CN104174863B - A kind of germanium nanocluster, Its Preparation Method And Use - Google Patents
A kind of germanium nanocluster, Its Preparation Method And Use Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of germanium fluorescence cluster, in aqueous germanium fluorescence cluster and the application in bio-imaging thereof.Described synthetic method is using germanium dioxide as ge source, prepares the germanium nanocluster with photoluminescent property of monolayer protection as protective agent, sodium borohydride as reducing agent using biological micromolecule cysteine.The present invention raw materials used simple, be easy to get, stable in properties, there is no toxicity；Course of reaction is without high temperature and the protection of noble gas, simple to operation；Emerald green or yellow fluorescence the germanium quantum point that has obtained has higher fluorescence quantum yield compared with the noble metal nano cluster reported before, cluster size is about at about 1nm, there is good water solublity, no cytotoxicity, it is possible to be advantageously applied to imaging biological cells.
Description
Technical field
The present invention relates to a kind of germanium nanocluster, Its Preparation Method And Use, particularly relate to one and have by force
The germanium nanocluster of photoluminescent property, its preparation method and the application on bio-imaging thereof.
Background technology
The silicon of the 4th main group, germanium, as indirect bandgap material, are led in microelectronics the decades in past
Territory obtains a lot of application, but owing at room temperature fluorescence quantum yield is extremely low, at optics and photoelectron device
The application in part field is constantly subjected to limitation.Developing rapidly recently as nanotechnology, semi-conducting material
Silicon, the research of germanium also achieve new breakthrough, when it is in nanoscale, due to quantum confined effect,
Will convert to as direct band gap nano material, present the unique physical chemistry being different from conventional silicon Germanium material
Character.
As silicon, the germanium semiconductor quantum dot of nm regime study hotspot, show the strongest fluorescent characteristic,
There is compared with traditional fluorescent material the advantages such as light stability is strong, photoluminescent property is adjustable, fluorescence lifetime length.
Past 20 years there is a lot of seminar prepared by the quantum dot of silicon and application conducts in-depth research,
Compared with silicon, the research work of germanium quantum point is the most relatively fewer.But it is known that germanium has compared with silicon
Bigger exciton Bohr radius, shows higher quantum confined effect, therefore germanium quantum point the most also by
Gradually start to cause the concern of people, but we have seen that the research report about germanium is the most simply confined to germanium and prepares
Poromerics and germanium quantum point on, except in physics field, stability for germanium cluster in theory is entered
Outside row research, the report of the germanium cluster prepared with chemical means almost without, and about having photoluminescent property
The report of germanium cluster do not have especially.
Owing to cluster is in a transition and linkage region of atom and macroscopic material, it is the evolution growth of material
The research of process provides new model and support, has become as a big study hotspot in past 20 years.
Especially gold nano cluster, due to quantum confined effect, Aurum clusters presents discontinuous electronic state, and
Show the character being similar to molecule, there is stronger fluorescence and light stability, also show the catalysis of uniqueness
Activity and magnetic property.The synthetic method of gold nano cluster had the most once been referred to as the hot subject that people are interested,
Finance is super and substantial amounts of work has been done, also right for the synthetic technology of gold nano cluster by Zeng Xiaochengdeng seminar
The structure of gold nano cluster has carried out a large amount of theoretical research.About gold nano cluster fluorescence formed mechanism and
There has been substantial amounts of report in the optically active source of chirality, in report metal cluster as be one super
Molecule, the electronics that the Fluorescence Mechanism of metal cluster is attributed between intramolecule HOMO and LUMO jumps
Move, the chirality optical activity of metal cluster then can be attributed to chiral induction and the metal core of protective layer molecule
Two parts of the chirality stack manner of the metallic atom at heart position.At present the metal cluster of report concentrate on gold,
These several transition metals of silver, copper, platinum, metal cluster is not solely restricted to the cluster of single metal, also
There is the report of gold, silver hydridization cluster.
But up to the present, we do not see the report of the semiconductor alloy cluster with photoluminescent property.
Between 1-100nm, plasma primitive covibration is only shown different from the nanoparticle of noble metal
Being that the quantum dot of quasiconductor also has good photoluminescent property, in our invention, first observed is to when half
Conductor germanium be smaller in size than 1nm namely with elementide state in the presence of, also show good fluorescence live
Property, and showing more higher fluorescence quantum yield than noble metal, our invention not only provides a class new
Fluorescent material, also opens a brand-new research field.
Summary of the invention
It is an object of the invention to provide and a kind of there is stronger photoluminescent property germanium nanocluster, and preparation side
Method, the method material therefor is simple, be easy to get, and building-up process is simple, practical, it is extensive to can be used for industrialization
Produce, it is thus achieved that germanium nanocluster stable, fluorescence quantum yield high, and shows in experiment good in vitro
Good imaging biological cells characteristic, can be used for bio-imaging.
The preparation method of germanium nanocluster provided by the present invention, comprises the steps:
(1) ge source is dissolved in aqueous slkali prepared ge source solution；
(2) protective agent is dissolved in water and prepares protectant aqueous solution；
(3) step (1) gained ge source solution is joined in step (2) protectant aqueous solution；
(4) reducing agent is joined in step (3) gained solution；
(5) solution of heating steps (4), obtains germanium nanocluster.
