CN102127428B - Fluorescent silver cluster, and preparation method and application thereof - Google Patents
Fluorescent silver cluster, and preparation method and application thereof Download PDFInfo
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- CN102127428B CN102127428B CN 201010586429 CN201010586429A CN102127428B CN 102127428 B CN102127428 B CN 102127428B CN 201010586429 CN201010586429 CN 201010586429 CN 201010586429 A CN201010586429 A CN 201010586429A CN 102127428 B CN102127428 B CN 102127428B
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Abstract
The invention relates to a fluorescent silver cluster, and a preparation method and application thereof. The average particle size of the fluorescent silver cluster is 1nm, and the fluorescent silver cluster can emit fluorescence, of which the wavelength is 650nm or so, under the excitation of light with different wavelengths. The preparation method comprises the following steps: reacting a silver salt and a protective agent in a water solution to generate a soluble silver complex, and slowly adding a reducer to generate the water-soluble fluorescent silver cluster. The fluorescent silver cluster can be used as a reagent for detecting mercury ions. The high-stability nano silver cluster, which can emit strong red fluorescence within the range of quantum scale, is formed by using common and cheap chemical reagents through a simple and practical synthesis technique. The nano silver cluster has very high sensitivity and specificity when being used as a reagent for detecting metallic ions, especially mercury ions. The invention can be widely used in the technical fields of environment detection, food safety and the like.
Description
Technical field
The present invention is specifically related to a kind of fluorescent silver cluster, its preparation method and application, and this fluorescent silver cluster can be used for the mercury ion in qualitative or sxemiquantitative ground detection water surrounding, and susceptibility and selectivity are high.
Background technology
Mercury ion and salt are the very large chemical substances of a kind of toxicity, because it has persistence, and the bioconcentration of easy transport property and height, the mankind and environment have been caused serious threat, and it can not pass through physics, chemistry, biological method is effectively degraded, and can only transfer to another kind of form from a kind of form.Mercury element is owing to there being its unique chemical physics performance to be widely used in various industrial production flow processs, and they mostly finally are converted into the mercury positively charged ion and are discharged into nature, and the source that the side Mercury In Environment pollutes is mainly the mercury-containing waste water of discharging from industrial production.In environment, the inorganic mercury ion can be converted into the methyl mercury of severe toxicity under certain condition by organism.Inorganic mercury major effect kidney, and methyl mercury is mainly encroached on neural system after entering human body.Both all can be highly rich long-pending in biological tissue by food chain, thereby Man ﹠ Nature circle are caused huge harm.Therefore, how effectively detecting mercury ion all is of great importance for biological chemistry, environmental science and medical science etc.
In recent years, scientist is devoted to develop highly selective, efficient feasible mercury ion chemical detection method, and particularly based on fluorescence, visible uv-absorbing, the detection method of the change in physical such as variable color has obtained some achievements.For example, Qian Xuhong etc. have reported a kind of water miscible mercury ion chemical sensor (" A Highly Selective and Sensitive Fluorescent Chemosensor for Hg 2+in Neutral Buffer Aqueous Solution " that simply has, J.Am.Chem.Soc.2004,126,2272-2273), it can detect the mercury ion of ppm/ppb level concentration in Natural Water.The people such as C.J.Chang reported a kind of water miscible fluorescence chemical sensor MF1 (" Screening Mercury Levels in Fish with a Selective Fluorescent Chemosensor ", J.Am.Chem.Soc.2005,127,16030), it can detect the mercury ion of ppm in Natural Water, this molecule has very high selectivity to mercury ion, when being used for the analyzing and testing to fish body mercury ion, in 0.1 to 8ppm ion concentration of mercury category, check out reliably ion concentration of mercury.The human hairs such as Wu Dayu understand that a kind of fluorescent color-developing agent (patent publication No. CN101135644) is incorporated into fluorescence chromophoric group rhodamine-6G with ferrocene units, obtained luxuriant iron-based rhodamine fluorescent color-developing agent, be used for mercury ion detecting, can further improve water-soluble, selectivity and sensitivity.Zheng Hong etc. and thank to the method (patent publication No. is respectively CN1752750 and CN101038286) that beautiful fine jade philosophy has proposed to detect with synthetic organic chemical reagent mercury ion in addition.
But, often relate to organism and the organic reaction of a lot of complexity in the synthesis process of above-mentioned mercury ion detecting technology detection used, complex process, poor controllability, and cost is higher.
