CN105238394B - 3 mercaptopropionic acid human serum fluorescent au nanocluster materials and preparation method thereof - Google Patents
3 mercaptopropionic acid human serum fluorescent au nanocluster materials and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of 3 mercaptopropionic acid human serum fluorescent au nanocluster material and preparation method thereof, using gold chloride, 3 mercaptopropionic acids, human serum as raw material one-step synthesis water-soluble gold nano cluster fluorescent material.The present invention is to be well mixed the human blood clear solution of dilution with chlorauric acid solution, then sodium hydroxide solution and 3 mercaptopropionic acids are added, shaking is mixed, reaction certain time obtains 3 mercaptopropionic acid human serum gold nano clusters, fluorescent au nanocluster material powder is can obtain after the freeze-drying of the fluorescent au nanocluster material aqueous solution, has the advantages that to prepare quick, simple and environmentally-friendly.3 synthesized mercaptopropionic acid human serum albumins gold nano clusters show strong orange-yellow fluorescence（The nm of maximum emission wavelength 575）, Stokes shift is big（225 nm）, good water solubility has the advantages that higher stability.
Description
Technical field
The present invention relates to 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material and preparation method thereof, belong to a nanometer skill
Art field.
Background technology
Cluster chemistry is one of field of forefront in the subjects such as present material science, organometallic chemistry.So-called group
Cluster, exactly a class have the core of 3 or more than 3 atom Direct Bondings, the original of periphery one layer of organic molecule of parcel
Submanifold compound, be otherwise known as monolayer protected cluster.In recent years, fluorescence metal nanocluster, especially gold nano cluster（gold
nanoclusters, AuNCs）, received much concern as a kind of new fluorescent nano material.Because it is closely sized in electronics
Fermi's wavelength, continuous energy state property is split into discrete energy state, and the size of similar molecule occurs and rely on effect.With small point
Sub- fluorescent dye is compared with fluorescin, and gold nano cluster material has that photophysical property is good, specific surface area as fluorescence probe
Greatly, the advantages of surface is easy to modification and adjustable photoluminescent property.Therefore in compound test, bio-sensing and imaging, photoelectron
The field such as and nanosecond medical science has a wide range of applications.
The technology of preparing of fluorescent au nanocluster material mainly includes chemical reduction method, reverse microemulsion process, templated synthesis
Method monolayer protection technique and part etching method etc..Wherein monolayer protection technique is a kind of cluster synthesis of Simple temperature sum
Method, by the use of the small molecule containing certain functional group as protection group, protective layer is formed on cluster surface, so that stable gold nano group
Cluster, makes it be difficult to reunite.In recent decades, researchers both domestic and external propose a variety of different methods and prepare high fluorescent quantum
The adjustable gold nano cluster of yield, good water solubility, glow color.
The present invention is using gold chloride, 3- mercaptopropionic acids, human serum as raw material one-step synthesis water-soluble gold nano cluster phosphor
Material.Human serum is as stabilizer, and 3- mercaptopropionic acids are the formation that reducing agent and dressing agent control gold nano cluster.Prepared 3-
Mercaptopropionic acid-human serum-gold nano cluster has strong orange-yellow fluorescence, and Stokes shift is big, good water solubility.
The content of the invention
It is an object of the invention to provide a kind of 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material and its with 3- mercaptos
Base propionic acid is reducing agent and dressing agent, using human serum as the method for stabilizer one-step synthesis fluorescent au nanocluster material.
To achieve these goals, the present invention uses following technical scheme：3- mercaptopropionic acids-human blood of the present invention
Clearly-fluorescent au nanocluster material and preparation method thereof, it is characterized in that it is made up of following steps：By the human blood clear solution of dilution
It is well mixed with chlorauric acid solution, then adds sodium hydroxide solution and 3- mercaptopropionic acids, shaking is mixed, the timing of reaction one
Between obtain 3- mercaptopropionic acids-human serum-gold nano cluster, can obtain gold after the freeze-drying of the fluorescent au nanocluster material aqueous solution
Nanocluster fluorescent material powder.
Described 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material and preparation method thereof, it is characterized in that with human blood
Clearly as stabilizer, 3- mercaptopropionic acids are the formation that reducing agent and dressing agent control gold nano cluster.
The chlorauric acid solution, human blood clear solution, the volume ratio of sodium hydroxide solution and 3- mercaptopropionic acids are 10：
10：1：2.
The concentration of chlorauric acid solution used can be 1 ~ 100 mmol/L, and optimal concentration is 10 mmol/L, people used
Serum solution is preferably to be obtained after deionized water dilutes three times, and the concentration of sodium hydroxide solution can be 0.1 ~ 0.5 mol/L,
The concentration of optimal concentration 0.25 mol/L, 3- mercaptopropionic acid can be 0.1 ~ 3 mol/L, and optimal concentration is 2 mol/L.
