to form simultaneously stirs evenly, before acquisition
Drive liquid solution；
Step 2, sodium hydroxide is added in the precursor solution obtained to the step 1 and adjusts pH value to 9, before obtaining alkalinity
Drive liquid solution；
Step 3, the thioacetamide of 7.5mL 0.1mol/L is added in the alkaline precursor solution obtained to the step 2
Aqueous solution stir evenly, obtain the mixed aqueous solution containing alkaline presoma and thioacetamide；
Step 4, autoclave is set into the mixed aqueous solution transfer containing alkaline presoma and thioacetamide that step 3 obtains
In be heated to 60 DEG C and constant temperature 30min, be again heated to 110 DEG C and constant temperature 120min, it is cooling, then with the centrifugation of excessive ethyl alcohol, obtain
It must precipitate, this is precipitated as quaternary water-soluble quantum dot (i.e.：The AgInGaS quantum dots of surface capping agents cladding).
Embodiment 2
A kind of preparation method of quaternary water-soluble quantum dot, this method are achieved by the steps of：
Step 1, respectively by the silver nitrate aqueous solution of 5ml 0.02mol/L, 1mL 0.05mol/L, indium nitrate aqueous solution,
The gallium sulfate aqueous solution of 6mL 0.02mol/L is mixed evenly, and adds the Glu-Cys-Pro oligopeptides of 1.5mL0.2mol/L
Covering aqueous solution that aqueous solution and the sodium citrate aqueous solution of 4.5mL 0.1mol/L are mixed to form simultaneously stirs evenly, before acquisition
Drive liquid solution；
Step 2, the sodium hydroxide that a concentration of 1mol/mL is added in the precursor solution obtained to the step 1 adjusts pH
Value obtains alkaline precursor solution to 9；
Step 3, the water-soluble of the thiocarbamide of 15mL 0.05mol/L is added in the alkaline precursor solution obtained to the step 2
Liquid stirs evenly, and obtains the mixed aqueous solution containing alkaline presoma and thiocarbamide；
Step 4, the mixed aqueous solution transfer containing alkaline presoma and thiocarbamide that step 3 obtains is set in autoclave and is heated
To 60 DEG C and constant temperature 30min, 110 DEG C of simultaneously constant temperature 130min are again heated to, it is cooling, then centrifuged with excessive ethyl alcohol, it is precipitated,
This is precipitated as quaternary water-soluble quantum dot (i.e.：The AgInGaS quantum dots of surface capping agents cladding).
Embodiment 3
A kind of preparation method of quaternary water-soluble quantum dot, this method are achieved by the steps of：
Step 1, respectively by the silver nitrate aqueous solution of 5ml 0.02mol/L, 1.2mL 0.05mol/L, indium nitrate it is water-soluble
Liquid, 7.5mL 0.02mol/L gallium nitrate aqueous solution be mixed evenly, add the Glu-Cys-Pro of 8mL0.05mol/L
Covering aqueous solution that oligopeptides aqueous solution and the sodium citrate aqueous solution of 2.65mL 0.2mol/L are mixed to form simultaneously stirs evenly,
Obtain precursor solution；
Step 2, the sodium hydroxide that a concentration of 1mol/mL is added in the precursor solution obtained to the step 1 adjusts pH
Value obtains alkaline precursor solution to 9；
Step 3, the vulcanized sodium of 10.33mL 0.09mol/L is added in the alkaline precursor solution obtained to the step 2
Aqueous solution stir evenly, obtain the mixed aqueous solution containing alkaline presoma and vulcanized sodium；
Step 4, the mixed aqueous solution transfer containing alkaline presoma and vulcanized sodium that step 3 obtains is set in autoclave and is added
Heat is again heated to 110 DEG C of simultaneously constant temperature 130min to 60 DEG C and constant temperature 30min, cooling, then is centrifuged with excessive ethyl alcohol, is sunk
It forms sediment, this is precipitated as quaternary water-soluble quantum dot (i.e.：The AgInGaS quantum dots of surface capping agents cladding).
