CN105238394A - 3-mercaptopropionic acid-human serum-gold nanometer clusters fluorescent material and preparation method thereof - Google Patents
3-mercaptopropionic acid-human serum-gold nanometer clusters fluorescent material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a 3-mercaptopropionic acid-human serum-gold nanometer clusters fluorescent material and a preparation method thereof, wherein chloroauric acid, 3-mercaptopropionic acid and human serum are adopted as raw materials to synthesize the water-soluble gold nanometer clusters fluorescent material in one step. According to the present invention, the diluted human serum solution and the chloroauric acid solution are uniformly mixed, the sodium hydroxide solution and the 3-mercaptopropionic acid solution are added, vibration shake is performed to uniformly mix, the reaction is performed for a certain time to obtain 3-mercaptopropionic acid-human serum-gold nanometer cluster, and the gold nanometer cluster fluorescent material is subjected to freeze-drying so as to obtain the gold nanometer cluster fluorescent material powder, wherein the gold nanometer cluster fluorescent material powder has advantages of rapid and simple preparation, environmental protection and the like. According to the present invention, the synthesized 3-mercaptopropionic acid-human serum albumin-gold nanometer cluster show strong orange fluorescence (the maximum emission wavelength of 575 nm), has advantages of high Stokes shift (225 nm), good water-solubility, high stability, and the like.
Description
Technical field
The present invention relates to 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material and preparation method thereof, belong to field of nanometer technology.
Background technology
Cluster chemistry is one of field of forefront in the subjects such as present material science, organometallic chemistry.So-called cluster, a class has the core of more than 3 or 3 atom Direct Bonding exactly, and the clusters of peripheral parcel one deck organic molecule, be otherwise known as monolayer protected cluster.In recent years, fluorescence metal nanocluster, especially gold nano cluster (goldnanoclusters, AuNCs), receive much concern as a kind of novel fluorescent nano material.Because its size is close to Fermi's wavelength of electronics, continuous print energy state character is split into discrete energy state, and occurs the Size dependence effect of similar molecule.Compare with fluorescin with small molecule fluorescent dyestuff, gold nano cluster material is used as that fluorescent probe has that photophysical property is good, specific surface area is large, surface is easy to modify and the advantage such as photoluminescent property is adjustable.Therefore have a wide range of applications in fields such as compound test, bio-sensing and imaging, photoelectronics and nanosecond medical sciences.
The technology of preparing of fluorescent au nanocluster material mainly comprises chemical reduction method, reverse microemulsion process, template synthesis method unimolecular layer resist technology and part etching method etc.Wherein unimolecular layer resist technology be a kind of Simple temperature and cluster synthetic method, utilize containing the small molecules of certain functional group as protecting group, form protective layer on cluster surface, thus stablize gold nano cluster, make it not easily reunite.In recent decades, investigators both domestic and external propose multiple diverse ways and prepare high-fluorescence quantum yield, good water solubility, gold nano cluster that glow color is adjustable.
The present invention with hydrochloro-auric acid, 3-thiohydracrylic acid, human serum for raw material one-step synthesis water-soluble gold nano cluster fluorescent material.Human serum is as stablizer, and 3-thiohydracrylic acid is the formation that reductive agent and modifier control gold nano cluster.Prepared 3-thiohydracrylic acid-human serum-gold nano cluster has strong orange-yellow fluorescence, and Stokes shift is large, good water solubility.
Summary of the invention
The object of this invention is to provide a kind of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material and with 3-thiohydracrylic acid for reductive agent and modifier, take human serum as the method for stablizer one-step synthesis fluorescent au nanocluster material.
To achieve these goals, the present invention by the following technical solutions: of the present invention
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster materialit is characterized in that it is made up of following steps: mixed with chlorauric acid solution by the human serum solution of dilution, then sodium hydroxide solution and 3-mercaptopropionic acid is added, jolting mixes, reaction certain hour obtains 3-thiohydracrylic acid-human serum-gold nano cluster, can obtain fluorescent au nanocluster material powder after the lyophilize of the fluorescent au nanocluster material aqueous solution.
Described
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material, it is characterized in that using human serum as stablizer, 3-thiohydracrylic acid is the formation that reductive agent and modifier control gold nano cluster.
The volume ratio of described chlorauric acid solution, human serum solution, sodium hydroxide solution and 3-mercaptopropionic acid is 10:10:1:2.
The concentration of chlorauric acid solution used can be 1 ~ 100mmol/L, optimal concentration is 10mmol/L, human serum solution used is preferably after deionized water dilutes three times and obtains, the concentration of sodium hydroxide solution can be 0.1 ~ 0.5mol/L, optimal concentration 0.25mol/L, the concentration of 3-mercaptopropionic acid can be 0.1 ~ 3mol/L, and optimal concentration is 2mol/L.
