CN106244146A - A kind of method preparing CdTe/CdS quantum dot simultaneously as stabilizer and sulfur source with 2,3 dimercaptopropansulfonate sodium - Google Patents
A kind of method preparing CdTe/CdS quantum dot simultaneously as stabilizer and sulfur source with 2,3 dimercaptopropansulfonate sodium Download PDFInfo
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Abstract
The invention discloses a kind of with 2, the method that 3 dimercaptopropansulfonate sodium prepare CdTe/CdS quantum dot simultaneously as stabilizer and sulfur source, comprise the steps: 1) Caddy (Cleary) and N acetyl L cysteine are dissolved in deionized water, obtain mixed solution A, with sodium hydroxide solution regulation pH value to 9.0, it is transferred to after stirring in hydrothermal reaction kettle, at 200 DEG C, reacts 15min 30min, obtain CdTe quantum crude product；2) CdTe quantum crude product is purified, obtains the CdTe quantum of purification；3) by Caddy (Cleary) and 2,3 dimercaptopropansulfonate sodium are dissolved in deionized water, obtain mixed solution B, with sodium hydroxide solution regulation pH value to 9.0, add CdTe quantum solution, be transferred to after stirring in hydrothermal reaction kettle, at 200 DEG C, react 15min 30min, by the mixture ultra-filtration centrifuge tube ultrafiltration 4 times of gained after reaction, i.e. obtain CdTe/CdS quantum dot.The method, without nitrogen atmosphere, simplifies synthetic operation step, shortens response time, and available stability more preferable CdTe/CdS QDs.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, be specifically related to one and make with Unithiol simultaneously
The method preparing CdTe/CdS quantum dot for stabilizer and sulfur source.
Background technology
Quantum dot is a kind of diameter quasi-zero dimensional nanometer materials between 1-100nm, has special fluorescence property.Containing cadmium
Quantum dot is one of the most commonly used quantum dot, and its quantum yield is high, photochemical stability is good, at photoelectric material, molecular biosciences
The fields such as and bio-medical analysis demonstrate the most tempting application prospect.The quantum yield of CdTe QDs is high, absorption spectrum
Width, emission spectrum are narrow and adjustable, are biomedical and nano material conventional in optoelectronic information.But CdTe QDs still exists
Anti-light drift ability and the problem easily disturbed by ambient impurities, limit it in biochemistry detection, bio-imaging and biological effect etc.
The research of biomedical sector.
Our seminar has successively synthesized CdTe QDs and Zn that NAC modifies with NAC for part2+: CdTe QDs (Zhao D
Et al, J.Mater.Chem., 2011,21,13365), take in terms of quantum yield, anti-light drift ability and reduction bio-toxicity
Obtain certain progress, but be still difficult to meet the requirement of biomedical applications；We the most once and stablized with NAC for sulfur source
Agent, use one-step synthesis method CdTe/CdS QDs (Zhao D et al, J.Phys.Chem.C, 2009,113,1293-
1300), there is good anti-light drift ability, but its response time length, there is wider half-peak breadth and in visible-range
It is difficult to involucrum.Seminar is had successively to synthesize CdS QDs simultaneously as sulfur source with stabilizer with 2,3-dimercaptosuccinic acid
With AgS QDs (Sevinc E et al, J.Mater.Chem., 2012,22,5137；Hocaoglu I et al,
Nanoscale,2014,6,11921-11931).Many research work show, compared to single thiol ligand, double thiol ligand are made
Quantum dot for stabilizer synthesis has more preferable stability.Mono dentate is modified synthesis with many thiol ligand by Susumu etc.
Quantum dot performance has carried out the comparison of system, it was demonstrated that the quantum dot that many thiol ligand are modified has more preferable anti-light drift ability
(Susumu K et al,J.Am.Chem.Soc.,2011,133,9480-9496).But Hyeon et al. thinks double sulfydryl modification
The advantage (Ling D et al, Nano Today, 2014,9,457-477) the most not absolute in performance of quantum dot.