As optimal technical scheme, preparation method of the present invention, wherein the ge source described in step (1) is two
Germanium oxide is or/and germanium salt；It is preferably germanium dioxide or/and sodium metagermanate；More preferably germanium dioxide.
Preferably, step (1) described aqueous slkali is the solution of the hydroxide of alkali metal containing, preferably hydroxide
Sodium is or/and potassium hydroxide；
Preferably, step (2) described protective agent is the little molecule with sulfydryl, preferably cysteine；
Preferably, step (4) described reducing agent is the inorganic salts with reducing power, preferably hydroboration
Sodium；
Preferably, the temperature of step (5) described heating is 50-90 DEG C, preferably 60-80 DEG C, further preferably
It is 65 DEG C-75, particularly preferably 70 DEG C.
Germanium dioxide can be dissolved in the aqueous solution of sodium hydroxide under ultrasonication；Cysteine is a kind of own
There is the biological micromolecule of certain reducing power, often as protective agent in the preparation of various nano materials；
And sodium borohydride is a kind of reducing agent with the strongest reducing power, can germanium be reduced to low by high-valence state
Valence state.The bio-toxicity of germanium is little, therefore considers germanium quantum point is applied to bio-imaging.
As optimal technical scheme, preparation method of the present invention, wherein said method includes walking as follows
Rapid:
(1) under the conditions of Ultrasonic Radiation, ge source is dissolved in aqueous slkali, is prepared as ge source solution, molten with acid
The pH value of ge source solution is regulated to 6-9 by liquid, for example, 6.1,6.5,6.7,7,7.4,7.5,7.8,
8,8.2,8.5,8.6 etc.；
(2) protective agent is joined in ultra-pure water, stirring, dissolve, obtain protectant aqueous solution；
(3) the ge source solution of step (1) is joined in step (2) protectant aqueous solution；
(4) reducing agent is added in step (3) gained solution, stirring, dissolve；
(5) by lower for the heating of step (4) gained solution stirring, continue reacting by heating and obtain germanium nanocluster；
Optionally carry out the inorganic salt in the germanium nanocluster aqueous solution of (6) removal step (5) gained ,-50 DEG C～-60
At a temperature of DEG C, lyophilization preserves.
As optimal technical scheme, preparation method of the present invention, wherein ultrasonic amplitude described in step (1)
Penetrate employing ultrasonic cleaning instrument.For ultrasonic power not particularly requirement.
Preferably, described aqueous slkali is sodium hydroxide solution or potassium hydroxide solution；The most described aqueous slkali
Concentration is 2-10mg/ml, for example, 3mg/ml, 4.5mg/ml, 5mg/ml, 6.3mg/ml, 7mg/ml,
8mg/ml, 9mg/ml, 9.1mg/ml, 9.5mg/ml etc..The concentration of aqueous slkali is for the preparation of ge source solution
Process has material impact, and alkaline concentration is too low, and ge source can not fully be dissolved wherein, alkaline concentration mistake
Height then ge source can form milky insoluble matter wherein, and ge source should be filled by the aqueous slkali of suitable concentration
Dividing to dissolve and will not form the most again insoluble matter, therefore the present invention selects the concentration of aqueous slkali to be 2-10mg/ml,
More preferably 5-8mg/ml；Particularly preferably 6mg/ml.
Preferably, described ge source is germanium dioxide or/and germanium salt；It is preferably germanium dioxide or/and sodium metagermanate；
More preferably germanium dioxide；
Preferably, in described ge source solution, the content of ge source is 2.6-26mg/ml, for example, 2.8mg/ml,
3mg/ml、5mg/ml、7.5mg/ml、10mg/ml、11.5mg/ml、14.2mg/ml、15mg/ml、16.8mg/ml、
20mg/ml, 22.7mg/ml, 24mg/ml, 25.2mg/ml, 25.8mg/ml etc., preferably 5-20mg/ml,
More preferably 10mg/ml.
Preferably, described acid solution is dilute hydrochloric acid.Kind and the concentration of acid solution do not specially require, as long as
The pH value of ge source solution can be regulated to required scope, preferably dilute hydrochloric acid.
Preferably, it is 6-7.5 after the pH value regulation of described ge source solution；More preferably 7.
As optimal technical scheme, preparation method of the present invention, wherein described in step (2), protective agent is
With the little molecule of sulfydryl, preferably cysteine；
Preferably, described protectant concentration is 0.05-1.5mmol/ml, for example, 0.06mmol/ml,
0.10mmol/ml、0.15mmol/ml、0.30mmol/ml、0.50mmol/ml、0.70mmol/ml、
0.85mmol/ml, 1.0mmol/ml, 1.15mmol/ml, 1.30mmol/ml etc., protectant concentration pair
Formation in germanium cluster has considerable influence, the present invention select protectant concentration be 0.05-1.5mmol/ml with
Cluster is made easily and quickly to be formed, preferably 0.1-1mmol/ml；More preferably 1mmol/ml.
Preferably, the mode of described stirring is magnetic agitation.
As optimal technical scheme, preparation method of the present invention, wherein described in step (4), reducing agent is
Sodium borohydride, addition is 3.2-64mg/ml, can be such as 3.5mg/ml, 6.4mg/ml, 12.8mg/ml,
25.6mg/ml, 32.0mg/ml, 38.6mg/ml, 45.0mg/ml, 51.6mg/ml, 62.0mg/ml etc., also
The impact that the consumption of former dose is carried out for reaction is relatively big, for solution ph and the initial reduction of initial reaction stage
Speed all has a great impact, and therefore the present invention selects addition to be that 3.2-64mg/ml is beneficial to entering of reaction
OK, addition is preferably 10-48mg/ml, more preferably 32mg/ml.
