CN103289684B - Fluorescent silver nanocluster as well as preparation method and application thereof - Google Patents
Fluorescent silver nanocluster as well as preparation method and application thereof Download PDFInfo
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- CN103289684B CN103289684B CN201210048387.9A CN201210048387A CN103289684B CN 103289684 B CN103289684 B CN 103289684B CN 201210048387 A CN201210048387 A CN 201210048387A CN 103289684 B CN103289684 B CN 103289684B
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Abstract
The invention belongs to the technical fields of preparation and application of metal optical function nano materials and in particular relates to a fluorescent silver nanocluster as well as a simple preparation method and application thereof. The fluorescent silver nanocluster is synthesized by reacting soluble silver salt with a stabilizer, wherein the fluorescent silver nanocluster has the mean particle size of more than 1.5nm and less than 2nm; the fluorescence emitted by the fluorescent silver nanocluster has the wavelength of 610nm under excitation of light with the wavelength of 510nm; the emitted fluorescence has high illumination stability. The method is readily available in raw materials, simple in process, convenient to operate, low in biotoxicity and easy to popularize and apply. The synthesized fluorescent silver nanocluster can be applied to the fields of optical imaging, biological markers, biological or chemical sensors and the like, and especially can be used for qualitative and quantitative detection on the activity of alpha-L-fucosidase.
Description
Technical field
The preparation and the applied technical field that the invention belongs to metal light function nano material, particularly relate to a kind of fluorescence ag nano-cluster and its preparation method and application.
Background technology
Metal nanometer cluster generally refers to and comprises several to dozens of atoms, and particle diameter is less than the particle of 2 nanometers.Now the particle diameter of nanocluster has reached Fermi's wavelength region (about 0.7nm), and bill of material reveals a series of peculiar optics, electricity and chemical property.For example, under this nanoscale, metal nanometer cluster is because splitting of energy levels becomes discrete energy level, thereby has excellent photoluminescent property.These metal nanometer clusters have the much character that is better than conventional fluorescent dyestuff, and as small size, light stability is strong, and Stokes displacement is large etc., are expected to realize application on fluorescence imaging, unit molecule spectrum, photoelectric device and biological or chemical sensor.Particularly fluorescence metal nanocluster has good biocompatibility, and the toxicity of organism, lower than current conventional semiconductor fluorescence quantum dot, is applicable to the application of biological field more.
The synthetic of fluorescence metal nanocluster made some progress in recent years, wherein the research of Dickson group of U.S. Georgia Tech system comparatively.During 2002-2005, they have developed the synthetic gold of emitting fluorescence of polyamide-amide type dendrimer and the method for silver nano-grain that to use with the tiopronin molecule of a sulfydryl and the hydroxyl of take be terminal, metal nanometer cluster fluorescence property is brought up to the level (J.Zheng that approaches semiconductor-quantum-point, R.M.Dickson, J.Am.Chem.Soc, 2002,124,13982-13983).But this method is raw materials used uncommon, and preparation method is more complicated.Afterwards again development take the synthetic method (W.W.Guo that the biomacromolecules such as DNA, polypeptide are template, J.P.Yuan, Q.Z.Dong, E.K.Wang, J.Am.Chem.Soc, 2010,132,932-934), and reverse micelle or microemulsion synthesis method (CN200710168372.5) also all exist raw material costliness, preparation process is long, and complicated operation is introduced the defects such as impurity is many.Although employing ultraviolet lighting method or the microwave method of developed recently also can synthesize the metal nanometer cluster that luminescent properties is good, because output is lower, need special specific equipment, limited its application.Another is conventional metal-salt liquid phase reduction (CN201010586429.5), and its synthetic method is comparatively simple, but also cannot avoid using part to have the reductive agent (for example sodium borohydride) of bio-toxicity.Therefore, in order to meet the requirement of biological field practical application, also need to develop a kind of raw material and be easy to get, technique is simple, easy to operate, and bio-toxicity is low, the synthetic method of the fluorescence metal nanocluster that is easy to apply.