Summary of the invention
The problem existed for above-mentioned prior art, the invention provides one and makees with Unithiol simultaneously
The method preparing CdTe/CdS quantum dot for stabilizer and sulfur source, the method uses DMPS to do modified ligand and sulfur source, it is not necessary to nitrogen
Atmosphere is enclosed, and simplifies synthetic operation step, shortens response time, and available stability more preferable CdTe/CdS QDs.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
A kind of method preparing CdTe/CdS quantum dot simultaneously as stabilizer and sulfur source with Unithiol,
Comprise the steps:
1) Caddy (Cleary) and N-acetyl-L-cysteine are dissolved in deionized water, obtain mixed solution A, use hydroxide
The pH value of sodium solution regulation mixed solution A, to 9.0, adds Sodium tellurite. and borane reducing agent sodium hydride, wherein Caddy (Cleary), N-second
The mol ratio of acyl-Cys, Sodium tellurite. and sodium borohydride is 1:2.4:0.2:1.8, is transferred to hydro-thermal after stirring
In reactor, at 200 DEG C, react 15min-30min, obtain CdTe quantum crude product；
2) CdTe quantum crude product is joined in enough isopropanols, stir, obtain quantum dot turbid solution, will amount
Son point turbid solution is centrifuged, washs 4 times, is vacuum dried by gained solids, obtains purification, dry CdTe quantum, puts
Save backup at 4 DEG C；
3) Caddy (Cleary) and Unithiol are dissolved in deionized water, obtain mixed solution B, use sodium hydroxide
The pH value of solution regulation mixed solution B, to 9.0, adds CdTe quantum solution, wherein CdTe quantum, Caddy (Cleary) and 2,3-
The mol ratio of dimercaptopropansulfonate sodium is 1:500:1200, is transferred in hydrothermal reaction kettle after stirring, and reacts at 200 DEG C
15min-30min, by the mixture ultra-filtration centrifuge tube ultrafiltration 4 times of gained after reaction, i.e. obtains CdTe/CdS quantum dot.
Preferably, step 1) and step 3) in the concentration of used sodium hydroxide solution be 1mol/L.
Preferably, step 2) in, the rotating speed time the most centrifugal is 8000r/min, and centrifugation time is 10min.
Preferably, step 2) in, vacuum drying temperature is 60 DEG C, and the time is 24h.
Preferably, step 2) in, CdTe quantum crude product is 1:3 with the volume ratio of isopropanol.
Compared with prior art, its beneficial effect and advantage are the present invention:
1, the method is simple to operation, can be obtained by CdTe/CdS QDs, and building-up process by two-step hydrothermal route
In need not inflated with nitrogen and protect, synthesis condition becomes simple and easy to control, thus enormously simplify operating procedure, saves people
Power and material resources (i.e. providing cost savings), improve combined coefficient.
2, the raw material needed for the method is cheap and easily-available, and required equipment is conventional equipment, cheap.
3, compared with conventional CdTe QDs, CdTe/CdS QDs prepared by the method has the advantage that 1) preferably
Anti-light drift ability；2) more preferable anti-salt-stable；3) the broader pH scope of application；4) under high temperature fluorescence substantially without self-quenching；
5) there is longer fluorescence lifetime.The raising of stability has important work for quantum dot in terms of bio-imaging and bio-sensing
With；The broader pH scope of application also can widen quantum dot range of application in cell or live body, bio-medical analysis with become
Image space face, is particularly significant in the relatively low ph conditions such as canceration；Quantum dot can be made to give birth to the stability of temperature
Thing sensing aspect has preferably application, and longer fluorescence lifetime can reduce the interference of tissue autofluorescence.