Above-mentioned chlorauric acid solution, human serum, sodium hydroxide solution and 3- mercaptopropionic acids are placed in 4 DEG C of reactions after mixing
0.1 ~ 2 hour, most preferably 1 h.
The obtained gold nano cluster material aqueous solution is produced strong orange-yellow glimmering under ultra violet lamp to be colourless
Light, maximum excitation wavelength and launch wavelength are respectively 350 nm and 575 nm.
The preparation method of the optimal fluorescent au nanocluster material of the present invention is as follows：
All glasswares used in procedure below soak by chloroazotic acid, and use distilled water thoroughly cleaning, dry.Gold
Preparing for nanocluster fluorescent material is as follows：2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）With 2.5
ML concentration is well mixed for 10 mmol/L chlorauric acid solution, adds the NaOH that 0.25 mL concentration is 0.25 mol/L
Solution and the 3- mercaptopropionic acids that 0.5 mL concentration is 2 mol/L, shaking are mixed, and react 1 h at 4 DEG C, reaction solution is by pale yellow
Color becomes colorless, and obtains 3- mercaptopropionic acids-human serum-gold nano cluster, uviol lamp（365 nm）Have strong orange-yellow under irradiation
Fluorescence.
3- mercaptopropionic acids-human serum-gold nano cluster made from the above-mentioned preparation method of the present invention, it is characterized in that being soluble in
Water, the aqueous solution is colourless, and strong orange-yellow fluorescence, maximum excitation wavelength and launch wavelength difference are produced under ultra violet lamp
For 350 nm and 575 nm.
The gold nano cluster average grain diameter is 2.8 nm.
Described 3- mercaptopropionic acids-human serum-gold nano cluster, it is characterized in that the aqueous solution is placed under 4 DEG C of dark places
Occur without precipitum within 2 months, fluorescence intensity and maximum emission peak position keep constant.
Described 3- mercaptopropionic acids-human serum-gold nano cluster, it is characterized in that using gold chloride as Jin Yuan, 3- mercaptopropionic acids
For reducing agent and dressing agent, human serum is prepared for stabilizer.
Advantages of the present invention：
（1）The present invention is using 3- mercaptopropionic acids as reducing agent and dressing agent, the one-step synthesis water under conditions of human serum presence
Dissolubility fluorescent au nanocluster material, has the advantages that to prepare quick, simple and environmentally-friendly.
（2）Gold nano cluster prepared by the present invention has strong orange-yellow fluorescence（Maximum emission wavelength is 575
nm）, larger Stokes shift（225 nm）The features such as.
Brief description of the drawings
Fig. 1 is gold nano cluster fluorescent nano material in visible ray（A）Under uviol lamp（B）Outside drawing.
Fig. 2 is the UV-visible absorption spectrum of gold nano cluster fluorescent nano material.
Fig. 3 is the excitation and emission spectra figure of gold nano cluster fluorescent nano material.
Fig. 4 is the Energy Dispersive X energy spectrum diagram of gold nano cluster fluorescent nano material.
Fig. 5 is the transmission electron microscope picture of gold nano cluster fluorescent nano material.
Fig. 6 is the x-ray photoelectron energy spectrum diagram of gold nano cluster fluorescent nano material.
Embodiment
Example 1：
2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）It is 10 mmol/L's with 2.5 mL concentration
Chlorauric acid solution is well mixed, and then adds sodium hydroxide solution and 0.5 mL concentration that 0.25 mL concentration is 0.25 mol/L
For 2 mol/L 3- mercaptopropionic acids, shaking is mixed, and is reacted 1 h at 4 DEG C, is obtained human serum -3- mercaptopropionic acids-gold nano
Cluster.It is colourless transparent liquid under resulting gold nano cluster solution visible ray（See Figure 1A）, produce under ultra violet lamp strong
Strong orange-yellow fluorescence（See Figure 1B）.
Example 2：
2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）It is 10 mmol/L's with 2.5 mL concentration
Chlorauric acid solution is well mixed, and then adds sodium hydroxide solution and 0.5 mL concentration that 0.25 mL concentration is 0.25 mol/L
For 2 mol/L 3- mercaptopropionic acids, shaking is mixed, and is reacted 1 h at 4 DEG C, is obtained human serum -3- mercaptopropionic acids-gold nano
Cluster.Resulting gold nano cluster solution carries out ultraviolet-visible spectrum scanning, obtains it at 520 nm wavelength without Jenner's grain of rice
Subcharacter absworption peak（See Fig. 2）.