Summary of the invention
One of object of the present invention is to provide a kind of fluorescence of transmitting to have the fluorescence ag nano-cluster of very high stability.
A further object of the present invention is to provide a kind of raw material and is easy to get, and technique is simple, easy to operate, the preparation method of the fluorescence ag nano-cluster that production cost is low.
Another object of the present invention is to provide a kind of purposes of fluorescence ag nano-cluster.
The median size of fluorescence ag nano-cluster of the present invention (three-dimensional simulation structure iron as shown in Figure 7) is 1.5nm < median size < 2nm, under the exciting of the light of 510nm wavelength, the wavelength of described fluorescence ag nano-cluster institute emitting fluorescence is 610nm, and the fluorescence of transmitting has very high light durability (as shown in Figure 6 within continuous light 5 minutes, fluorescence intensity does not significantly change).
Fluorescence ag nano-cluster of the present invention is to adopt liquid phase method to be prepared, and by silver soluble salt brine solution and the water-soluble liquid-phase mixing of stablizer, under heating condition, reacts, and obtains described fluorescence ag nano-cluster, and this preparation method comprises the following steps:
(1). soluble silver salt is mixed with water, and obtaining concentration is 3 * 10
-4～8 * 10
-2rub/liter (be preferably 2 * 10
-3～4 * 10
-2rub/liter) silver soluble salt brine solution; Stablizer is mixed with water, and obtaining concentration is 4.7 * 10
-5～3 * 10
-2rub/liter (be preferably 1 * 10
-4～6 * 10
-3rub/liter) the stablizer aqueous solution;
(2). silver soluble salt brine solution and the stablizer aqueous solution of step (1) preparation are obtained to mixed solution, and the concentration of the soluble silver salt in mixed solution is 2.5 * 10
-4～6.4 * 10
-2rub/liter (be preferably 1 * 10
-3～2 * 10
-2rub/liter), the concentration of stablizer is 8 * 10
-6～6 * 10
-3rub/liter (be preferably 5 * 10
-5～8 * 10
-4rub/liter); Stir, obtain fluorescence ag nano-cluster.
Described stirring is to be to stir at 60～95 ℃ in temperature.The time of described stirring is 2～12 hours.
Described soluble silver salt comprises Silver Nitrate or silver acetate.
Described stablizer is polymethyl acrylic acid.
Fluorescence ag nano-cluster of the present invention can be used as a kind of novel fluorescent marker, is expected to use, as biomarker fluorescent material, use, as the fluorescent material in biosensor or chemical sensor, use as photoimaging fluorescent material.
Described uses as the fluorescent material in biosensor, is to detect for the active qualitative and quantitative of alpha-L-fucosidase (AFu).Fluorescence ag nano-cluster of the present invention is when being used as such use, and it is highly sensitive, reproducible.
Described detects for the active qualitative and quantitative of alpha-L-fucosidase (AFu), it is the aqueous solution with the alpha-L-fucosidase of the different concns of preparing by gradient by the aqueous solution that contains described fluorescence ag nano-cluster, fluorescence with fluorescent spectrophotometer assay mixing solutions, under the exciting of the light of 510nm wavelength, the amount by 610nm wavelength place fluorescence intensity change realizes the qualitative and quantitative of alpha-L-fucosidase activity is detected.
Tool of the present invention has the following advantages:
1. preparation method of the present invention is simple, without use complicated reagent as biological macromolecular template method, does not need the special equipment such as microwave instrument, has overcome the deficiency that illumination reaction resultant quantity is little, productive rate is low, is more easy to apply.
2. the light durability of synthetic fluorescence ag nano-cluster is high, and within continuous light 5 minutes, fluorescence intensity does not significantly change (as Fig. 6), and bio-toxicity is lower than semiconductor fluorescence quantum dot, is more conducive to the application of biological field.