4, the CdTe/CdS QDs particle diameter of the method synthesis is little and homogeneous, and biocompatibility is preferable, can be widely applied to raw
Change detection, cell and the biomedical sector such as living imaging, target tracing, it is possible to as opto-electronic conversion and luminescence display material.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture (TEM figure) of DMPS-CdTe/CdS QDs.
Fig. 2 is the X ray diffracting spectrum (XRD figure) of DMPS-CdTe/CdS QDs.
Fig. 3 is the uv-visible absorption spectra of the DMPS-CdTe/CdS QD of differential responses time synthesis in embodiment 1-4
Figure.
Fig. 4 is the fluorescence spectrum figure of the DMPS-CdTe/CdS QDs of differential responses time synthesis in embodiment 1-4.
Fig. 5 is DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs, DMSA-CdTe/
The anti-light drift of CdS QDs and NAC-CdTe QDs can be tried hard to.
Fig. 6 is DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs, DMSA-CdTe/
The anti-salt-stable figure of CdS QDs and NAC-CdTe QDs.
Fig. 7 is the heat stability figure of NAC-CdTe QDs and DMPS-CdTe/CdS QDs.
Fig. 8 is the pH stability diagram of DMPS-CdTe/CdS QDs and NAC-CdTe/CdS QDs.
Fig. 9 is the fluorescence lifetime phenogram of DMPS-CdTe/CdS QDs under different emission.
Detailed description of the invention
Being specifically described the present invention below in conjunction with specific embodiment, what specific embodiment only optimized most preferably synthesizes bar
Part.
Embodiment 1
1, weigh 171mg Caddy (Cleary) 2.5 hydrate and 294mgN-acetyl-Cys in there-necked flask, add
40ml deionized water, stirring, to being completely dissolved, obtains mixed solution A, regulates mixed solution A with the sodium hydroxide solution of 1mol/L
PH value to 9.0, add 33.2mg Sodium tellurite. and 51mg borane reducing agent sodium hydride, after stirring, be transferred to hydro-thermal reaction
In still, at 200 DEG C, react 20min, obtain CdTe quantum crude product；
2, CdTe quantum crude product is placed in beaker, in beaker, adds the isopropanol of 3 times of volumes, stir,
To quantum dot turbid solution, by quantum dot turbid solution centrifugal (centrifugal condition: 8000r/min, 10min), washing 4 times, gained is solid
Body thing proceeds in vacuum drying oven, is vacuum dried 24h, obtains purification, dry CdTe quantum (CdTe QDs) at 60 DEG C,
It is labeled as NAC-CdTe QDs, is placed at 4 DEG C and saves backup；
3,57mg Caddy (Cleary) 2.5 hydrate and 127mg 2,3-dimercaptopropansulfonate sodium (DMPS) are weighed in there-necked flask
In, obtaining mixed solution B, add 40ml deionized water, stirring, to being completely dissolved, regulates mixing with the sodium hydroxide solution of 1mol/L
The pH value of solution B is to 9.0, then takes 0.4mL mixed solution B, adds 2.5mL 2 × 10-6Mol/L CdTe quantum solution, stirring
It is transferred to after Jun Yun in hydrothermal reaction kettle, at 200 DEG C, reacts 30min, by the mixture molecular cut off of gained after reaction
For the ultra-filtration centrifuge tube ultrafiltration 4 times of 30KD, i.e. obtain CdTe/CdS quantum dot (CdTe/CdS QDs), be labeled as DMPS-CdTe/
CdS QDs。
The DMPS-CdTe/CdS QDs preparing the present embodiment carries out transmission electron microscopy, its transmission electron microscope picture (TEM figure)
As it is shown in figure 1, from figure 1 it appears that DMPS-CdTe/CdS QDs has preferable dispersibility, and uniform particle diameter.
The DMPS-CdTe/CdS QDs preparing the present embodiment carries out X-ray diffraction analysis, its XRD figure as in figure 2 it is shown,
From figure 2 it can be seen that 2 θ of CdTe/CdS QDs move to big angular direction, and the crystal plane structure showing CdS occurs, thus
Prove the generation of CdS shell.