Preferably, the mode of described stirring is magnetic agitation.The speed of stirring does not specially require, and is preferably
200-2000r/min, for example, 200-875r/min, 440-1682r/min, 1015-2000r/min, 200r/min,
350r/min、489r/min、500r/min、750r/min、998r/min、1000r/min、1167r/min、
1250r/min, 1344r/min, 1500r/min, 1710r/min, 1983r/min, 2000r/min etc.；Enter one
Step is preferably 500-1500r/min.
As optimal technical scheme, preparation method of the present invention, the wherein temperature of heating described in step (5)
Degree for 50-90 DEG C, for example, 61.7 DEG C, 63.6 DEG C, 65 DEG C, 66.2 DEG C, 69 DEG C, 70 DEG C, 72.5 DEG C, 74
DEG C, 75 DEG C, 77.3 DEG C, 79 DEG C, 85 DEG C etc., preferably 60-80 DEG C, more preferably 65 DEG C-75, special
You Xuanwei 70 DEG C.
Preferably, described in step (5), the mode of heating is oil bath or water-bath, preferably oil bath；
Preferably, described in step (5) stirring time be 5-60min, for example, 8min, 15min, 20min,
26min, 34min, 46min, 55min etc., preferably 10-30min；More preferably 15-25min,
Particularly preferably 20min；
Preferably, the temperature continuing reacting by heating described in step (5) is 50-90 DEG C, for example, 55 DEG C, 61
DEG C, 65 DEG C, 68 DEG C, 72 DEG C, 76 DEG C, 79 DEG C, 84 DEG C, 88 DEG C etc., preferably 60-80 DEG C, further
Preferably 65 DEG C-75, particularly preferably 70 DEG C；
Preferably, the time continuing reacting by heating described in step (5) is 12-48h, for example, 15h, 28h,
23h, 26h, 33h, 39h, 42h, 45h etc., preferably 20-40h, more preferably 36h；
Preferably, remove the inorganic salt in germanium nanocluster aqueous solution described in step (6) and use dialyzer dialysis
Mode, preferably carry out with the dialyzer of MW500-2000, the dialyzer of further preferred MW500
Carry out.Dialysis is any technique commonly known means.The germanium cluster of the present invention only need to be by simple dialysis etc.
Method can be separated from reaction system, and in prior art, the preparation of a lot of noble metal clusters is reacted all
It is to carry out in organic facies, separates difficulty.
As optimal technical scheme, preparation method of the present invention, described method comprises the steps:
(1) under the conditions of Ultrasonic Radiation, germanium dioxide is dissolved in the sodium hydroxide that concentration is 2-10mg/ml molten
In liquid, being prepared as ge source solution, the ge source content dissolved in ge source solution is 2.6-26mg/ml, uses dilute hydrochloric acid
The pH value of ge source solution is regulated to 6-9；Wherein concentration of sodium hydroxide solution is preferably 5-8mg/ml；Especially
Being preferably 6mg/ml, the ge source content dissolved in ge source solution is preferably 5-20mg/ml, more preferably
10mg/ml, is preferably 6-7.5 after the pH value regulation of ge source solution；More preferably 7；
(2) joining in ultra-pure water by cysteine, stirring makes cysteine fully dissolve, and prepares half Guang ammonia
Aqueous acid, the concentration of the aqueous solution of cysteine is 0.05-1.5mmol/ml；The wherein water of cysteine
The concentration of solution is preferably 0.1-1mmol/ml；More preferably 1mmol/ml；
(3) solution of step (1) is joined in the aqueous solution of step (2)；
(4) sodium borohydride is added in step (3) gained solution so that the concentration of sodium borohydride is
3.2-64mg/ml, continue stirring；Wherein the concentration of sodium borohydride is preferably 10-48mg/ml, further preferably
For 32mg/ml；
(5) step (4) gained solution is placed in the oil bath of 50 DEG C-90 DEG C, stirs 5-60min, until reactant liquor
The substantial amounts of orange-yellow insoluble matter of middle appearance, continues reaction in the oil bath of 50 DEG C-90 DEG C, crocus insoluble matter is gradually
Disappear, after 12-48h, obtain germanium nanocluster solution；Wherein oil bath temperature is preferably 60-80 DEG C, the most excellent
Elect 65 DEG C-75 as, particularly preferably 70 DEG C；Mixing time is preferably 10-30min；More preferably
15-25min, particularly preferably 20min；The time continuing reaction is 12-48h, preferably 20-40h, enters
One step is preferably 36h；
The germanium nanocluster of dialyzer dialysis removal step (5) gained optionally carrying out (6) MW500-2000 is water-soluble
Inorganic salt in liquid, the germanium cluster water solution obtained, at a temperature of-50 DEG C～-60 DEG C, lyophilization preserves.Its
Middle dialyzer is preferably the dialyzer of MW500.
An object of the present invention also resides in the germanium of the monolayer protection providing method of the present invention to obtain
Nanocluster.Germanium cluster provided by the present invention is when using fluorescein sodium as reference material, and quantum yield is permissible
Reach more than 40%.