3. in the method for the invention, polymethyl acrylic acid had both been made stablizer and had also been made reductive agent.Polymethyl acrylic acid is a kind of high molecular polymer, usually used as the stablizer of synthesis of nano particle, owing to containing a certain amount of carboxyl, can form ligand with silver ions, thereby the reduction potential that reduces silver ions, makes silver ions under heating condition can be reduced to ag nano-cluster.Method of the present invention is only used two kinds of raw materials, and not only method is simple, and raw material is inexpensive, and product impurity is few, and purity is high.
4. adopt the synthetic fluorescence intensity of fluorescence ag nano-cluster of method of the present invention and the amount of alpha-L-fucosidase to be good linear relationship, can realize the qualitative and quantitative of alpha-L-fucosidase activity is detected.
Accompanying drawing explanation
Fig. 1. the electromicroscopic photograph of the fluorescence ag nano-cluster of the embodiment of the present invention 1.
Fig. 2. the uv-absorbing of the fluorescence ag nano-cluster of the embodiment of the present invention 1 and fluorescence spectrum figure.
Fig. 3. the fluorescence ag nano-cluster of the embodiment of the present invention 1 detects the fluorescence spectrum figure of alpha-L-fucosidase (AFu).In figure, " U/L " represents the activity unit of containing alpha-L-fucosidase in every liter of solution.
Fig. 4. the Linear Fit Chart of the fluoroscopic examination of the embodiment of the present invention 1.
Fig. 5. the column comparison diagram of the different enzymes of the embodiment of the present invention 2 on the fluorescence intensity impact of fluorescence ag nano-cluster.In figure, " Ag " represents fluorescence ag nano-cluster, and " AFu " represents alpha-L-fucosidase, and " NADH " represents Reduced nicotinamide-adenine dinucleotide reduction-state, and " AChE " represents acetylcholinesterase, and " ALP " represents alkaline phosphatase.
Fig. 6. the fluorescence ag nano-cluster of the embodiment of the present invention 3 is in the variation of fluorescence intensity that continues to excite lower transmitting of 510nm wavelength light.
Fig. 7. the three-dimensional simulation structure iron of fluorescence ag nano-cluster of the present invention, middle yellow bead representative " silver atoms ", fluorescence ag nano-cluster is the combination that includes several to dozens of silver atoms.
Embodiment
Embodiment 1
1, the preparation of fluorescence ag nano-cluster
(1). prepare respectively silver nitrate aqueous solution and polymethyl aqueous acid, wherein in silver nitrate aqueous solution, the concentration of Silver Nitrate is 8.3 * 10
-3rub/liter; In polymethyl aqueous acid, the concentration of polymethyl acrylic acid is 2.6 * 10
-3rub/liter.
(2). by silver nitrate aqueous solution and the polymethyl acrylic acid aqueous solution of step (1) preparation, the concentration that makes to mix the Silver Nitrate in rear solution is 6.4 * 10
-3rub/liter; The concentration of polymethyl acrylic acid is 3.2 * 10
-4rub/liter.At 70 ℃, stir 8 hours, obtain the fluorescence ag nano-cluster aqueous solution, electromicroscopic photograph is shown in Fig. 1, and the median size of fluorescence ag nano-cluster is 1.7nm.Under the exciting of the light of 510nm wavelength, the wavelength of institute's emitting fluorescence is 610nm, sees Fig. 2.
2, by the change in fluorescence of fluorescence ag nano-cluster, detect the activity of alpha-L-fucosidase
Alpha-L-fucosidase is made into the aqueous solution of various different concns by gradient, the solution of volume respectively takes a morsel from these alpha-L-fucosidase aqueous solution with pipettor, join respectively in the fluorescence ag nano-cluster aqueous solution of same volume and obtain mixing solutions, use rapidly the fluorescence intensity of the above-mentioned mixing solutions of fluorescence spectrophotometer measurement, under the exciting of the light of 510nm wavelength, the fluorescence spectrum figure that detection obtains is shown in Fig. 3, and the Linear Fit Chart of fluoroscopic examination is shown in Fig. 4.
