CN105950135A - Quantum dot of core-shell structure as well as preparation method and application of quantum dot - Google Patents
Quantum dot of core-shell structure as well as preparation method and application of quantum dot Download PDFInfo
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- CN105950135A CN105950135A CN201610305476.5A CN201610305476A CN105950135A CN 105950135 A CN105950135 A CN 105950135A CN 201610305476 A CN201610305476 A CN 201610305476A CN 105950135 A CN105950135 A CN 105950135A
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Abstract
The invention provides a quantum dot of a core-shell structure. The quantum dot is characterized by comprising following components: a Zn/In:Ag2S core, a ZnS shell and a surface coating, wherein the surface of the quantum dot is coated with the surface coating and is selected from groups formed by following components: glutathione, cysteine and combination of glutathione and cysteine. The invention further provides a method for preparing the quantum dot of the core-shell structure and an application of the quantum dot as a fluorescence probe in the biological and medical fields.
Description
Technical field
The present invention relates to quanta point material field, be specifically related to the quantum dot of a kind of nucleocapsid structure, its system
Preparation Method and purposes.
Background technology
Quantum dot (Quantum Dots, QDs) is otherwise known as " nanocrystalline ", is made up of a small amount of atom
Nano material.Due to quantum confined effect, quantum dot can send difference after stimulated luminescence excites
The fluorescence of wavelength.Quantum dot is narrow (glimmering because having diameter little (1～10nm, easily enter cell), fluorescence peak
Light interference is little, can multi-color marking) and the feature such as fluorescent brightness lasting (>=12 days, be easy to biological tracing),
From succeeding in developing, (poisonous, volume is big, light peak width, Yi to be just endowed replacement organic dyestuff
Optical quenching in short time) carry out the expectation of biotic experiment.
At present research highly developed and the most popular for many years be II-VI group quantum dot (as
CdSe, SeTe) and iii-v binary quantum dot (such as GaAs), the advantage of these quantum dots is fluorescence volume
Sub-productivity higher (about 40%), but because these quantum dots all synthesize in organic solution, and
And comprise hypertoxic element, such as Cd and As, therefore research in environmental and biological materials is caused the biggest
Obstacle.Though experienced by long-term development course, the imaging technique of quantum dot still may not apply to human body
Medical domain.
Recent study successful I-III-VI race's ternary quantum dots (such as AgInS, CuInSe) is not owing to containing
The element of severe toxicity, and defect is had the strongest toleration, and also emission wavelength depends on composition,
Therefore it is a kind of good luminescent material.But these synthesize the ternary quantum dots obtained in aqueous
Fluorescence quantum yield the lowest (less than 20%), it is impossible to apply well at illumination field and bioluminescence
Imaging field.
Additionally, the problem that existing quantum dot there is also biocompatibility.
Therefore, for nontoxic and there is good biocompatibility thus be applicable to biology or medical science fluorescence
The quantum dot of the high-fluorescence quantum yield of probe, also exists needs.
Summary of the invention
To achieve these goals, the invention provides techniques below scheme:
[1] quantum dot of a kind of nucleocapsid structure, it is characterised in that be made up of the following:
Zn/In:Ag2The core of S；
The shell of ZnS；With
Cladding surface capping agents from the teeth outwards, described surface capping agents selects free the following composition
Group: glutathion, cysteine and combinations thereof.