Summary of the invention
In view of the deficiencies in the prior art, purpose of the present invention aims to provide a kind of fluorescent silver cluster, its preparation method and application, and this fluorescent silver cluster has very high stability, can be directly used in the detection of water sample mercury ion, highly sensitive, selectivity is good, and preparation technology is simple, and is with low cost.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of fluorescent silver cluster is characterized in that, the median size of described fluorescent silver cluster is 1nm, and can be under the exciting of different wave length the fluorescence of emission the same band.
To further, the wavelength of described fluorescent silver cluster institute's emitting fluorescence under the exciting of different wave length is at the 650nm wave band.
Described different wave length comprises UV-light and visible light.
The preparation method of fluorescent silver cluster, is characterized in that as mentioned above, and the method is: silver salt and protective material are reacted generation silver soluble complex compound in the aqueous solution, more slowly add reductive agent, generate the water soluble fluorescence Silver Clusters.
Particularly, the method is specially:
At first protective material is soluble in water, form the aqueous solution;
To the above-mentioned aqueous solution in slowly add water soluble silver salt, form mixing solutions thereafter
Then slowly add reductive agent in above-mentioned mixing solutions, generate fluorescent silver cluster.
The method comprises following concrete steps:
I, protective material is added to the water, and slowly adds alkali or alkaline solution, dissolve fully to protective material, and the aqueous solution is neutrality or weakly alkaline;
II, continue stirring under the condition of the above-mentioned aqueous solution, slowly add water soluble silver salt or its aqueous solution, form mixing solutions;
III, slowly add reductive agent in above-mentioned mixing solutions, lucifuge stirs thereafter, and ambient temperature overnight is to generating target product;
Above-mentioned protective material adopts has sulfhydryl-group activity, and can form with silver ions the compound of water soluble complex, as Thioctic Acid etc.; Above-mentioned reductive agent can be selected from but be not limited to the reagent such as sodium borohydride, Trisodium Citrate and triethylamine, and the consumption of above-mentioned protective material and reductive agent be enough to silver salt in silver ions complete reaction or slightly excessive.Described protective material can be selected from but be not limited to the reagent such as Thioctic Acid.
Described alkali can adopt any one in mineral alkali and organic bases, and described mineral alkali can be selected from but be not limited to NaOH, KOH etc.
Described water soluble silver salt preferably adopts Silver Nitrate, Silver monoacetate or other similar silver salt.
The pH value of the aqueous solution described in step I is 7-9.
Fluorescent silver cluster is as the application of mercury ion detecting reagent as mentioned above.
Technical scheme of the present invention compares to prior art, and its remarkable advantage is embodied in:
Adopt Thioctic Acid, AgNO
3, NaBH
4Etc. common cheap chemical reagent, through simple synthesis technique, formation can be launched very strong red fluorescence in the scope of quantum yardstick, and the nanometer silver cluster of excellent in stability, this nanometer silver cluster is being applied as metal ion, particularly during the detection reagent of mercury ion, can show high sensitivity and specificity.
Description of drawings
Fig. 1 is the transmission electron microscope photo of obtained fluorescent silver cluster in a preferred embodiment of the present invention;
Fig. 2 is the fluorescent emission graphic representation of fluorescent silver cluster shown in Figure 1 under different excitation wavelengths;
Fig. 3 is that fluorescent silver cluster shown in Figure 1 is to the fluorescence intensity response curve of different metal ion;
Fig. 4 is that fluorescent silver cluster shown in Figure 1 is to the fluorescence intensity response curve of various concentration mercury ions.
Embodiment
The present invention adopts the cost degradation compound as reaction raw materials, in the suitable aqueous phase system of potential of hydrogen, react under room temperature, prepare a kind of water-soluble goodly, stable and have the nanometer silver cluster of red fluorescence, this Silver Clusters shows high detectability and specificity in the detection to mercury ion
Particularly, the preparation method of this fluorescent silver cluster is:
Silver salt and protective material are reacted generation silver soluble complex compound in the aqueous solution, more slowly add reductive agent, generate the water soluble fluorescence Silver Clusters.
Say further, the method is: at first that protective material is soluble in water, form the aqueous solution; To the above-mentioned aqueous solution in slowly add water soluble silver salt, form mixing solutions thereafter; Then slowly add reductive agent in above-mentioned mixing solutions, generate fluorescent silver cluster.
Further say, the method comprises following concrete steps:
I, protective material is added to the water, and slowly add any one material that is selected from mineral alkali or organic bases, dissolve fully to protective material and (in fact add the purpose of alkaline matter to be to assist the dissolving protective material, therefore, unrestricted to its kind), and the aqueous solution is neutrality or weakly alkaline;
II, continue stirring under the condition of the above-mentioned aqueous solution, slowly add water soluble silver salt or its aqueous solution, form mixing solutions;
III, slowly add reductive agent in above-mentioned mixing solutions, lucifuge stirs thereafter, and ambient temperature overnight is to generating target product.