Embodiment 2
1, with embodiment 1；
2, with embodiment 1；
3,57mg Caddy (Cleary) 2.5 hydrate and 127mg 2,3-dimercaptopropansulfonate sodium (DMPS) are weighed in there-necked flask
In, obtaining mixed solution B, add 40ml deionized water, stirring, to being completely dissolved, regulates mixing with the sodium hydroxide solution of 1mol/L
The pH value of solution B is to 9.0, then takes 0.4mL mixed solution B, adds 2.5mL 2 × 10-6mol/L CdTe quantum solution, stirs
It is transferred in hydrothermal reaction kettle after mixing uniformly, at 200 DEG C, reacts 15min, by the mixture of gained after reaction with retaining molecule
The ultra-filtration centrifuge tube ultrafiltration that amount is 30KD 4 times, i.e. obtains CdTe/CdS quantum dot (CdTe/CdS QDs).
Embodiment 3
1, with embodiment 1；
2, with embodiment 1；
3,57mg Caddy (Cleary) 2.5 hydrate and 127mg 2,3-dimercaptopropansulfonate sodium (DMPS) are weighed in there-necked flask
In, obtaining mixed solution B, add 40ml deionized water, stirring, to being completely dissolved, regulates mixing with the sodium hydroxide solution of 1mol/L
The pH value of solution B is to 9.0, then takes 0.4mL mixed solution B, adds 2.5mL 2 × 10-6mol/L CdTe quantum solution, stirs
It is transferred in hydrothermal reaction kettle after mixing uniformly, at 200 DEG C, reacts 20min, by the mixture of gained after reaction with retaining molecule
The ultra-filtration centrifuge tube ultrafiltration that amount is 30KD 4 times, i.e. obtains CdTe/CdS quantum dot (CdTe/CdS QDs).
Embodiment 4
1, with embodiment 1；
2, with embodiment 1；
3,57mg Caddy (Cleary) 2.5 hydrate and 127mg 2,3-dimercaptopropansulfonate sodium (DMPS) are weighed in there-necked flask
In, obtaining mixed solution B, add 40ml deionized water, stirring, to being completely dissolved, regulates mixing with the sodium hydroxide solution of 1mol/L
The pH value of solution B is to 9.0, then takes 0.4mL mixed solution B, adds 2.5mL 2 × 10-6mol/L CdTe quantum solution, stirs
It is transferred in hydrothermal reaction kettle after mixing uniformly, at 200 DEG C, reacts 25min, by the mixture of gained after reaction with retaining molecule
The ultra-filtration centrifuge tube ultrafiltration that amount is 30KD 4 times, i.e. obtains CdTe/CdS quantum dot (CdTe/CdS QDs).
The CdTe/CdS QDs (being configured to solution post analysis) of embodiment 1-4 synthesis is carried out uv-visible absorption spectra
Analyzing, the uv-visible absorption spectra figure of gained is as it is shown on figure 3, from figure 3, it can be seen that along with the increase in response time, purple
The continuous red shift of outer absorption, illustrates that the particle diameter of quantum dot increases, and the shell of quantum dot is in growth.
Spectrofluorimetry to the CdTe/CdS QDs (being configured to solution post analysis) of embodiment 1-4 synthesis, gained
Fluorescence spectrum figure as shown in Figure 4, figure 4, it is seen that along with the increase in response time, the continuous red shift of fluorescence of quantum dot,
Illustrate that the wavelength of this nuclear shell structure quantum point is the most adjustable.