The mixing of above-mentioned chlorauric acid solution, human serum, sodium hydroxide solution and 3-mercaptopropionic acid is placed on 4 DEG C of reactions 0.1 ~ 2 hour, most preferably 1h.
Obtained gold nano cluster material water solution is colourless, and under ultra violet lamp, produce strong orange-yellow fluorescence, maximum excitation wavelength and emission wavelength are respectively 350nm and 575nm.
The preparation method of the fluorescent au nanocluster material of the best of the present invention is as follows:
The all glasswares used in following process all soak through chloroazotic acid, and thoroughly clean with distilled water, dry.Being prepared as follows of fluorescent au nanocluster material: 2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, add the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L, jolting mixes, 1h is reacted at 4 DEG C, reaction solution is become colorless by light yellow, obtain 3-thiohydracrylic acid-human serum-gold nano cluster, ultraviolet lamp (365nm) has strong orange-yellow fluorescence under irradiating.
The above-mentioned preparation method of the present invention obtains
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that soluble in water, the aqueous solution is colourless, and under ultra violet lamp, produce strong orange-yellow fluorescence, maximum excitation wavelength and emission wavelength are respectively 350nm and 575nm.
Described gold nano cluster median size is 2.8nm.
Described
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that the described aqueous solution is placed under 4 DEG C of dark places to occur without sediment for 2 months, fluorescence intensity and emission maximum peak position remain unchanged.
Described
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that taking hydrochloro-auric acid as Jin Yuan, 3-thiohydracrylic acid is reductive agent and modifier, and human serum is stablizer preparation.
advantage of the present invention:
(1) the present invention is with 3-thiohydracrylic acid for reductive agent and modifier, in next step synthesizing water-solubility fluorescent au nanocluster material of human serum existent condition, has and prepares advantage that is quick, simple, environmental protection.
(2) gold nano cluster prepared by the present invention has strong orange-yellow fluorescence (maximum emission wavelength is 575nm), the features such as larger Stokes shift (225nm).
Accompanying drawing explanation
Fig. 1 is gold nano cluster fluorescent nano material outside drawing of (B) under visible ray (A) and ultraviolet lamp.
Fig. 2 is the uv-visible absorption spectra figure 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 spectrogram 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 spectrogram of gold nano cluster fluorescent nano material.
Embodiment
example 1:
2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, then the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L is added, jolting mixes, react 1h at 4 DEG C, obtain human serum-3-thiohydracrylic acid-gold nano cluster.Be colourless transparent liquid (see Figure 1A) under the gold nano cluster solution visible ray obtained, under ultra violet lamp, produce strong orange-yellow fluorescence (see Figure 1B).
example 2:
2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, then the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L is added, jolting mixes, react 1h at 4 DEG C, obtain human serum-3-thiohydracrylic acid-gold nano cluster.The gold nano cluster solution obtained carries out ultraviolet-visible spectrum scanning, obtains it at 520nm wavelength place without golden nanometer particle charateristic avsorption band (see figure 2).
example 3:
2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, then the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L is added, jolting mixes, react 1h at 4 DEG C, obtain human serum-3-thiohydracrylic acid-gold nano cluster.The gold nano cluster solution obtained carries out fluorescence spectrum scanning, obtains its maximum excitation wavelength and emission wavelength and is respectively 350nm and 575nm(and sees Fig. 3).
example 4:
2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, then the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L is added, jolting mixes, react 1h at 4 DEG C, obtain human serum-3-thiohydracrylic acid-gold nano cluster.The gold nano cluster solution obtained drips and is coated on copper mesh.Energy Dispersive X energy spectrum analysis (see figure 4) shows that product contains gold element.
example 5:
2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, then the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L is added, jolting mixes, react 1h at 4 DEG C, obtain human serum-3-thiohydracrylic acid-gold nano cluster.The gold nano cluster solution obtained carries out the mensuration of transmission electron microscope, and the median size recording gold nano cluster is that 2.8nm(is shown in Fig. 5).
example 6:
2.5mL dilutes the human serum (33.3% of three times with deionized water, v/v) be that the chlorauric acid solution of 10mmol/L mixes with 2.5mL concentration, then the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L is added, jolting mixes, react 1h at 4 DEG C, obtain human serum-3-thiohydracrylic acid-gold nano cluster.Obtain powder after the gold nano cluster solution lyophilize obtained, get gained powder and carry out x-ray photoelectron power spectrum mensuration, the 4f of XPSAu (4f) display gold
7/2peak and 4f
5/2peak lays respectively at 84.8eV and 88.5eV, to show in gold nano cluster that the valence state of gold to coexist (see figure 6) with 0 valency and+1 valency mode.