Dried germanium cluster is highly stable when preserving in atmospheric conditions, and after the several months, fluorescence there will not be bright
Aobvious weakens, and traditional fluorescent dye is then susceptible to degraded.
Even if germanium cluster does not the most show any cytotoxicity in milligram level, there is good bio-compatible
Property.
An object of the present invention also resides in the answering on imaging biological cells of the germanium nanocluster described in offer
With.Study through cell imaging, find that described germanium cluster has green fluorescence, it is possible to be advantageously applied to thin
Born of the same parents' fluorescence imaging, and according to the result of cell fluorescence imaging research, find that germanium cluster quantum dot is mainly distributed
Non-core position at cell.
As optimal technical scheme, the cell culture condition of described purposes described imaging biological cells therein
It is the CO of 37 DEG C and 5vol%2.When the germanium quantum point of the present invention is applied to bio-imaging, for cell
Kind does not has special requirement.
All expression technological parameters of using in the specification and in the claims, reaction condition etc. are in love in institute
The modification plus term " about " all it is appreciated that under condition.Therefore, unless indicated to the contrary, in description
The difference of the character that can obtain desired by the present invention with the numerical value gone out given in claims and become
Change.At bottom line, it is not used to be defined to the application of equivalent principle the scope of claim, each
Numerical value all should at least be solved by the common rounding method of use according to the value of the significant digits reported
Release.And, all scopes announced at this are all appreciated that the beginning and end value comprising scope, bag
Containing any and all little scopes being included in.Such as, certain scope " 1-10 " should be considered bag
Containing any and all little scope (being included) between minima 1 and maximum 10；The most all with more than or
Minima equal to 1 initiates, and all little scope terminated with the maximum less than or equal to 10, such as
5-10,3.3-6.7, or 1.5-8.8.In the present invention, the volume of all gases mentioned and liquid is at 20 DEG C
And the numerical value of a standard atmosphere pressure.The all lists of references mentioned in the present invention are all appreciated that
All include for reference.
The primary raw material material used in the present invention, ge source germanium dioxide, borane reducing agent sodium hydride and protection
Agent cysteine is common chemical substance, stable in properties, is prone to preserve, and does not substantially have biological poison
Property.The synthetic method that the present invention uses is without high temperature and the protection of noble gas, simple to operation, simultaneously
Reaction does not has intermediate link, and a step can complete, it is simple to large-scale industrial expands.The germanium group that the present invention obtains
Bunch there is the quantum yield of up to more than 40%, it is easy to separating from system, lyophilization can be protected for a long time
Deposit, the most also there is stable photoluminescent property and no cytotoxicity, it is possible to be advantageously applied to biological cell
Imaging, is the green fluorescent material of a kind of inanimate object toxicity.
Accompanying drawing explanation
Fig. 1 is emerald green fluorescence germanium cluster fluorescence picture under uviol lamp in embodiment 1；
Fig. 2 is the fluorescence excitation of germanium cluster in embodiment 1 and transmitting；
Fig. 3 is yellow fluorescence germanium cluster fluorescence picture under uviol lamp in comparative example 1；
Fig. 4 is fluorescence excitation and the emission spectrum of yellow germanium cluster in comparative example 1；
Fig. 5 is glimmering under different excitation wavelengths that fluorescence spectrophotometer records the germanium cluster that embodiment 1 obtains
Light spectrum；
Fig. 6 is the mass spectrum of the germanium cluster in the embodiment 1 that electrospray ionization mass spectrometry records；
Fig. 7 is that in embodiment 2, CCK-8 method detects apoptosis water in the case of variable concentrations cluster concentration
The flat cytoactive block diagram obtained；
Fig. 8 is that the germanium cluster obtained in embodiment 1 cell under the fluorescence microscope of imaging biological cells becomes
As design sketch.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that
The only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
Synthesizing water-solubility germanium cluster as follows:
(1) weigh 0.06g sodium hydroxide to be dissolved in 10ml water, ultrasonic dissolution, make sodium hydroxide solution；
(2) 0.26g germanium dioxide (GeO is weighed2, purchased from Sigma-Aldrich Shanghai trade Co., Ltd,
Production number is 483702) it is dissolved in the sodium hydroxide solution of step (1), ultrasonic dissolution, obtain ge source solution；
(3) under the conditions of Ultrasonic Radiation, ge source is dissolved in sodium hydroxide solution, is prepared as ge source molten
Liquid, between the pH value of the ge source solution of dilute hydrochloric acid regulating step (2) to 6-7；
(4) by 1.21g cysteine (purchased from Sigma-Aldrich Shanghai trade Co., Ltd, production number
30089-25G) joining in 9ml ultra-pure water, stirring makes cysteine fully dissolve, and prepares cysteine
Aqueous solution；The concentration of the aqueous solution of cysteine is 1.0mmol/ml；
(5) take in the aqueous solution that the ge source solution 1ml prepared joins cysteine, weigh 0.32g boron
Sodium hydride, then adds in aqueous cystein solution by sodium borohydride so that the concentration of sodium borohydride is
32mg/ml, continues stirring, then is placed in the oil bath of 70 DEG C, stirs 20min, until occurring big in reactant liquor
The orange-yellow insoluble matter of amount；Continuing reaction in the oil bath of 70 DEG C, crocus insoluble matter fades away, after 24h
Obtain the transparent germanium cluster solution with emerald green fluorescence of glassy yellow；
(6) with the dialyzer of Mw=500, step (5) gained reactant liquor is dialysed, remove germanium cluster
Inorganic salt in solution；
(8) according to the germanium cluster solution lyophilization at a temperature of-50 DEG C～-60 DEG C by removing inorganic salt.