Comparative example 1
1, weigh 171mg Caddy (Cleary) 2.5 hydrate and 294mgN-acetyl-Cys in there-necked flask, add
40ml deionized water, stirring, to being completely dissolved, obtains mixed solution A, regulates mixed solution A with the sodium hydroxide solution of 1mol/L
PH value to 9.0, add 33.2mg Sodium tellurite. and 51mg borane reducing agent sodium hydride, after stirring, be transferred to hydro-thermal reaction
In still, at 200 DEG C, react 20min, obtain CdTe quantum crude product；
2, CdTe quantum crude product is placed in beaker, in beaker, adds the isopropanol of 3 times of volumes, stir,
To quantum dot turbid solution, by quantum dot turbid solution centrifugal (centrifugal condition: 8000r/min, 10min), washing 4 times, gained is solid
Body thing proceeds in vacuum drying oven, is vacuum dried 24h, obtains purification, dry CdTe quantum (CdTe QDs) at 60 DEG C,
It is placed at 4 DEG C and saves backup；
3,57mg Caddy (Cleary) 2.5 hydrate and 98mg N-acetyl-L-cysteine (NAC) are weighed in there-necked flask,
Mixed solution B, adds 40ml deionized water, and stirring, to being completely dissolved, regulates mixed solution B with the sodium hydroxide solution of 1mol/L
PH value to 9.0, then take 0.4mL mixed solution B, add 2.5mL 2 × 10-6mol/L CdTe quantum, turn after stirring
Move in hydrothermal reaction kettle, at 200 DEG C, react 30min, i.e. obtain CdTe/CdS quantum dot (CdTe/CdS QDs), be labeled as
NAC-CdTe/CdS QDs。
Comparative example 2
1, weigh 171mg Caddy (Cleary) 2.5 hydrate and 294mgN-acetyl-Cys in there-necked flask, add
40ml deionized water, stirring, to being completely dissolved, obtains mixed solution A, regulates mixed solution A with the sodium hydroxide solution of 1mol/L
PH value to 9.0, add 33.2mg Sodium tellurite. and 51mg borane reducing agent sodium hydride, after stirring, be transferred to hydro-thermal reaction
In still, at 200 DEG C, react 20min, obtain CdTe quantum crude product；
2, CdTe quantum crude product is placed in beaker, in beaker, adds the isopropanol of 3 times of volumes, stir,
To quantum dot turbid solution, by quantum dot turbid solution centrifugal (centrifugal condition: 8000r/min, 10min), washing 4 times, gained is solid
Body thing proceeds in vacuum drying oven, is vacuum dried 24h, obtains purification, dry CdTe quantum (CdTe QDs) at 60 DEG C,
It is placed at 4 DEG C and saves backup；
3, mistabrom (MSA) solution of 57mg Caddy (Cleary) 2.5 hydrate and 0.2mL 3mol/L is weighed in three mouthfuls
In flask, obtaining mixed solution B, add 40ml deionized water, stirring, to being completely dissolved, regulates mixed with the sodium hydroxide solution of 1mol/L
The pH value of conjunction solution B is to 9.0, then takes 0.4mL mixed solution B, adds 2.5mL 2 × 10-6mol/L CdTe quantum, stirring
It is transferred to after Jun Yun in hydrothermal reaction kettle, at 200 DEG C, reacts 30min, i.e. obtain CdTe/CdS quantum dot (CdTe/CdS
QDs), MSA-CdTe/CdS QDs it is labeled as.