[2] method that one prepares the quantum dot according to the nucleocapsid structure described in [1], described method includes
Following steps:
(1) Ag that bovine serum albumin (BSA) is coated with is prepared2S quantum dot:
The mixed solution of silver salt solution and BSA aqueous solution is provided；
Regulation pH value；
Sodium sulfide solution is mixed with described mixed solution, obtains BSA by coprecipitation
The Ag of cladding2S quantum dot；
(2) In:Ag of surface capping agents cladding is prepared2S quantum dot:
The Ag that BSA obtained by step (1) is coated with2S is dispersed in water；
Add indium salts and the mixed liquor of first surface covering, wherein said first surface covering
Select the group that free the following forms: glutathion, cysteine and their group
Close；
Regulation pH value；
The In:Ag of surface capping agents cladding is obtained by partial cation exchanged water thermal response2S measures
Sub-point；
(3) Zn/In:Ag of surface capping agents cladding is prepared2S quantum dot
The In:Ag that surface capping agents obtained by step (2) is coated with2S quantum dot is dispersed in water；
Add zinc salt and the mixed liquor of second surface covering, wherein said second surface covering
Select the group that free the following forms: glutathion, cysteine and their group
Close；
Regulation pH value；
The Zn/In:Ag of surface capping agents cladding is obtained by partial cation exchanged water thermal response2S
Quantum dot；
(4) quantum dot of nucleocapsid structure is prepared
Make the Zn/In:Ag that step (3) prepares2S quantum dot is obtained by hydro-thermal reaction with zinc salt
Surface capping agents cladding with Zn/In:Ag2S be core, ZnS be the nucleocapsid structure quantum of shell
Point.
[3] according to the method described in [2], it is characterised in that
Described silver salt is selected from silver nitrate, silver acetate or their mixture；
Described indium salts is selected from indium nitrate, indium acetate, indium chloride or their mixture；
Described zinc salt is selected from zinc nitrate, zinc acetate, zinc chloride, zinc sulfate or their mixture.
[4] according to the method described in [2], it is characterised in that in step (1), at described silver salt solution
The concentration of middle silver ion is that in 0.01-0.15mol/L, BSA aqueous solution, the concentration of BSA is 10-30
Mg/mL, silver salt solution is 1: 10-10: 1 with the volume ratio of BSA aqueous solution, at described sodium sulfide
In aqueous solution, the concentration of sodium sulfide is 0.01-0.15mol/L, and the molar ratio of silver and sulfur is 1: 0.5-1: 2,
Regulate described pH value to 8-12, and the reaction temperature of described coprecipitation is 25-40 DEG C.
[5] according to the method described in [2], it is characterised in that in step (2), Ag2S quantum dot and described
The mol ratio of the In in indium salts is 1: 0.5-1: 16, the In in described indium salts and described first surface cladding
The mol ratio of agent is 1: 1-1: 2, regulates described pH value to 7.5-8.5, and reaction temperature is
100-120℃。
[6] according to the method described in [2], it is characterised in that in step (3), In:Ag2S quantum dot and
The mol ratio of the Zn in described zinc salt is 1: 0.5-1: 8, the Zn in described zinc salt and described second surface
The mol ratio of covering is 1: 1-1: 2, regulates described pH value to 7.5-8.5, and reaction temperature is
110-120℃。
[7] according to the method described in [2], it is characterised in that in step (4), Zn/In:Ag2S quantum dot
Being 1: 0.5-1: 2 with the mol ratio of the Zn in described zinc salt, reaction temperature is 100-110 DEG C.
[8] quantum dot of the nucleocapsid structure described in [1] is as the purposes of fluorescent probe.
[9] according to the purposes described in [8], it is characterised in that described fluorescent probe is led for biological and medical science
Territory.
The beneficial effect comprise that relative to traditional hydrothermal synthesis method, the core that the present invention prepares
Core-shell structure quantum dots internal crystal framework defect is few, and has been passivated surface defect, therefore at biological living mark
The visible/near infrared wave band fluorescence quantum yield of note application is the highest (up to more than 38%, even up to
48%), exceed the most popular Cd system having bio-toxicity and Te system quantum dot, and eliminate
Bio-toxicity and photobleaching phenomenon；Additionally, due to the surface capping agents good paddy that is biocompatibility
The sweet peptide of Guang (GSH)/cysteine (CySH), therefore can be directly applied to photoelectric material and living body biological
In fluorescent labeling.
Accompanying drawing explanation
Fig. 1 is the glutathione-coated according to one embodiment of the invention
Zn/In:Ag2The synthesis schematic diagram of the S@polynary non-toxic quantum dot of ZnS core shell structure；
Fig. 2 is the glutathione-coated according to one embodiment of the invention
Zn/In:Ag2The high-resolution-ration transmission electric-lens picture of the S@polynary non-toxic quantum dot of ZnS core shell structure；
Fig. 3 is the glutathione-coated according to one embodiment of the invention
Zn/In:Ag2The absorption spectrum of the S@polynary non-toxic quantum dot of ZnS core shell structure；
Fig. 4 is the glutathione-coated according to one embodiment of the invention
Zn/In:Ag2The fluorescence spectrum of the S@polynary non-toxic quantum dot of ZnS core shell structure；
Fig. 5 is the glutathione-coated according to one embodiment of the invention
Zn/In:Ag2The fluorescence quantum yield of the S@polynary non-toxic quantum dot of ZnS core shell structure.