Embodiment 2
1, the preparation of fluorescence ag nano-cluster
(1). prepare respectively silver nitrate aqueous solution and polymethyl aqueous acid, wherein in silver nitrate aqueous solution, the concentration of Silver Nitrate is 8 * 10
-2rub/liter; In polymethyl aqueous acid, the concentration of polymethyl acrylic acid is 3 * 10
-2rub/liter.
(2). by silver nitrate aqueous solution and the polymethyl acrylic acid aqueous solution of step (1) preparation, the concentration that makes to mix the Silver Nitrate in rear solution is 6.4 * 10
-2rub/liter; The concentration of polymethyl acrylic acid is 6 * 10
-3rub/liter.At 95 ℃, stir 2 hours, obtain the fluorescence ag nano-cluster aqueous solution, the median size of fluorescence ag nano-cluster is 1.8nm.Under the exciting of the light of 510nm wavelength, the wavelength of institute's emitting fluorescence is 610nm.
2, fluorescence ag nano-cluster detects the selectivity of alpha-L-fucosidase activity
By several frequently seen enzyme [alpha-L-fucosidase (AFu), Reduced nicotinamide-adenine dinucleotide reduction-state (NADH), acetylcholinesterase (AChE), alkaline phosphatase (ALP)] be made into the aqueous solution of same concentrations, the solution of volume respectively takes a morsel from these enzymes with pipettor, join respectively in the fluorescence ag nano-cluster aqueous solution of same volume, above-mentioned mixing solutions is used rapidly to fluorescence spectrophotometer measurement fluorescence intensity, under the exciting of the light of 510nm wavelength, detect the fluorescence intensity column comparison diagram obtaining and see Fig. 5.
Embodiment 3
1, the preparation of fluorescence ag nano-cluster
(1). prepare respectively the silver acetate aqueous solution and polymethyl aqueous acid, wherein in the silver acetate aqueous solution, the concentration of silver acetate is 3 * 10
-4rub/liter; In polymethyl aqueous acid, the concentration of polymethyl acrylic acid is 4.7 * 10
-5rub/liter.
(2). by the silver acetate aqueous solution and the polymethyl acrylic acid aqueous solution of step (1) preparation, the concentration that makes to mix the silver acetate in rear solution is 2.5 * 10
-4rub/liter; The concentration of polymethyl acrylic acid is 8 * 10
-6rub/liter.At 60 ℃, stir 5 hours, obtain the fluorescence ag nano-cluster aqueous solution, the median size of fluorescence ag nano-cluster is 1.6nm.Under the exciting of the light of 510nm wavelength, the wavelength of institute's emitting fluorescence is 610nm.Fluorescence ag nano-cluster continues to excite in 5 minutes 510nm wavelength light, and the fluorescence intensity of transmitting is almost constant, sees Fig. 6.
2, the activity operation that the change in fluorescence by fluorescence ag nano-cluster detects alpha-L-fucosidase is with embodiment 1.
Embodiment 4
1, the preparation of fluorescence ag nano-cluster
(1). prepare respectively the silver acetate aqueous solution and polymethyl aqueous acid, wherein in the silver acetate aqueous solution, the concentration of silver acetate is 2.2 * 10
-3rub/liter; In polymethyl aqueous acid, the concentration of polymethyl acrylic acid is 1.5 * 10
-4rub/liter.
(2). by the silver acetate aqueous solution and the polymethyl acrylic acid aqueous solution of step (1) preparation, the concentration that makes to mix the silver acetate in rear solution is 1.8 * 10
-3rub/liter; The concentration of polymethyl acrylic acid is 5.2 * 10
-5rub/liter.At 80 ℃, stir 12 hours, obtain the fluorescence ag nano-cluster aqueous solution, the median size of fluorescence ag nano-cluster is 1.9nm.Under the exciting of the light of 510nm wavelength, the wavelength of institute's emitting fluorescence is 610nm.
2, the activity operation that the change in fluorescence by fluorescence ag nano-cluster detects alpha-L-fucosidase is with embodiment 1.