Comparative example 3
1, weigh 171mg Caddy (Cleary) 2.5 hydrate and 294mgN-acetyl-Cys in there-necked flask, add
40ml deionized water, stirring, to being completely dissolved, obtains mixed solution A, regulates mixed solution A with the sodium hydroxide solution of 1mol/L
PH value to 9.0, add 33.2mg Sodium tellurite. and 51mg borane reducing agent sodium hydride, after stirring, be transferred to hydro-thermal reaction
In still, after being heated to 200 DEG C, react 20min, obtain CdTe quantum crude product；
2, CdTe quantum crude product is placed in beaker, in beaker, adds the isopropanol of 3 times of volumes, stir,
To quantum dot turbid solution, by quantum dot turbid solution centrifugal (centrifugal condition: 8000r/min, 10min), washing 4 times, gained is solid
Body thing proceeds in vacuum drying oven, is vacuum dried 24h, obtains purification, dry CdTe quantum (CdTe QDs) at 60 DEG C,
It is placed at 4 DEG C and saves backup；
3,57mg Caddy (Cleary) 2.5 hydrate and 108mg DMSA (DMSA) are weighed in there-necked flask,
Obtaining mixed solution B, add 40ml deionized water, stirring, to being completely dissolved, regulates mixing with the sodium hydroxide solution of 1mol/L molten
Liquid B regulation pH value is 9.0, then takes 0.4mL mixed solution B, adds 2.5mL 2 × 10-6mol/L CdTe quantum, and stirring is all
It is transferred to after even in hydrothermal reaction kettle, after being heated to 200 DEG C, reacts 30min, i.e. obtain CdTe/CdS quantum dot (CdTe/CdS
QDs), DMSA-CdTe/CdS QDs it is labeled as.
To DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs, DMSA-CdTe/CdS
QDs, NAC-CdTe QDs carries out energy spectrum analysis (transmitting consistent wavelength), and its result is as shown in table 1 below:
As it can be seen from table 1 compared with NAC-CdTe QDs, in DMPS-CdTe/CdS QDs, the content of S increases and Te
Content significantly reduces, and combines with XRD structure, further illustrates and generates CdS shell.
Test one, the anti-light drift ability test of the CdTe/CdS quantum dot (DMPS-CdTe/CdS QDs) of the present invention
Test method: take 16 pipe DMPS-CdTe/CdS QDs (prepared by embodiment 1) solution, 16 pipe NAC-CdTe/ respectively
CdS QDs solution, 16 pipe MSA-CdTe/CdS QDs solution, 16 pipe DMSA-CdTe/CdS QDs and 16 pipe NAC-CdTe QDs
(prepared by embodiment 1) solution, first by dilute for solution 20mM tri-(methylol) aminomethane (Tris-HCl) buffer in each pipe
Release to same concentrations (about 80nM), more each pipe is placed under the uviol lamp of 356nm wavelength (U=32V) irradiates 90min, 0,
5,10,15,20,25,30,35,40,45,50,60,70,80,90min time measure the fluorescence intensity of solution in each pipe, thus
Obtain DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs, DMSA-CdTe/CdS QDs and
Fluorescence intensity (average fluorescent strength) under NAC-CdTe QDs irradiates under uviol lamp is schemed over time.
Result of the test:
DMPS-CdTe/CdS QDs、NAC-CdTe/CdS QDs、MSA-CdTe/CdS QDs、DMSA-CdTe/CdS QDs
Under irradiating under uviol lamp with NAC-CdTe QDs fluorescence intensity (average fluorescent strength) scheme (the most anti-light over time
Drift can be tried hard to) as it is shown in figure 5, from fig. 5, it can be seen that DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/
The fluorescence intensity of CdS QDs and DMSA-CdTe/CdS QDs does not weakens, and the fluorescence of NAC-CdTe QDs reduces by 60% left side
The right side, illustrates DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs and DMSA-CdTe/CdS QDs
There is good anti-light drift ability.
Test two, the anti-salt-stable test of the CdTe/CdS quantum dot (DMPS-CdTe/CdS QDs) of the present invention
Test method: by DMPS-CdTe/CdS QDs (prepared by embodiment 1) solution, NAC-CdTe/CdS QDs solution,
MSA-CdTe/CdS QDs solution, DMSA-CdTe/CdS QDs and NAC-CdTe QDs (prepared by embodiment 1) solution 20mM tri-
The high-salt buffer of (methylol) aminomethane (Tris-HCl)+600mM NaCl is diluted to same concentrations (about 80nM), then
It is respectively placed at dark and places 24 hours, measure DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS
QDs, DMSA-CdTe/CdS QDs and NAC-CdTe QDs solution was the fluorescence intensity of 0,24 hours, thus obtained DMPS-
CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs, DMSA-CdTe/CdS QDs and NAC-CdTe
QDs fluorescence intensity under high salt schemes (the most anti-salt is stably schemed) over time.