Fig. 6 is the cells viability datagram according to one embodiment of the invention.
Detailed description of the invention
Below in conjunction with the accompanying drawings and detailed description of the invention is discussed in detail the present invention.But the protection side of the present invention
Position is not limited to following instance, should comprise the full content in claims.
In order to realize the higher fluorescence quantum yield of quantum dot, an object of the present invention is to provide one
Plant the nontoxic quaternary quantum dot with chemistry and stability of photoluminescence.It is a further object of the present invention to provide one
The method planting the quaternary quantum dot preparing high-fluorescence quantum yield.
In order to realize the purpose of the present invention, one embodiment of the invention provides a kind of high fluorescence volume
The polynary quantum dot of sub-productivity, it is Zn/In:Ag the most successively2S quantum dot and ZnS shell,
And being coated with surface capping agents from the teeth outwards, described surface capping agents selects free the following composition
Group: glutathion, cysteine and combinations thereof.This polynary quantum dot use progressively sun from
Prepared by sub-exchange process: first with the Ag of Co deposited synthesis BSA cladding2S quantum dot；Then profit
Introduce indium by partial cation exchange process, form the In:Ag of surface capping agents cladding2S quantum dot；So
Rear continuation partial cation exchange process introduces zinc, forms the Zn/In:Ag of surface capping agents cladding2S measures
Sub-point；Introduce zinc finally by base exchange method, form ZnS shell.The product finally given is
The quantum dot of a kind of nucleocapsid structure, it is characterised in that be made up of the following: Zn/In:Ag2The core of S；
The shell of ZnS；With cladding surface capping agents from the teeth outwards, the choosing of described surface capping agents is the most following
The group of item composition: glutathion, cysteine and combinations thereof.
The symbol used in the present invention and formula have implication known to this area.Specifically, Ag2S
Represent Argentous sulfide., In:Ag2S represents Ag2A part of Ag in S is replaced by In.Zn/In:Ag2S table
Show Ag2A part of Ag in S is replaced by Zn, and another part is replaced by In.Zn/In:Ag2S@ZnS
Representing nucleocapsid structure, its center is Zn/In:Ag2S, shell is ZnS.BSA represents bovine serum albumin,
Also known as bovine albumin.GSH represents glutathion.CySH represents cysteine.
The glutathion being coated on quantum dot surface and/or cysteine are the biologies modifying surface
Compatibility part, itself and the metal ion complexation on surface.Although it should be appreciated that herein will
They are referred to as surface capping agents, but are not intended to limit them and the most only play surface
The effect of cladding.
The method preparing above-mentioned quantum dot according to one embodiment of the invention can be illustrated by Fig. 1
Property illustrates.First the Ag of synthesis BSA cladding2S, the subsequently In:Ag of synthesis GSH cladding2S quantum
Point, and then the Zn/In:Ag of synthesis GSH cladding2S quantum dot, final synthesis GSH cladding
Zn/In:Ag2S@ZnS quantum dot.The surface capping agents that figure 1 illustrates is glutathion.But,
Can also use cysteine, or the mixture of glutathion and cysteine.In building-up process,
Can be general or mixed as surface capping agents, glutathion and cysteine, both act on identical.