Claims (3)
1. a preparation method for fluorescence ag nano-cluster, is characterized in that, described preparation method comprises the following steps:
(1). soluble silver salt is mixed with water, and obtaining concentration is 3 * 10
-4～8 * 10
-2rub/liter silver soluble salt brine solution; Stablizer is mixed with water, and obtaining concentration is 4.7 * 10
-5～3 * 10
-2rub/liter the stablizer aqueous solution;
(2). silver soluble salt brine solution and the stablizer aqueous solution of step (1) preparation are obtained to mixed solution, and the concentration of the soluble silver salt in mixed solution is 2.5 * 10
-4～6.4 * 10
-2rub/liter, the concentration of stablizer is 8 * 10
-6～6 * 10
-3rub/liter; In temperature, be at 60～95 ℃, to stir 2～12 hours, obtain fluorescence ag nano-cluster;
Described soluble silver salt comprises Silver Nitrate or silver acetate; Described stablizer is polymethyl acrylic acid.
2. preparation method according to claim 1, is characterized in that: the concentration of described silver soluble salt brine solution is 2 * 10
-3～4 * 10
-2rub/liter; The concentration of the described stablizer aqueous solution is 1 * 10
-4～6 * 10
-3rub/liter.
3. preparation method according to claim 1, is characterized in that: the concentration of the soluble silver salt in described mixed solution is 1 * 10
-3～2 * 10
-2rub/liter, the concentration of stablizer is 5 * 10
-5～8 * 10
-4rub/liter.
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| CN103624268B (en) * | 2013-11-13 | 2016-06-29 | 苏州大学 | The preparation method of the sugary ag nano-cluster of anticancer fluorescence |
| CN104722779B (en) * | 2013-12-23 | 2017-05-10 | 华东理工大学 | Silver nanocluster preparation method with hydrogen serving as reducing agent |
| CN103817347B (en) * | 2014-03-17 | 2016-01-27 | 中国科学院新疆理化技术研究所 | The preparation method of the core-shell structure copolymer Nanometer Copper of luminescence generated by light bunch |
| CN103878386A (en) * | 2014-03-28 | 2014-06-25 | 黑龙江大学 | Method for preparing fluorescent silver nano-clusters |
| CN103990811B (en) * | 2014-05-30 | 2015-11-18 | 吉林大学 | Electropositive metal fluorescence nano point, preparation method and the application in cell fluorescence imaging thereof |
| CN105017477B (en) * | 2015-06-30 | 2017-04-19 | 苏州大学 | Sugar-containing polymer based pH probe preparation method |
| CN105136757A (en) * | 2015-08-25 | 2015-12-09 | 武汉奥旷精密仪器有限公司 | Flower-shaped silver nanometer particle fluorescence-enhanced substrate and preparation method thereof |
| CN105798328B (en) * | 2016-05-18 | 2018-01-30 | 深圳市国华光电科技有限公司 | The preparation method of silver nano-grain |
| CN105965028A (en) * | 2016-05-20 | 2016-09-28 | 中国科学院新疆理化技术研究所 | Method for preparing water-soluble glowing metal clusters of platinum, gold, silver and copper and application |
| CN109266333B (en) * | 2018-10-23 | 2020-06-12 | 山西大学 | Preparation method and application of fluorescent silver nanocluster probe |
| CN112126672A (en) * | 2020-08-19 | 2020-12-25 | 四川大学华西医院 | alpha-L-fucosidase activity determination method, alpha-L-fucosidase diagnostic reagent and application |
| CN112690286A (en) * | 2020-12-15 | 2021-04-23 | 华侨大学 | Rare earth-silver nanocluster antibacterial agent and preparation method thereof |
| CN112916863B (en) * | 2021-01-19 | 2022-05-20 | 山西大学 | Water-soluble luminescent silver nanocluster and preparation method and application thereof |
| CN114523123B (en) * | 2022-02-24 | 2023-10-20 | 华南理工大学 | Nanocellulose-based fluorescent silver nanocluster and preparation method and application thereof |
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