Above-mentioned protective material preferably adopts has sulfhydryl-group activity group; and can form with silver ions the compound of water soluble complex; as Thioctic Acid etc., above-mentioned reductive agent preferably adopts boration sodium, and the consumption of above-mentioned protective material and reductive agent be enough to silver salt in silver ions complete reaction or slightly excessive.
Described water soluble silver salt preferably adopts Silver Nitrate, Silver monoacetate etc.
Utilize the grain diameter of the fluorescent silver cluster that preceding method makes very little, only have the 1nm left and right, and with the fluorescent effect of semiconductor-quantum-point, closely similar character is arranged, can launch the fluorescence of the same band under different excitation wavelengths.
Again further, the fluorescent silver cluster that is synthesized has the sensitivity of height and the specificity of height to the detection of mercury ion, and only needs seldom to measure the detection that just can complete mercury ion.
Below in conjunction with accompanying drawing and some preferred embodiments, technical scheme of the present invention is described further.
The embodiment 1 water miscible Silver Clusters of preparation:
Add 20.63mg Thioctic Acid (Hla) and 10ml deionized water in round-bottomed flask, rapid stirring, the Thioctic Acid major part is not dissolved; Then slowly dripping 100ul concentration is the NaOH aqueous solution of 1mol/L, and the hydrogen ion of the carboxyl of Thioctic Acid is neutralized and is dissolved in the water by NaOH; Then adding concentration is the AgNO3 solution 100ul of 25mM, stirs after five minutes, and slowly the NaBH4 solution 100ul that concentration is 300mM is newly joined in dropping, observes solution and can gradually become brown, then uses the masking foil lucifuge, ambient temperature overnight; Second day takes out, solution becomes light yellow, namely generate required fluorescent silver cluster particle, use transmission electron microscope observing, find that the size of cluster is in 1nm left and right (consulting Fig. 1), its optical property as shown in Figure 2, the emission wavelength that excites with ultraviolet, visible various excitation wavelengths all near 650nm, can't change because of the variation of the wavelength that excites.Find by the NaCl solution contrast that adds high density, this Silver Clusters adds without any reaction NaCl's, does not generate white precipitate, illustrate that silver ions has been reduced the silver atoms cluster of generation fully.
The structural formula of aforementioned Thioctic Acid is as follows:
The optionally fluorescence experiments of embodiment 2 Silver Clusters particles to various ions:
Get the Silver Clusters solution of equal volume, with metal cation salt (Hg
2+, Mg
2+, Pb
2+, Zn
2+, Cu
2+) be made into identical strength of solution, the solution of volume respectively takes a morsel from these metal cation salts with pipettor, add in the off-the-shelf Silver Clusters aqueous solution, the concentration of last various ions is all 20uM, add the solution after ion to survey its fluorescence with spectrophotofluorometer rapidly with above-mentioned, select the 420nm place to excite, survey its fluorogram, the results are shown in accompanying drawing 3.
Get the Silver Clusters solution of equal volume, the another solution of various different concns that mercury salt is made into by gradient, then the solution of volume respectively takes a morsel from these mercury ion salt with pipettor, add in the off-the-shelf Silver Clusters aqueous solution, add the solution after ion to survey its fluorescence with spectrophotofluorometer rapidly with above-mentioned, select the 420nm place to excite, survey its fluorogram, the results are shown in accompanying drawing 4.
In sum, the present invention utilizes the solubility of Thioctic Acid under alkaline condition and the character of element sulphur and the easy coordination of silver ions, a kind of water miscible fluorescent silver cluster and preparation method thereof is proposed, this kind fluorescent silver cluster size is very little, excellent in stability, and in for detection of the aqueous solution during mercury ion, show efficient, single-minded advantage.
Above-mentioned description by concrete enforcement example is intended to easy to understand technical scheme feature of the present invention, and protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, within all dropping on rights protection scope of the present invention.