Embodiment 4
A kind of preparation method of quaternary water-soluble quantum dot, this method are achieved by the steps of：
Step 1, respectively that the indium nitrate of the silver nitrate aqueous solution of 2.5ml 0.04mol/L, 1.4mL 0.05mol/L is water-soluble
Liquid, 10mL 0.02mol/L gallium chloride aqueous solution be mixed evenly, the Glu-Cys-Pro for adding 1mL 0.4mol/L is few
Covering aqueous solution that peptide aqueous solution and the sodium citrate aqueous solution of 4.5mL 2.7mol/L are mixed to form simultaneously stirs evenly, and obtains
Precursor solution；
Step 2, the sodium hydroxide that a concentration of 1mol/mL is added in the precursor solution obtained to the step 1 adjusts pH
Value obtains alkaline precursor solution to 9；
Step 3, the thioacetyl of 10.1mL 0.11mol/L is added in the alkaline precursor solution obtained to the step 2
The aqueous solution of amine stirs evenly, and obtains the mixed aqueous solution containing alkaline presoma and thioacetamide；
Step 4, autoclave is set into the mixed aqueous solution transfer containing alkaline presoma and thioacetamide that step 3 obtains
In be heated to 60 DEG C and constant temperature 30min, be again heated to 110 DEG C and constant temperature 130min, it is cooling, then with the centrifugation of excessive ethyl alcohol, obtain
It must precipitate, this is precipitated as quaternary water-soluble quantum dot (i.e.：The AgInGaS quantum dots of surface capping agents cladding).
Embodiment 5
A kind of preparation method of quaternary water-soluble quantum dot, this method are achieved by the steps of：
Step 1, respectively by the silver nitrate aqueous solution of 1ml 0.1mol/L, 1.6mL 0.05mol/L indium nitrate aqueous solution,
The gallium sulfate aqueous solution of 15mL 0.02mol/L is mixed evenly, and adds the Glu-Cys-Pro oligopeptides of 2mL 0.3mol/L
Covering aqueous solution that aqueous solution and the sodium citrate aqueous solution of 4.5mL 2.64mol/L are mixed to form simultaneously stirs evenly, and obtains
Precursor solution；
Step 2, the sodium hydroxide that a concentration of 1mol/mL is added in the precursor solution obtained to the step 1 adjusts pH
Value obtains alkaline precursor solution to 9；
Step 3, the thioacetyl of 9.6mL 0.15mol/L is added in the alkaline precursor solution obtained to the step 2
The aqueous solution of amine stirs evenly, and obtains the mixed aqueous solution containing alkaline presoma and thioacetamide；
Step 4, autoclave is set into the mixed aqueous solution transfer containing alkaline presoma and thioacetamide that step 3 obtains
In be heated to 60 DEG C and constant temperature 30min, be again heated to 110 DEG C and constant temperature 130min, it is cooling, then with the centrifugation of excessive ethyl alcohol, obtain
It must precipitate, this is precipitated as quaternary water-soluble quantum dot (i.e.：The AgInGaS quantum dots of surface capping agents cladding).
The performance detection examination experiment of quantum dot：
The pattern of the quantum dot obtained to embodiment 1 to embodiment 5 using high resolution transmission electron microscopy is observed,
As shown in Fig. 2, from fig. 2 it can be seen that the size of quantum dot is in 3nm or so；The diffraction fringe observed is apparent from, and illustrates to produce
The crystalline quality of object is very high, and defect is few.This makes the fluorescence quantum yield of the quantum dot of the present invention all very high, following article institute
It states.
The quantum dot obtained to embodiment 1 to embodiment 5 using Fluorescence Spectrometer is measured, measurement result such as Fig. 3 institutes
Show, it can be seen in figure 3 that the emission wavelength of quantum dot is respectively 525nm, 545nm, 562nm, 573nm and 605nm, this says
The bright parameter by changing the present invention can obtain the different product of emission wavelength；It is furthermore observed that embodiment 1 is to embodiment 5
The size of the quantum dot of acquisition does not have significant change, caused by this illustrates that the change of emission wavelength is not due to the change of size,
This is the significantly different place of the quantum dot and traditional binary quantum dot of the present invention.
The fluorescence quantum yield of the quantum dot obtained to embodiment 1 to embodiment 5 is detected, testing result such as Fig. 4 institutes
Show, it can be seen from figure 4 that quantum yield is respectively 23%, 26%, 33%, 28% and 35%, is all higher than 20%.