According to document (Zheng, J., Petty, etc. JACS (J.Am.Chem.Soc.) 2003,125,
Method described in 7780-7781), utilizes fluorescence spectrophotometer to measure the present embodiment 1 and germanium that comparative example 1 obtains
The fluorescence spectrum of cluster, as shown in figures 1-4, Fig. 1 and Fig. 2 can be seen that presenting of germanium cluster is emerald green to result
The fluorescence of color, emission peak is at 504nm, Fig. 3 and Fig. 4 shows that the fluorescence obtained in comparative example 1 is Huang
Green, the emission peak of fluorescence is at 530nm, it is seen that the concentration between part and ge source is compared to the cluster of synthesis
Photoluminescent property have a certain impact.
Fig. 5 can be seen that fluorescence emission spectrum excitation wavelength does not exist obvious dependence, along with exciting
The change of wavelength, emission spectrum has almost no change.
Fig. 6 is the mass spectrum of the germanium cluster in the embodiment 1 that electrospray ionization mass spectrometry records, to cluster molecule
The scope of amount is characterized, it can be seen that within the molecular weight basic 4000 of cluster.
According to document (chemical communication (chemical communication) 2011 such as Wang J.Sun, 17,
Method described in 4941-443), utilizes fluorescein sodium as standard substance, measures the present embodiment 1
The fluorescence quantum yield of the cluster obtained is more than 40%, and the fluorescence quantum yield that embodiment 2 obtains is also 20%
Above.
Embodiment 2:
The present embodiment prepares germanium cluster according to method same as in Example 1, unique unlike: used half
The amount of cystine is 0.121g.
According to the identical characterizing method in embodiment 1, fluorescence spectrophotometer is utilized to record what this comparative example obtained
The fluorescence spectrum of germanium cluster is the most different from embodiment 1, and transmitting Dependent Red Shift, to 530nm, excites peak position blue shift
To 385nm, fluorescein sodium is utilized to record the fluorescence of the germanium cluster that the present embodiment obtains as fluorescence standard material
Quantum yield, more than 20%, illustrates the matched proportion density of cysteine and the ge source fluorescence to the cluster of synthesis
Matter has a certain impact.
Embodiment 3
(1) weigh 0.02g potassium hydroxide to be dissolved in 10ml water, ultrasonic dissolution, make sodium hydroxide solution；
(2) 0.026g germanium dioxide (GeO is weighed2, purchased from the limited public affairs of Sigma-Aldrich Shanghai trade
Department, production number is 483702) be dissolved in the sodium hydroxide solution of step (1), ultrasonic dissolution, obtain ge source molten
Liquid；
(3) under the conditions of Ultrasonic Radiation, ge source is dissolved in sodium hydroxide solution, is prepared as ge source molten
Liquid, with the pH value of the ge source solution of dilute hydrochloric acid regulating step (2) to 9；
(4) by 0.0605g cysteine (purchased from Sigma-Aldrich Shanghai trade Co., Ltd, product
Number 30089-25G) join in 9ml ultra-pure water, stirring makes cysteine fully dissolve, and prepares half Guang
Ammonia aqueous acid；The concentration of the aqueous solution of cysteine is 0.05mmol/ml；
(5) take in the aqueous solution that the ge source solution 1ml prepared joins cysteine, weigh 0.032g
Sodium borohydride, then adds in aqueous cystein solution by sodium borohydride so that the concentration of sodium borohydride is
3.2mg/ml, continues stirring, then is placed in the oil bath of 50 DEG C, stirs 50min, until occurring in reactant liquor
Substantial amounts of orange-yellow insoluble matter；Continuing reaction in the oil bath of 50 DEG C, crocus insoluble matter fades away, 48h
After obtain the transparent germanium cluster solution with emerald green fluorescence of glassy yellow；
(6) with the dialyzer of Mw=2000, step (5) gained reactant liquor is dialysed, remove germanium cluster
Inorganic salt in solution；
(8) according to the germanium cluster solution lyophilization at a temperature of-50 DEG C～-60 DEG C by removing inorganic salt.
Utilizing fluorescein sodium as standard substance, the fluorescent quantum measuring the cluster that the present embodiment obtains produces
Rate is more than 20%.