Claims (7)
1. a fluorescent silver cluster, is characterized in that, the median size of described fluorescent silver cluster is 1nm, and can be under the exciting of different wave length the fluorescence of emission the same band, the preparation method of described fluorescent silver cluster comprises:
I, protective material is added to the water, and slowly adds alkali or alkaline solution, dissolve fully to protective material, and the aqueous solution is neutrality or weakly alkaline;
II, continue stirring under the condition of the above-mentioned aqueous solution, slowly add water soluble silver salt or its aqueous solution, form mixing solutions;
III, slowly add reductive agent in above-mentioned mixing solutions, lucifuge stirs thereafter, and ambient temperature overnight is to generating target product;
Above-mentioned protective material adopts has sulfhydryl-group activity, and can form with silver ions the compound of water soluble complex, and above-mentioned reductive agent adopts sodium borohydride, Trisodium Citrate or triethylamine;
And the consumption of above-mentioned protective material and reductive agent be enough to silver salt in silver ions complete reaction or slightly excessive, in step I, the pH value of the described aqueous solution is 7-9.
2. fluorescent silver cluster according to claim 1, is characterized in that, the wavelength of described fluorescent silver cluster institute's emitting fluorescence under the exciting of different wave length is at the 650nm wave band.
3. fluorescent silver cluster according to claim 1 and 2, is characterized in that, described different wave length comprises UV-light and visible light.
4. the preparation method of a fluorescent silver cluster, is characterized in that, the median size of described fluorescent silver cluster is 1nm, and can be under the exciting of different wave length the fluorescence of emission the same band, the preparation method of described fluorescent silver cluster comprises:
I, protective material is added to the water, and slowly adds alkali or alkaline solution, dissolve fully to protective material, and the aqueous solution is neutrality or weakly alkaline;
II, continue stirring under the condition of the above-mentioned aqueous solution, slowly add water soluble silver salt or its aqueous solution, form mixing solutions;
III, slowly add reductive agent in above-mentioned mixing solutions, lucifuge stirs thereafter, and ambient temperature overnight is to generating target product;
Above-mentioned protective material adopts has sulfhydryl-group activity, and can form with silver ions the compound of water soluble complex, and above-mentioned reductive agent adopts sodium borohydride, Trisodium Citrate or triethylamine;
And the consumption of above-mentioned protective material and reductive agent be enough to silver salt in silver ions complete reaction or slightly excessive, in step I, the pH value of the described aqueous solution is 7-9.
5. the preparation method of fluorescent silver cluster according to claim 4, is characterized in that, described alkali adopts any one in mineral alkali and organic bases, and described mineral alkali comprises NaOH and KOH; Described water soluble silver salt is Silver Nitrate or Silver monoacetate.
6. the preparation method of fluorescent silver cluster according to claim 4, is characterized in that, described protective material adopts Thioctic Acid.
As claimed in claim 1 fluorescent silver cluster as the application of mercury ion detecting reagent.
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| WO2013061109A1 (en) | 2011-10-28 | 2013-05-02 | Indian Institute Of Technology Madras | Methods of preparing metal quantum clusters in molecular confinement |
| CN102627966A (en) * | 2012-03-23 | 2012-08-08 | 山西大学 | Nano-silver fluorescent probe for detection of cyanide ion |
| CN103226103B (en) * | 2013-04-04 | 2015-02-04 | 哈尔滨师范大学 | Colorimetric detection probe of mercury ion and application method thereof |
| 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 |
| CN105798322B (en) * | 2016-03-17 | 2018-04-24 | 湖北大学 | The preparation method and applications of silver nanoclusters |
| US20180055083A1 (en) * | 2016-08-23 | 2018-03-01 | Goldred Nanobiotech Co., Ltd. | Process for forming a solution containing gold nanoclusters binding with ligands |
| CN106854286B (en) * | 2016-12-22 | 2020-04-28 | 郑州大学 | Mercapto-silver cluster coordination polymer, and preparation method and application thereof |
| CN110883341B (en) * | 2018-09-11 | 2021-03-30 | 清华大学 | Preparation method of gold nanoclusters |
| CN109794616A (en) * | 2019-01-15 | 2019-05-24 | 南通纺织丝绸产业技术研究院 | The preparation of the silver nanoclusters of sericin package and fluorescence probe |
| CN110655651B (en) * | 2019-10-12 | 2020-07-07 | 中国空气动力研究与发展中心高速空气动力研究所 | Lipoic acid-silver nano self-repairing material as well as preparation method and application thereof |
| CN116463118B (en) * | 2023-03-15 | 2024-01-30 | 河南大学 | Silver cluster with aggregation-induced emission effect and preparation method and application thereof |
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| 以聚甲基丙烯酸为模版微波法合成荧光银纳米簇和1D银纳米离子及应用研究;崔强;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090815;B020-69 * |
| 崔强.以聚甲基丙烯酸为模版微波法合成荧光银纳米簇和1D银纳米离子及应用研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2009,B020-69. |
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