The method preparing quantum dot according to one embodiment of the invention comprises the following steps:
(1) system of the Argentous sulfide. quantum dot that bovine serum albumin (also referred to as bovine albumin, BSA) is coated with
Standby
The mixed solution of silver salt and BSA is provided, regulates pH value, be subsequently added sodium sulfide solution,
Coprecipitation is used to prepare the Ag of BSA cladding2S quantum dot, by controlling addition silver salt and sodium sulfide
Ratio, obtain different luminous Ag2S quantum dot；
Specifically, the silver salt solution of the 0.01-0.15mol/L of 1-10mL (is included silver nitrate and acetic acid
Silver) and the BSA solution of 10-30mg/mL of 1-10mL under agitation mix, regulating pH value is
8-12, the lower sodium sulfide solution adding 0.5-20mL 0.01-0.15mol/L of stirring, anti-at 25-40 DEG C
Should, preferably react about 6 hours, then high speed centrifugation, be precipitated, be Ag2S quantum dot；
(2) Argentous sulfide. (the alternatively referred to as sulfur indium silver) quantum dot of the indium doping of surface capping agents cladding
Preparation
By the Ag obtained by step (1)2S is dispersed in water, and is subsequently adding indium salts and first surface cladding
The mixed liquor of agent (it can be glutathion, cysteine or their mixture), suitably regulates
PH, at high temperature hydro-thermal reaction, centrifuge washing, obtain the In:Ag of surface capping agents cladding2S quantum
Point；
Specifically, by 0.01-1.5mmol according to the Ag obtained by the process of step (1)2S is dispersed in
In 20mL water, under agitation add the mixed liquor of 10mL indium salts and first surface covering (wherein
The amount of the material of indium salts is 0.005-24mmol, and indium salts includes indium nitrate, indium chloride and indium acetate,
The amount of the material of first surface covering is 0.005-48mmol), by pH regulator to 7.5-8.5, so
Rear mixed liquor is transferred in autoclave, 100-120 DEG C of reaction, preferably reacts about 10 hours, and product adds
The ethanol centrifuge washing of excess, obtains the In:Ag of surface capping agents cladding2S quantum dot；
(3) preparation of the Argentous sulfide. quantum dot of the indium/zinc doping of surface capping agents cladding
By the In:Ag obtained by step (2)2S quantum dot is dispersed in water, and adds zinc salt and second surface
The mixed liquor of covering (it can be glutathion, cysteine or their mixture), suitably
Regulation pH, at high temperature hydro-thermal reaction, centrifuge washing, obtain the Zn/In:Ag of surface capping agents cladding2S
Quantum dot；
Specifically, by 0.01-3mmol according to the In:Ag obtained by the process of step (2)2S quantum dot
Be dispersed in 20mL water, under agitation add 10mL zinc salt (include zinc nitrate, zinc acetate,
Zinc chloride and zinc sulfate) and the mixed liquor of second surface covering (wherein the amount of the material of zinc is
0.005-24mmol, the amount of the material of second surface covering is 0.005-48mmol), pH is adjusted
Joint, to 7.5-8.5, during then autoclave transferred to by mixed liquor, 110-120 DEG C, preferably reacts about 10 little
Time, product adds the ethanol centrifuge washing of excess, obtains the Zn/In:Ag of surface capping agents cladding2S quantum
Point；
(4) the nucleocapsid knot with indium/zinc doping sulfuration galactic nucleus and sulfuration cadmia of surface capping agents cladding
The preparation of structure quantum dot
The Zn/In:Ag that step (3) prepares2S quantum dot adds the aqueous solution of zinc salt, then at high temperature
Lower stirring reaction, is then centrifuged for washing, obtains the Zn/In:Ag of surface capping agents cladding2S@ZnS core
Core-shell structure quantum dots.
Specifically, Zn/In:Ag 0.005-3mmol prepared according to the process of step (3)2S measures
Son point be dissolved in 20mL water, add 10mL zinc salt (include zinc nitrate, zinc sulfate, zinc chloride,
Zinc acetate, the amount of material is 0.0025-6mmol) aqueous solution, then at 100-110 DEG C, stirring is anti-
Should, preferably react about 4 hours, be then centrifuged for washing, obtain surface capping agents cladding
Zn/In:Ag2S@ZnS core-shell structured quantum dot.
The quaternary quantum dot of the present invention and conventional II-VI group or iii-v binary quantum dot important
One of difference is, conventional II-VI group or iii-v binary quantum dot (such as CdS and CdTe)
It is dependent on the size of quantum point to change emission wavelength, and the luminous ripple of the quantum dot of the present invention
Length does not relies on size and is adjusted, and is to rely on and is adjusted composition.Owing to composition is different,
So cause the band gap difference of quantum dot, thus emission wavelength is adjusted.So, just without in order to
Change the size of emission wavelength quantum point.