Embodiment 4
(1) weigh 0.1g sodium hydroxide to be dissolved in 10ml water, ultrasonic dissolution, make sodium hydroxide solution；
(2) 0.1g germanium dioxide (GeO is weighed2, purchased from Sigma-Aldrich Shanghai trade Co., Ltd,
Production number is 483702) it is dissolved in the sodium hydroxide solution of step (1), ultrasonic dissolution, obtain ge source solution；
(3) under the conditions of Ultrasonic Radiation, ge source is dissolved in sodium hydroxide solution, is prepared as ge source molten
Liquid, with the pH value of the ge source solution of dilute hydrochloric acid regulating step (2) to 7.5；
(4) by 1.8150g cysteine (purchased from Sigma-Aldrich Shanghai trade Co., Ltd, product
Number 30089-25G) join in 9ml ultra-pure water, stirring makes cysteine fully dissolve, and prepares half Guang
Ammonia aqueous acid；The concentration of the aqueous solution of cysteine is 1.5mmol/ml；
(5) take in the aqueous solution that the ge source solution 1ml prepared joins cysteine, weigh 0.64g boron
Sodium hydride, then adds in aqueous cystein solution by sodium borohydride so that the concentration of sodium borohydride is
64mg/ml, continues stirring, then is placed in the oil bath of 90 DEG C, stirs 60min, until occurring big in reactant liquor
The orange-yellow insoluble matter of amount；Continuing reaction in the oil bath of 90 DEG C, crocus insoluble matter fades away, after 12h
Obtain the transparent germanium cluster solution with emerald green fluorescence of glassy yellow；
(6) with the dialyzer of Mw=1000, step (5) gained reactant liquor is dialysed, remove germanium cluster
Inorganic salt in solution；
(8) according to the germanium cluster solution lyophilization at a temperature of-50 DEG C～-60 DEG C by removing inorganic salt.
Utilizing fluorescein sodium as standard substance, the fluorescent quantum measuring the cluster that the present embodiment obtains produces
Rate is more than 40%.
Comparative example 1
This comparative example prepares germanium cluster according to method same as in Example 1, unique unlike: in step
(4) in, cysteine is changed into the sodium ascorbate of equimolar concentration.
Observing response liquid after 12h, discovery solution is water white transparency, but does not has fluorescence under uviol lamp.
Comparative example 2
This comparative example prepares germanium cluster according to method same as in Example 1, unique unlike: in step
(3) in, the pH value of step (2) gained reactant liquor is regulated between 5-6.
Observing response liquid after 12h, finds have a large amount of white precipitate to produce in solution, and solution is under uviol lamp
Observation does not has fluorescence.From the selection of ge source solution ph seen from comparative example 1 and 2, the method for the present invention there is weight
Affect, whether directly affect the carrying out of reaction.
Comparative example 3
This comparative example prepares germanium cluster according to method same as in Example 1, unique unlike: in step
(3) by between ge source pH value of solution regulation to 10-11 in.
After step (5) carries out 12h, observe and find that reactant liquor becomes colorless transparent, but under uviol lamp
Observation does not has fluorescence.PH value during visible preparation ge source solution must select also to be had follow-up reaction to closing weight
The impact wanted.
Embodiment 5
The germanium cluster obtained in embodiment 1 is used for cytotoxicity experiment:
By lung carcinoma cell (A549 cell line, purchased from ATCC, numbering CCL-185) with every 35mm internal diameter
Culture dish 103Individual density is inoculated in the DMEM culture medium containing 2ml (purchased from Gibco, the trade mark
Sh30022.01B, and containing the hyclone of 10vol%) culture dish in, at the CO of 37 DEG C He 5vol%2
After cultivating 24h under concentration, sucking-off culture medium, add buffer, according to document (Qinghua Miao etc., life
Thing material (Biomaterials), 2010,31 (28): 7364-75) the CCK-8 method described in is deposited at germanium quantum point
Detect Level of Apoptosis in case.
Concrete operation step is as follows:
(1) in 64 orifice plates, the cell suspending liquid of 100 μ L is configured, by culture plate preculture in incubator
24h(37 DEG C, CO25vol%)；
(2) to culture plate add the germanium cluster of 10 μ L variable concentrations make in culture fluid germanic cluster dense
Degree is respectively 0.2 μ g/ml, 2 μ g/ml, 20 μ g/ml, 200 μ g/ml；
(3) culture plate is hatched in incubator 24h；
(4) in culture plate, every hole adds 10 μ L CCK solution；
(5) culture plate is hatched 1h(37 DEG C in incubator, CO25vol%)；
(6) absorbance at 450nm is measured by microplate reader.
Result is as shown in Figure 7, it can be seen that when the concentration of germanium quantum point be respectively 2 μ g/ml, 50 μ g/ml,
When 100 μ g/ml, 200 μ g/ml, 2000 μ g/ml, corresponding cytoactive is respectively 100.08 ± 3.71%,
100.33 ± 1.48%, 100.93 ± 8.21%, 101.61 ± 1.45%, 101.86 ± 5.32%, it is seen that the present invention
Even if the germanium quantum point of synthesis does not the most show any cytotoxicity under the high concentration of 2000 μ g/ml.
Embodiment 6
The germanium quantum point obtained in embodiment 1 is used for Cellular imaging assays:
By lung carcinoma cell (A549 cell line, purchased from ATCC, numbering CCL-185) with every 35mm internal diameter
Culture dish 103Individual density is inoculated in the DMEM culture medium containing 2ml (purchased from Gibco, the trade mark
Sh30022.01B), in culture dish and containing the hyclone of 10 volume %), at the CO of 37 DEG C He 5vol%2
Cultivating after 24h under concentration, sucking-off culture medium, by 2ml, dissolved with the culture medium of germanium cluster, (drug level is
2mg/ml) add in culture dish, by culture dish at the CO of 37 DEG C He 5vol%2Hatch 12h under concentration, inhale
Go out culture medium, (purchasing Propbs containing ten thousand/lysosome beta galactosidase staining reagent, producing afterwards
Product numbering GMS10121) phosphate buffer (purchased from Gibco, trade mark P1020-500) in cultivate five
Minute, wash 3 times (each 5ml) with phosphate buffer, and use fluorescence microscope imaging.