Example 3：
2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）It is 10 mmol/L's with 2.5 mL concentration
Chlorauric acid solution is well mixed, and then adds sodium hydroxide solution and 0.5 mL concentration that 0.25 mL concentration is 0.25 mol/L
For 2 mol/L 3- mercaptopropionic acids, shaking is mixed, and is reacted 1 h at 4 DEG C, is obtained human serum -3- mercaptopropionic acids-gold nano
Cluster.Resulting gold nano cluster solution carries out fluorescence spectrum scanning, obtains its maximum excitation wavelength and launch wavelength is respectively
350 nm and 575 nm（See Fig. 3）.
Example 4：
2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）It is 10 mmol/L's with 2.5 mL concentration
Chlorauric acid solution is well mixed, and then adds sodium hydroxide solution and 0.5 mL concentration that 0.25 mL concentration is 0.25 mol/L
For 2 mol/L 3- mercaptopropionic acids, shaking is mixed, and is reacted 1 h at 4 DEG C, is obtained human serum -3- mercaptopropionic acids-gold nano
Cluster.Resulting gold nano cluster solution drop coating is on copper mesh.Energy Dispersive X energy spectrum analysis（See Fig. 4）Show product
Contain gold element.
Example 5：
2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）It is 10 mmol/L's with 2.5 mL concentration
Chlorauric acid solution is well mixed, and then adds sodium hydroxide solution and 0.5 mL concentration that 0.25 mL concentration is 0.25 mol/L
For 2 mol/L 3- mercaptopropionic acids, shaking is mixed, and is reacted 1 h at 4 DEG C, is obtained human serum -3- mercaptopropionic acids-gold nano
Cluster.Resulting gold nano cluster solution carries out the measure of transmission electron microscope, and the average grain diameter for measuring gold nano cluster is 2.8
nm （See Fig. 5）.
Example 6：
2.5 mL dilute the human serum of three times with deionized water（33.3%, v/v）It is 10 mmol/L's with 2.5 mL concentration
Chlorauric acid solution is well mixed, and then adds sodium hydroxide solution and 0.5 mL concentration that 0.25 mL concentration is 0.25 mol/L
For 2 mol/L 3- mercaptopropionic acids, shaking is mixed, and is reacted 1 h at 4 DEG C, is obtained human serum -3- mercaptopropionic acids-gold nano
Cluster.Powder is obtained after resulting gold nano cluster solution freeze-drying, takes gained powder to carry out x-ray photoelectron power spectrum survey
It is fixed, the 4f of XPS Au (4f) display gold7/2Peak and 4f5/2Peak is located at 84.8 eV and 88.5 eV respectively, shows in gold nano cluster
The valence state of gold is coexisted with 0 valency and+1 valency mode（See Fig. 6）.
Claims (5)
1. a kind of preparation method of 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material, it is characterized in that it is by following steps
It is made：The human blood clear solution of dilution is well mixed with chlorauric acid solution, sodium hydroxide solution and 3- mercaptopropionic acids is then added
Solution, shaking is mixed, and reaction certain time obtains 3- mercaptopropionic acids-human serum-gold nano cluster, fluorescent au nanocluster material
Fluorescent au nanocluster material powder is can obtain after aqueous solution freeze-drying.
2. the preparation method of 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material according to claim 1, it is special
Levy is that the volume ratio of chlorauric acid solution, human blood clear solution, sodium hydroxide solution and 3- mercaptopropionic acids is 10：10：1：2.
3. the preparation method of 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material according to claim 1 or 2, its
The concentration for being characterized in chlorauric acid solution used is 10 mmol/L, human blood clear solution used for deionized water dilution three times it
After obtain, the concentration of concentration 0.25 mol/L, the 3- mercaptopropionic acid of sodium hydroxide solution is 2 mol/L.
4. the preparation method of 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material according to claim 1 or 2, its
It is characterized in that 4 DEG C of 1 h of reaction are placed in after chlorauric acid solution, human serum, sodium hydroxide solution and 3- mercaptopropionic acids are mixed.
5. the preparation method of 3- mercaptopropionic acids-human serum-fluorescent au nanocluster material according to claim 1 or 2, its
It is characterized in that 2.5 mL are mixed using the human serum and 2.5 mL concentration of deionized water dilution three times as 10 mmol/L chlorauric acid solution
Close uniform, add the sodium hydroxide solution that 0.25 mL concentration is 0.25 mol/L and the 3- sulfydryls that 0.5 mL concentration is 2 mol/L
Propionic acid solution, shaking is mixed, and is reacted at 4 DEG C, and reaction solution is become colorless by light yellow, obtains 3- mercaptopropionic acids-human serum-Jenner
Rice cluster, produces strong orange-yellow fluorescence, maximum excitation wavelength and launch wavelength are respectively under 365 nm ultra violet lamps
350 nm and 575 nm.
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