The scope of many parameters in the method for the quantum dot that The present invention gives the synthesis present invention.Should manage
Solving, the parameter area mentioned is the optimizing technology parameters scope of the method implementing the present invention.But, choosing
The main purpose selecting these process parameters range is advantageous for the carrying out of each step reaction rather than to quantum
The final particular make-up of point accurately regulates.
Those skilled in the art can be actually needed according to emission wavelength, adjusts between various element
Suitably proportioning.Final emission wavelength depends on the particular make-up composition of quantum dot.To emission wavelength
Regulation mainly complete in step (3).In step (3), along with the content of the Zn added increases,
The emission wavelength of final quantum point shortens.On the other hand, the intermediate product In:Ag in step (2)2S's
Concrete component does not produce directly impact to final emission wavelength.
In step (2)-(4), the process of cation replacement and the generation of ZnS shell is had bright by the response time
Aobvious impact.Can be by adjusting the composition of response time quantum point.
Beneficial effects of the present invention specifically includes:
(1) present invention uses progressively base exchange method, the silver atoms that instead of in lattice progressively and
Phosphide atom, defines few nanocrystalline of defect, and therefore the electron capture trap within quantum dot is few,
Quantum yield is greatly improved, and is not susceptible to " photobleaching " phenomenon.
(2) one layer of ZnS shell of quantum dot external sheath, ZnS has wider band gap and excellent
Chemical stability, can protect Zn/In:Ag well2S kernel, and it has been passivated generation surface without spoke
Penetrate the defect of transition center, further increasing quantum yield and photochemical stability, and eliminate
Bio-toxicity.
(3) it is glutathion and/or cysteine due to surface capping agents, there is good bio-compatible
Property and environment friendly, therefore may be directly applied to photoelectric material and biological fluorescent labelling field.
(4) in the present invention, can by adjust quaternary quantum dot composition rather than size realizes difference
The luminescence of wavelength, it is only necessary to prepare an equal amount of Ag2S quantum dot as substrate, subsequently increase,
Adjust its composition, just can get the different emission wavelength in the range of width.
By the following examples preferred implementation is made concrete explaination.
Silver nitrate (AgNO used in embodiment3), silver acetate (AgOAc), indium nitrate (In (NO3)3)、
Indium acetate (In (OAc)3), indium chloride, dehydrated alcohol, bovine albumin (BSA), sodium sulfide, gluathione
Peptide, cysteine, zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, all commercially available from traditional Chinese medicines grouping of the world economy
Learn reagent company limited.Above medicine purity is analytical pure AR.
Embodiment 1:
(1) by the silver nitrate solution of the 0.01mol/L of 1mL and the BSA of the 10mg/mL of 1mL
Solution under agitation mixes, and regulation pH value is 8, the lower sulfuration adding 2mL 0.01mol/L of stirring
Sodium solution, reacts 6 hours at 30 DEG C, then high speed centrifugation, is precipitated, is Ag2S quantum
Point；
(2) by the Ag obtained by step (1)2S is dispersed in 20mL water and (measures), under agitation adds
10mL indium nitrate (0.07mmol) and the mixed liquor of glutathion (0.1mmol), arrive pH regulator
7.5, during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds the ethanol of excess
Centrifuge washing, obtains the In:Ag of glutathione-coated2S quantum dot；
(3) by the In:Ag obtained by step (2)2S quantum dot is dispersed in 20mL water and (measures), is stirring
Mix lower addition 5mL zinc nitrate (0.005mmol) and the mixed liquor of glutathion (0.005mmol), will
PH regulator is to 7.8, and during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds
The ethanol centrifuge washing of excess, obtains the In:Ag of glutathione-coated2S quantum dot；
(4) Zn/In:Ag prepared2S quantum dot is dissolved in 20mL water and (measures), adds 10mL
The aqueous solution of zinc sulfate (0.005mmol), then stirring reaction 4 hours at 100 DEG C, are then centrifuged for
Washing, obtains the Zn/In:Ag of glutathione-coated2S@ZnS core-shell structured quantum dot.