Imaging results is as shown in Figure 8, it can be seen that after germanium cluster enters cell, cell non-core position presents relatively
The fluorescence of amount, i.e. the germanium cluster of the present invention has good cell imaging ability, can be very after entering cell
Play well the effect of cell imaging, by the positioning action of lysosome stain, it can be seen that fluorescence germanium cluster
The mode entering cell is mainly lysosome mediation.
It should be noted that and understand, without departing from the spirit of the present invention required by appended claims and model
In the case of enclosing, it is possible to the present invention of foregoing detailed description is made various modifications and improvements.It is therefore desirable to
The scope of the technical scheme of protection is not limited by given any specific exemplary teachings.
Applicant states, the present invention illustrates the detailed process flow of the present invention by above-described embodiment, but this
Invention is not limited to above-mentioned detailed process flow, does not i.e. mean that the present invention has to rely on above-mentioned detailed process
Flow process could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, right
The equivalence of each raw material of product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within
Within the scope of protection scope of the present invention and disclosure.
Claims (62)
1. a preparation method for germanium nanocluster, comprises the steps:
(1) ge source is dissolved in aqueous slkali prepared ge source solution；The concentration of described aqueous slkali is 2-10mg/ml；
With acid solution, the pH value of ge source solution is regulated to 6-9；
(2) protective agent is dissolved in water and prepares protectant aqueous solution；Described protectant concentration is
0.05-1.5mmol/ml；
(3) step (1) gained ge source solution is joined in step (2) protectant aqueous solution；
(4) reducing agent is joined in step (3) gained solution；The addition of described reducing agent is
3.2-64mg/ml；
(5) solution of heating steps (4), obtains germanium nanocluster.
Method the most according to claim 1, it is characterised in that the ge source described in step (1) is dioxy
Change germanium or/and germanium salt.
Method the most according to claim 1, it is characterised in that the ge source described in step (1) is titanium dioxide
Germanium is or/and sodium metagermanate.
Method the most according to claim 1, it is characterised in that the ge source described in step (1) is titanium dioxide
Germanium.
Method the most according to claim 1, it is characterised in that step (1) described aqueous slkali is containing alkali gold
The solution of the hydroxide belonged to.
Method the most according to claim 1, it is characterised in that step (1) described aqueous slkali is hydroxide
Sodium is or/and potassium hydroxide.
Method the most according to claim 1, it is characterised in that step (2) described protective agent is with mercapto
The little molecule of base.
Method the most according to claim 1, it is characterised in that step (2) described protective agent is half Guang ammonia
Acid.
Method the most according to claim 1, it is characterised in that step (4) described reducing agent is for having also
The inorganic salts of proper energy power.
Method the most according to claim 1, it is characterised in that step (4) described reducing agent is boron hydrogen
Change sodium.
11. methods according to claim 1, it is characterised in that the temperature of step (5) described heating is
50-90℃。
12. methods according to claim 1, it is characterised in that the temperature of step (5) described heating is
60-80℃。
13. methods according to claim 1, it is characterised in that the temperature of step (5) described heating is
65-75℃。
14. methods according to claim 1, it is characterised in that the temperature of step (5) described heating is
70℃。
15. methods according to claim 1, it is characterised in that described method comprises the steps:
(1) under the conditions of Ultrasonic Radiation, ge source is dissolved in aqueous slkali, is prepared as ge source solution, molten with acid
The pH value of ge source solution is regulated to 6-9 by liquid；The concentration of described aqueous slkali is 2-10mg/ml；
(2) protective agent is joined in ultra-pure water, stirring, dissolve, obtain protectant aqueous solution；Described guarantor
The concentration protecting agent is 0.05-1.5mmol/ml；
(3) the ge source solution of step (1) is joined in step (2) protectant aqueous solution；
(4) reducing agent is added in step (3) gained solution, stirring, dissolve；The addition of described reducing agent
For 3.2-64mg/ml；
(5) by lower for the heating of step (4) gained solution stirring, continue reacting by heating and obtain germanium nanocluster.
16. methods according to claim 15, it is characterised in that described method also includes:
Carry out the inorganic salt in the germanium nanocluster aqueous solution of (6) removal step (5) gained ,-50 DEG C～-60 DEG C
At a temperature of lyophilization preserve.
17. methods according to claim 15, it is characterised in that ultrasonic amplitude described in step (1)
Penetrate employing ultrasonic cleaning instrument.
18. methods according to claim 15, it is characterised in that described in step (1), aqueous slkali is hydrogen
Sodium hydroxide solution or potassium hydroxide solution.
19. methods according to claim 15, it is characterised in that described in step (1), aqueous slkali is dense
Degree is 5-8mg/ml.
20. methods according to claim 15, it is characterised in that described in step (1), aqueous slkali is dense
Degree is 6mg/ml.
21. methods according to claim 15, it is characterised in that described in step (1), ge source is dioxy
Change germanium or/and germanium salt.
22. methods according to claim 15, it is characterised in that described in step (1), ge source is dioxy
Change germanium or/and sodium metagermanate.
23. methods according to claim 15, it is characterised in that described in step (1), ge source is dioxy
Change germanium.
24. methods according to claim 15, it is characterised in that described in step (1) in ge source solution
The content of ge source is 2.6-26mg/ml.