Result of the test:
DMPS-CdTe/CdS QDs、NAC-CdTe/CdS QDs、MSA-CdTe/CdS QDs、DMSA-CdTe/CdS QDs
(the most anti-salt is stably schemed) is schemed over time as shown in Figure 6 with NAC-CdTe QDs fluorescence intensity under high salt, can from Fig. 6
To find out, DMPS-CdTe/CdS QDs, NAC-CdTe/CdS QDs, MSA-CdTe/CdS QDs and DMSA-CdTe/CdS QDs
Anti-salt-stable be better than NAC-CdTe QDs.
Test three, the heat stabilization test of the CdTe/CdS quantum dot (DMPS-CdTe/CdS QDs) of the present invention
Test method: take 1 pipe DMPS-CdTe/CdS QDs (prepared by embodiment 1) solution and 1 pipe NAC-CdTe QDs is (real
Execute example 1 to prepare) solution, as a control group, separately take 1 pipe DMPS-CdTe/CdS QDs solution and 1 pipe NAC-CdTe QDs solution,
As experimental group, first solution 20mM tri-(methylol) aminomethane (Tris-HCl) buffer in each pipe is diluted to identical
Concentration (about 80nM), then experimental group is placed in the water-bath of 90 DEG C heating 10min, matched group is placed in room temperature (20-30 DEG C)
10min, measures the fluorescence spectrum of solution in each pipe respectively, obtain NAC-CdTe/CdS QDs and NAC-CdTe QDs not
Fluorescence spectrum figure (i.e. heat stability figure) under synthermal.
Result of the test:
The fluorescence spectrum figure (the most thermally-stabilised figure) at different temperatures of DMPS-CdTe/CdS QDs and NAC-CdTe QDs
As it is shown in fig. 7, from figure 7 it can be seen that DMPS-CdTe/CdS QDs will not occur self-quenching under the high temperature conditions, and NAC-
CdTe QDs can occur serious self-quenching phenomenon under the high temperature conditions, illustrates that DMPS-CdTe/CdS QDs has more preferable heat
Stability.
Test four, the pH stability test of the CdTe/CdS quantum dot (DMPS-CdTe/CdS QDs) of the present invention
Test method: take 9 pipe DMPS-CdTe/CdS QDs (prepared by embodiment 1) solution and 9 pipe NAC-CdTe/CdS QDs
Solution, first by 9 pipe DMPS-CdTe/CdS QDs solution respectively with pH value be 4.0,5.0,6.0,7.0,8.0,9.0,10.0,
11.0, three (methylol) aminomethane (Tris-HCl) buffer of 12.0 is diluted to same concentrations (about 80nM), 9 pipe NAC-
CdTe/CdS QDs solution is respectively by three (the hydroxyl first that pH value is 4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0,12.0
Base) aminomethane (Tris-HCl) buffer is diluted to same concentrations (about 80nM), then measure solution in each pipe respectively
Fluorescence intensity, obtains the fluorescence intensity change at various ph values of DMPS-CdTe/CdS QDs and NAC-CdTe/CdS QDs
Figure (i.e. pH stability diagram).
Result of the test:
The fluorescence intensity change figure at various ph values of DMPS-CdTe/CdS QDs and NAC-CdTe/CdS QDs is (i.e.
PH stability diagram) as shown in Figure 8, from figure 8, it is seen that NAC-CdTe/CdS QDs is when pH is less than 6.0, basic unstressed configuration；
And DMPS-CdTe/CdS QDs is when pH is equal to 4, still there is stronger fluorescence, illustrate that DMPS-CdTe/CdS QDs has wider
The pH scope of application, this has important effect for quantum dot application in cell and live body.