Embodiment 2:
(1) by the silver acetate solutions of the 0.01mol/L of 1mL and the BSA of the 10mg/mL of 1mL
Solution under agitation mixes, and regulation pH value is 9, the lower sulfuration adding 2mL 0.01mol/L of stirring
Sodium solution, reacts 6 hours at 30 DEG C, then high speed centrifugation, is precipitated, is Ag2S quantum
Point；
(2) by the Ag obtained by step (1)2S is dispersed in 20mL water and (measures), under agitation adds
The mixed liquor of 10mL indium chloride (0.05mmol) and glutathion (0.1mmol) (, pH regulator is arrived
8.5, during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds the ethanol of excess
Centrifuge washing, obtains the In:Ag of glutathione-coated2S quantum dot；
(3) by the In:Ag obtained by step (2)2S quantum dot is dispersed in 20mL water and (measures), is stirring
Mix lower addition 10mL zinc acetate (0.01mmol) and the mixed liquor of glutathion (0.02mmol), will
PH regulator is to 8.5, and during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds
The ethanol centrifuge washing of excess, obtains the In:Ag of glutathione-coated2S quantum dot；
(4) Zn/In:Ag prepared2S quantum dot is dissolved in 20mL water and (measures), adds 10mL
The aqueous solution of zinc sulfate (0.008mmol), then stirring reaction 4 hours at 100 DEG C, are then centrifuged for
Washing, obtains the Zn/In:Ag of glutathione-coated2S@ZnS core-shell structured quantum dot.
Embodiment 3:
(1) by the silver nitrate solution of the 0.01mol/L of 1mL and the BSA of the 10mg/mL of 1mL
Solution under agitation mixes, and regulation pH value is 9, the lower sulfuration adding 2mL 0.01mol/L of stirring
Sodium solution, reacts 6 hours at 30 DEG C, then high speed centrifugation, is precipitated, is Ag2S quantum
Point；
(2) by the Ag obtained by step (1)2S is dispersed in 20mL water and (measures), under agitation adds
10mL indium chloride (0.05mmol) and the mixed liquor of glutathion (0.1mmol), arrive pH regulator
7.9, during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds the ethanol of excess
Centrifuge washing, obtains the In:Ag of glutathione-coated2S quantum dot；
(3) by the In:Ag obtained by step (2)2S quantum dot is dispersed in 20mL water and (measures), is stirring
Mix lower addition 10mL zinc acetate (0.02mmol) and the mixed liquor of glutathion (0.02mmol), will
PH regulator is to 8.1, and during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds
The ethanol centrifuge washing of excess, obtains the In:Ag of glutathione-coated2S quantum dot；
(4) Zn/In:Ag prepared2S quantum dot is dissolved in 20mL water and (measures), adds 10mL
The aqueous solution of zinc sulfate (0.01mmol), then stirring reaction 4 hours at 100 DEG C, are then centrifuged for
Washing, obtains the Zn/In:Ag of glutathione-coated2S@ZnS core-shell structured quantum dot.
Embodiment 4:
(1) by the silver nitrate solution of the 0.01mol/L of 1mL and the BSA of the 10mg/mL of 1mL
Solution under agitation mixes, and regulation pH value is 9, the lower sulfuration adding 2mL 0.01mol/L of stirring
Sodium solution, reacts 6 hours at 30 DEG C, then high speed centrifugation, is precipitated, is Ag2S quantum
Point；
(2) by the Ag obtained by step (1)2S is dispersed in 20mL water and (measures), under agitation adds
10mL indium acetate (0.08mmol) and the mixed liquor of glutathion (0.15mmol), arrive pH regulator
7.9, during then autoclave transferred to by mixed liquor, 100 DEG C are reacted 10 hours, and product adds the ethanol of excess
Centrifuge washing, obtains the In:Ag of glutathione-coated2S quantum dot；
(3) by the In:Ag obtained by step (2)2S quantum dot is dispersed in 20mL water and (measures), is stirring
Mix the mixed liquor of lower addition 10mL zinc chloride (0.04mmol) and glutathion (0.08mmol) (wherein
The amount of the material of zinc chloride is, the amount of the material of glutathion is, by pH regulator to 8.4, then mixes
Closing liquid and transfer in autoclave, 100 DEG C are reacted 10 hours, and product adds the ethanol centrifuge washing of excess,
Obtain the In:Ag of glutathione-coated2S quantum dot；
(4) Zn/In:Ag prepared2S quantum dot is dissolved in 20mL water and (measures), adds 10mL
The aqueous solution of zinc chloride (0.008mmol), then stirring reaction 4 hours at 100 DEG C, are then centrifuged for
Washing, obtains the Zn/In:Ag of glutathione-coated2S@ZnS core-shell structured quantum dot.