25. methods according to claim 15, it is characterised in that described in step (1) in ge source solution
The content of ge source is 5-20mg/ml.
26. methods according to claim 15, it is characterised in that described in step (1) in ge source solution
The content of ge source is 10mg/ml.
27. methods according to claim 15, it is characterised in that described in step (1), acid solution is
Dilute hydrochloric acid.
28. methods according to claim 15, it is characterised in that ge source solution described in step (1)
It is 6-7.5 after pH value regulation.
29. methods according to claim 15, it is characterised in that described in step (2), protective agent is
Little molecule with sulfydryl.
30. methods according to claim 15, it is characterised in that described in step (2), protective agent is
Cysteine.
31. methods according to claim 15, it is characterised in that protectant described in step (2)
Concentration is 0.1-1mmol/ml.
32. methods according to claim 15, it is characterised in that protectant described in step (2)
Concentration is 1mmol/ml.
33. methods according to claim 15, it is characterised in that the side of stirring described in step (2)
Formula is magnetic agitation.
34. methods according to claim 15, it is characterised in that described in step (4), reducing agent is boron
Sodium hydride.
35. methods according to claim 15, it is characterised in that reducing agent described in step (4) adds
Amount is 10-48mg/ml.
36. methods according to claim 15, it is characterised in that reducing agent described in step (4) adds
Amount is 32mg/ml.
37. methods according to claim 15, it is characterised in that the mode of stirring described in step (4)
For magnetic agitation.
38. methods according to claim 15, it is characterised in that the temperature of heating described in step (5)
For 50-90 DEG C.
39. methods according to claim 15, it is characterised in that the temperature of heating described in step (5)
For 60-80 DEG C.
40. methods according to claim 15, it is characterised in that the temperature of heating described in step (5)
For 65-75 DEG C.
41. methods according to claim 15, it is characterised in that the temperature of heating described in step (5)
It it is 70 DEG C.
42. methods according to claim 15, it is characterised in that the mode of heating described in step (5)
For oil bath or water-bath.
43. methods according to claim 15, it is characterised in that the mode of heating described in step (5)
For oil bath.
44. methods according to claim 15, it is characterised in that the time of stirring described in step (5)
For 5-60min.
45. methods according to claim 15, it is characterised in that the time of stirring described in step (5)
For 10-30min.
46. methods according to claim 15, it is characterised in that the time of stirring described in step (5)
For 15-25min.
47. methods according to claim 15, it is characterised in that the time of stirring described in step (5)
For 20min.
48. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The temperature answered is 50-90 DEG C.
49. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The temperature answered is 60-80 DEG C.
50. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The temperature answered is 65-75 DEG C.
51. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The temperature answered is 70 DEG C.
52. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The time answered is 12-48h.
53. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The time answered is 20-40h.
54. methods according to claim 15, it is characterised in that continue heating described in step (5) anti-
The time answered is 36h.
55. methods according to claim 16, it is characterised in that remove germanium described in step (6) and receive
Inorganic salt in rice cluster water solution uses the mode of dialyzer dialysis.
56. methods according to claim 16, it is characterised in that remove germanium described in step (6) and receive
Inorganic salt in rice cluster water solution uses the dialyzer of MW500-2000 to carry out.
57. methods according to claim 16, it is characterised in that remove germanium described in step (6) and receive
Inorganic salt in rice cluster water solution uses the dialyzer of MW500 to carry out.
58. according to the method one of claim 1-15 Suo Shu, it is characterised in that described method includes as follows
Step:
(1) under the conditions of Ultrasonic Radiation, germanium dioxide is dissolved in the sodium hydroxide that concentration is 2-10mg/ml molten
In liquid, being prepared as ge source solution, the ge source content dissolved in ge source solution is 2.6-26mg/ml, uses dilute salt
The pH value of ge source solution is regulated to 6-9 by acid；
(2) joining in ultra-pure water by cysteine, stirring makes cysteine fully dissolve, and prepares half Guang ammonia
Aqueous acid, the concentration of the aqueous solution of cysteine is 0.05-1.5mmol/ml；
(3) solution of step (1) is joined in the aqueous solution of step (2)；
(4) sodium borohydride is added in step (3) gained solution so that the concentration of sodium borohydride is
3.2-64mg/ml, continue stirring；
(5) step (4) gained solution is placed in the oil bath of 50 DEG C-90 DEG C, stirs 5-60min, until reaction
Liquid occurs substantial amounts of orange-yellow insoluble matter, in the oil bath of 50 DEG C-90 DEG C continue reaction, crocus insoluble matter by
Fade mistake, obtains germanium nanocluster solution after 12-48h.
59. methods according to claim 58, it is characterised in that described method also includes:
Carry out in the germanium nanocluster aqueous solution of dialyzer dialysis removal step (5) gained of (6) MW500-2000
Inorganic salt, the germanium cluster water solution obtained, at a temperature of-50 DEG C～-60 DEG C lyophilization preserve.
The germanium nanoclusters of the 60. monolayer protections obtained according to the method one of claim 1-59 Suo Shu
Bunch.
The purposes of 61. germanium nanoclusters according to claim 60, it is characterised in that described germanium
Nanocluster is used for imaging biological cells.
The purposes of 62. germanium nanoclusters according to claim 61, it is characterised in that described biology
The cell culture condition of cell imaging is the CO of 37 DEG C and 5vol%2。
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