Cytotoxicity is carried out to the quantum dot that embodiment 1 to embodiment 5 obtains using method well known to life science
Detection, testing result as shown in figure 5, from fig. 5, it is seen that the quantum dot of all synthesis to normal cell hatch 48 hours after
Survival rate all 95% or more, toxicity is minimum, for biological field, can be called non-toxic quantum dot.
As it can be seen that there is good optical property and biocompatibility using the quantum dot that the embodiment of the present invention obtains, in light
Electrical domain, life science and medical domain all have preferable application prospect.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of quaternary water-soluble quantum dot, which is characterized in that it includes the core of AgGaInS and the core table for being coated on AgGaInS
Covering on face.
2. a kind of quaternary water-soluble quantum dot according to claim 1, which is characterized in that the covering is by glutathione
Analog and sodium citrate composition.
3. a kind of preparation method of quaternary water-soluble quantum dot, which is characterized in that this method is achieved by the steps of：
Step 1, to containing silver salt, indium salts, gallium salt mixed aqueous solution in be added and the aqueous solution containing covering and stir evenly,
Obtain precursor solution；
Step 2, the pH value for the precursor solution that the step 1 obtains is adjusted to 8~10.5, obtains alkaline precursor solution；
Step 3, the aqueous solution containing sulphur source is added in the alkaline precursor solution obtained to the step 2 to stir evenly, obtains
Mixed aqueous solution containing alkaline presoma and thioacetamide；
Step 4, substep hydro-thermal is carried out to the mixed aqueous solution containing alkaline presoma and thioacetamide that the step 3 obtains
Method processing, obtains quaternary water-soluble quantum dot.
4. wanting a kind of preparation method of quaternary water-soluble quantum dot described in 3 according to right, which is characterized in that in the step 1,
It is described containing silver salt, indium salts, gallium salt mixed aqueous solution in indium ion, gallium ion mole with silver ion of the sum of mole
The ratio between be 1:(0.05~1)；It is described containing silver salt, indium salts, gallium salt mixed aqueous solution in indium ion, gallium ion, silver ion
The sum of mole is 1 with the ratio between the mole of covering in the aqueous solution containing covering:(6~15).
5. a kind of preparation method of quaternary water-soluble quantum dot according to claim 4, which is characterized in that the step 1
In, it is described containing silver salt, indium salts, gallium salt mixed aqueous solution in silver ion substance withdrawl syndrome be 0.01~0.15mol/L,
The substance withdrawl syndrome of indium ion is 0.01~0.15mol/L, and the substance withdrawl syndrome of gallium ion is 0.01~0.15mol/L；
The substance withdrawl syndrome of covering is 0.01~0.6mol/L in the aqueous solution containing covering.
6. a kind of preparation method of quaternary water-soluble quantum dot according to claim 5, which is characterized in that the step 1
In, the silver salt is at least one of silver nitrate, silver acetate；The indium salts are indium nitrate, indium acetate, in inidum chloride at least
It is a kind of；The gallium salt is at least one of gallium nitrate, gallium sulfate, gallium chloride.
7. a kind of preparation method of quaternary water-soluble quantum dot according to claim 6, which is characterized in that the step 3
In, indium ion in the alkalinity presoma, gallium ion, silver ion the sum of mole with contain element sulphur in sulphur source aqueous solution
The ratio between mole is 1:(1~20)；The substance withdrawl syndrome of element sulphur is 0.01~0.15mol/L in the sulphur source aqueous solution；
The sulphur source is at least one of thioacetamide, thiocarbamide, vulcanized sodium.
8. a kind of preparation method of quaternary water-soluble quantum dot according to claim 3-7 any one, which is characterized in that
Specific method is in the step 4：The mixed aqueous solution containing alkaline presoma and sulphur source is heated to 60~80 DEG C, perseverance
30~50min of temperature, is heated to 110~120 DEG C, 120~240min of constant temperature, and cooling, centrifugation obtains quaternary water solubility amount
Sub- point.
9. purposes of a kind of quaternary water-soluble quantum dot as fluorescence probe according to claim 1-2 any one.
10. purposes according to claim 9, which is characterized in that the fluorescence probe is for photoelectricity, biology and medicine neck
Domain.
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