Embodiment 5:
In the way of substantially the same manner as Example 2, preparing nuclear shell structure quantum point, difference is,
In step (2), cysteine is used to replace glutathion.
The product finally given after step (4) is the Zn/In:Ag of glutathione-coated2S@ZnS core shell
Structure quantum point.Its character is essentially identical with the quantum dot of embodiment 2.No matter this shows surface ligand
It it is glutathion or cysteine all has substantially no effect on the core of quantum dot and the composition of shell.
Embodiment 6:
In the way of substantially the same manner as Example 3, preparing nuclear shell structure quantum point, difference is,
In step (3), cysteine is used to replace glutathion.
The product finally given after step (4) is the Zn/In:Ag of cysteine cladding2S@ZnS core shell
Structure quantum point.Its character is essentially identical with the quantum dot of embodiment 3.
Embodiment 7:
In the way of substantially the same manner as Example 4, preparing nuclear shell structure quantum point, difference is,
In step (2) and (3), the glutathion using mol ratio to be 1: 1 and the mixture of cysteine replace
Glutathion.
The product finally given after step (4) is that glutathion is coated with cysteine
Zn/In:Ag2S@ZnS core-shell structured quantum dot.Its character is essentially identical with the quantum dot of embodiment 4.
The performance characterization of quantum dot
The quantum dot using high resolution transmission electron microscopy to prepare embodiment 1-4 is observed, knot
Fruit is as shown in Figure 2.It will be seen that all have good by the quantum dot that the method for the present invention is prepared
Lattice structure, internal flaw and surface defect are the most few.It is the highest that this makes the quantum dot of the present invention have
Fluorescence quantum yield, as mentioned below.
Measuring the absorption spectrum of the quantum dot that embodiment 1-4 prepares, result is as shown in Figure 3.Can see
At 400-550nm visible light wave range, there is strong absorption to quantum dot.
Measuring the fluorescence spectrum of the quantum dot that embodiment 1-4 prepares, result is as shown in Figure 4.Can see
Arriving, its emission wavelength is respectively 630nm, 615nm, 570nm and 550nm.This explanation is logical
Cross the design parameter in the method changing the present invention, i.e. increase the amount of Zn in step (3), can obtain
The ever-reduced quantum dot of emission wavelength.
It is furthermore noted that the size of quantum dot does not has significant change in embodiment 1-4, luminous ripple is described
Long change is mainly caused by composition transfer.
Measuring the fluorescence quantum efficiency of the quantum dot that embodiment 1-4 prepares, result is as shown in Figure 5.Can
To see, its quantum yield more than 38%, up to 48%.
The quantum dot using method well known in the art to prepare embodiment 1-4 carries out cell survival assay.
Fig. 6 is cells viability datagram, correspond to embodiment 1-4 respectively.It will be seen that all synthesis
Quantum dot normal stem cell is hatched the survival rate after 48 hours all more than 95%, it is believed that
It it is non-toxic quantum dot.
Method that is visible, that utilize the present invention, can prepare and highlighted stablize nontoxic quaternary nucleocapsid structure
Quantum dot.This non-toxic quantum dot with chemistry and stability of photoluminescence may serve as biology and medicine
The compound fluorescent probe of purposes.
The above description of this invention is illustrative and not restrictive, and those skilled in the art is managed
Solve, within the spirit and scope that claim limits, it can be carried out many amendments, change or equivalence,
But they fall within protection scope of the present invention.