Test five, the fluorescence lifetime test of the CdTe/CdS quantum dot (DMPS-CdTe/CdS QDs) of the present invention
Test method:
4 pipes are launched wavelength and is respectively DMPS-CdTe/CdS QDs (the embodiment 1-4 system of 538,558,584 and 614nm
Standby) solution, it is diluted to same concentrations (about 80nM) respectively with 20mM tri-(methylol) aminomethane (Tris-HCl) buffer,
Measure its fluorescence lifetime again, thus obtain the fluorescence lifetime phenogram of the DMPS-CdTe/CdS QDs of different emission.
Result of the test:
The fluorescence lifetime phenogram of the DMPS-CdTe/CdS QDs of different emission is as it is shown in figure 9, can from Fig. 9
Going out, along with launching red shift of wavelength, the fluorescence lifetime of DMPS-CdTe/CdS QDs gradually increases, as a length of 614nm of transmitted wave,
Its life-span, the longer life-span can reduce the autofluorescence of tissue, extremely important for vivo applications up to 60ns.
Claims (5)
1. the method preparing CdTe/CdS quantum dot with Unithiol simultaneously as stabilizer and sulfur source, its
It is characterised by comprising the steps:
1) Caddy (Cleary) and N-acetyl-L-cysteine are dissolved in deionized water, obtain mixed solution A, molten with sodium hydroxide
The pH value of liquid regulation mixed solution A, to 9.0, adds Sodium tellurite. and borane reducing agent sodium hydride, wherein Caddy (Cleary), N-acetyl-
The mol ratio of Cys, Sodium tellurite. and sodium borohydride is 1:2.4:0.2:1.8, is transferred to hydro-thermal reaction after stirring
In still, at 200 DEG C, react 15min-30min, obtain CdTe quantum crude product；
2) CdTe quantum crude product is joined in enough isopropanols, stir, obtain quantum dot turbid solution, by quantum dot
Turbid solution is centrifuged, washs 4 times, is vacuum dried by gained solids, obtains purification, dry CdTe quantum, be placed in 4 DEG C
Under save backup；
3) Caddy (Cleary) and Unithiol are dissolved in deionized water, obtain mixed solution B, use sodium hydroxide solution
The pH value of regulation mixed solution B, to 9.0, adds CdTe quantum solution, wherein CdTe quantum, Caddy (Cleary) and 2,3-bis-mercapto
The mol ratio of base propanesulfonate is 1:500:1200, is transferred in hydrothermal reaction kettle after stirring, and reacts at 200 DEG C
15min-30min, by the mixture ultra-filtration centrifuge tube ultrafiltration 4 times of gained after reaction, i.e. obtains CdTe/CdS quantum dot.
The most according to claim 1 prepare CdTe/CdS with 2,3-dimercaptopropansulfonate sodium simultaneously as stabilizer and sulfur source
The method of quantum dot, it is characterised in that: step 1) and step 3) in the concentration of used sodium hydroxide solution be 1mol/L.
The most according to claim 1 prepare CdTe/CdS with 2,3-dimercaptopropansulfonate sodium simultaneously as stabilizer and sulfur source
The method of quantum dot, it is characterised in that: step 2) in, the rotating speed time the most centrifugal is 8000r/min, and centrifugation time is 10min.
The most according to claim 1 prepare CdTe/CdS with 2,3-dimercaptopropansulfonate sodium simultaneously as stabilizer and sulfur source
The method of quantum dot, it is characterised in that: step 2) in, vacuum drying temperature is 60 DEG C, and the time is 24h.
The most according to claim 1 prepare CdTe/CdS with 2,3-dimercaptopropansulfonate sodium simultaneously as stabilizer and sulfur source
The method of quantum dot, it is characterised in that: step 2) in, CdTe quantum crude product is 1:3 with the volume ratio of isopropanol.
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