Claims (10)
1. one kind
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster materialit is characterized in that it is made up of following steps: mixed with chlorauric acid solution by the human serum solution of dilution, then sodium hydroxide solution and 3-mercaptopropionic acid is added, jolting mixes, reaction certain hour obtains 3-thiohydracrylic acid-human serum-gold nano cluster, can obtain fluorescent au nanocluster material powder after the lyophilize of the fluorescent au nanocluster material aqueous solution.
2. according to claim 1
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material, it is characterized in that using human serum as stablizer, 3-thiohydracrylic acid is the formation that reductive agent and modifier control gold nano cluster.
3. according to claim 1
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material, it is characterized in that the volume ratio of chlorauric acid solution, human serum solution, sodium hydroxide solution and 3-mercaptopropionic acid is 10:10:1:2.
4. according to claim 1 or 3
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material, it is characterized in that the concentration of chlorauric acid solution used is 10mmol/L, human serum solution used is obtain after deionized water dilutes three times, and the concentration of the concentration 0.25mol/L of sodium hydroxide solution, 3-mercaptopropionic acid is 2mol/L.
5. according to claim 1 or 3
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster material, it is characterized in that the mixing of chlorauric acid solution, human serum, sodium hydroxide solution and 3-mercaptopropionic acid is placed on 4 DEG C of reaction 1h.
6. according to claim 1 or 3
the preparation method of 3-thiohydracrylic acid-human serum-fluorescent au nanocluster materialit is characterized in that the chlorauric acid solution that 2.5mL dilutes three times human serum with deionized water and 2.5mL concentration are 10mmol/L mixes, add the 3-mercaptopropionic acid that sodium hydroxide solution that 0.25mL concentration is 0.25mol/L and 0.5mL concentration are 2mol/L, jolting mixes, react at 4 DEG C, reaction solution is become colorless by light yellow, obtain 3-thiohydracrylic acid-human serum-gold nano cluster, under 365nm ultra violet lamp, produce strong orange-yellow fluorescence, maximum excitation wavelength and emission wavelength are respectively 350nm and 575nm.
7. the arbitrary described preparation method of claim 1-6 obtains
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that soluble in water, the aqueous solution is colourless, and under ultra violet lamp, produce strong orange-yellow fluorescence, maximum excitation wavelength and emission wavelength are respectively 350nm and 575nm.
8. according to claim 7
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that gold nano cluster median size is 2.8nm.
9. according to claim 7 or 8
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that the aqueous solution is placed under 4 DEG C of dark places to occur without sediment for 2 months, fluorescence intensity and emission maximum peak position remain unchanged.
10. according to claim 7 or 8
3-thiohydracrylic acid-human serum-gold nano cluster,it is characterized in that taking hydrochloro-auric acid as Jin Yuan, 3-thiohydracrylic acid is reductive agent and modifier, and human serum is stablizer preparation.
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CN105860963A (en) * | 2016-04-16 | 2016-08-17 | 福建医科大学 | Guanidine hydrochloride/6-aza-2-sulfo-thymine-gold nano cluster and preparation method thereof |
CN105860959A (en) * | 2016-04-16 | 2016-08-17 | 福建医科大学 | Arginine/6-aza-2-sulfo-thymine-au nanocluster and preparing method thereof |
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Cited By (6)
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CN105820809A (en) * | 2016-04-16 | 2016-08-03 | 福建医科大学 | 6-aza-2-sulfothymine-gold nanocluster and preparation method thereof |
CN105860963A (en) * | 2016-04-16 | 2016-08-17 | 福建医科大学 | Guanidine hydrochloride/6-aza-2-sulfo-thymine-gold nano cluster and preparation method thereof |
CN105860959A (en) * | 2016-04-16 | 2016-08-17 | 福建医科大学 | Arginine/6-aza-2-sulfo-thymine-au nanocluster and preparing method thereof |
CN105820809B (en) * | 2016-04-16 | 2018-04-17 | 福建医科大学 | 6 azepine, 2 thio-thymine gold nano cluster and preparation method thereof |
CN105860959B (en) * | 2016-04-16 | 2018-05-18 | 福建医科大学 | Arginine/6- azepines -2- thio-thymines-gold nano cluster and preparation method thereof |
CN105860963B (en) * | 2016-04-16 | 2018-06-22 | 福建医科大学 | Guanidine hydrochloride/6- azepines -2- thio-thymines-gold nano cluster and preparation method thereof |
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