Claims (9)
1. the quantum dot of a nucleocapsid structure, it is characterised in that be made up of the following:
Zn/In:Ag2The core of S；
The shell of ZnS；With
Cladding surface capping agents from the teeth outwards, described surface capping agents selects free the following composition
Group: glutathion, cysteine and combinations thereof.
2. the method preparing the quantum dot of nucleocapsid structure according to claim 1, described side
Method comprises the following steps:
(1) Ag that bovine serum albumin (BSA) is coated with is prepared2S quantum dot:
The mixed solution of silver salt solution and BSA aqueous solution is provided；
Regulation pH value；
Sodium sulfide solution is mixed with described mixed solution, obtains BSA by coprecipitation
The Ag of cladding2S quantum dot；
(2) In:Ag of surface capping agents cladding is prepared2S quantum dot:
The Ag that BSA obtained by step (1) is coated with2S is dispersed in water；
Add indium salts and the mixed liquor of first surface covering, wherein said first surface covering
Select the group that free the following forms: glutathion, cysteine and their group
Close；
Regulation pH value；
The In:Ag of surface capping agents cladding is obtained by partial cation exchanged water thermal response2S measures
Sub-point；
(3) Zn/In:Ag of surface capping agents cladding is prepared2S quantum dot
The In:Ag that surface capping agents obtained by step (2) is coated with2S quantum dot is dispersed in water；
Add zinc salt and the mixed liquor of second surface covering, wherein said second surface covering
Select the group that free the following forms: glutathion, cysteine and their group
Close；
Regulation pH value；
The Zn/In:Ag of surface capping agents cladding is obtained by partial cation exchanged water thermal response2S
Quantum dot；
(4) quantum dot of nucleocapsid structure is prepared
Make the Zn/In:Ag that step (3) prepares2S quantum dot is obtained by hydro-thermal reaction with zinc salt
Surface capping agents cladding with Zn/In:Ag2S be core, ZnS be the nucleocapsid structure quantum of shell
Point.
Method the most according to claim 2, it is characterised in that
Described silver salt is selected from silver nitrate, silver acetate or their mixture；
Described indium salts is selected from indium nitrate, indium acetate, indium chloride or their mixture；
Described zinc salt is selected from zinc nitrate, zinc acetate, zinc chloride, zinc sulfate or their mixture.
Method the most according to claim 2, it is characterised in that in step (1), at described silver
The concentration of BSA during the concentration of silver ion is 0.01-0.15mol/L, BSA aqueous solution in saline solution
For 10-30mg/mL, silver salt solution is 1: 10-10: 1 with the volume ratio of BSA aqueous solution, in institute
Stating the concentration of sodium sulfide in sodium sulfide solution is 0.01-0.15mol/L, and the molar ratio of silver and sulfur is
1: 0.5-1: 2, regulate described pH value to 8-12, and the reaction temperature of described coprecipitation is 25-40 DEG C.
Method the most according to claim 2, it is characterised in that in step (2), Ag2S quantum
The mol ratio of the In in point and described indium salts is 1: 0.5-1: 16, the In in described indium salts and described first
The mol ratio of surface capping agents is 1: 1-1: 2, regulates described pH value to 7.5-8.5, and reaction temperature
For 100-120 DEG C.
Method the most according to claim 2, it is characterised in that in step (3), In:Ag2S measures
The mol ratio of Zn in son point and described zinc salt is 1: 0.5-1: 8, Zn in described zinc salt and described the
The mol ratio of two surface capping agents is 1: 1-1: 2, regulates described pH value to 7.5-8.5, and reacts temperature
Degree is for 110-120 DEG C.
Method the most according to claim 2, it is characterised in that in step (4), Zn/In:Ag2S
The mol ratio of the Zn in quantum dot and described zinc salt is 1: 0.5-1: 2, and reaction temperature is 100-110 DEG C.
8. the quantum dot of the nucleocapsid structure described in claim 1 is as the purposes of fluorescent probe.
Purposes the most according to claim 8, it is characterised in that described fluorescent probe for biological and
Medical domain.
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