CN101905328B - Method for preparing water-soluble Au10 nano-cluster molecules - Google Patents
Method for preparing water-soluble Au10 nano-cluster molecules Download PDFInfo
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- CN101905328B CN101905328B CN2010102286927A CN201010228692A CN101905328B CN 101905328 B CN101905328 B CN 101905328B CN 2010102286927 A CN2010102286927 A CN 2010102286927A CN 201010228692 A CN201010228692 A CN 201010228692A CN 101905328 B CN101905328 B CN 101905328B
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Abstract
The invention discloses a method for preparing water-soluble Au10 nano-cluster molecules through a biomolecule induction one-step reaction. The method comprises the following steps of: 1) dissolving histidine in water and stirring the solution to obtain 0.0033 to 0.2 M aqueous solution of the histidine; 2) dissolving chloroauric acid in the water and stirring the solution to obtain 10 mM aqueous solution of the chloroauric acid; and 3) adding 3 mL of the 0.0033 to 0.2 M aqueous solution of the histidine into 1 mL of the 10 mM aqueous solution of the chloroauric acid, adjusting the Ph value of the solution to be between 2 and 11, fully mixing and standing for 1 hour to obtain the water-soluble Au10 nano-cluster molecules. A water-soluble Au10 nano-cluster obtained by the method emits blue-green fluorescent light and fluorescence quantum efficiency is 8.78 percent; and the water-soluble Au10 nano-cluster has the characteristics of high monodispersity, high stability, high biocompatibility and the like and has wide application prospects in the fields of nanocatalysis, monomolecular optoelectronics, biosensing, marking and the like.
Description
Technical field
The present invention relates to the cluster molecule preparation method, relate in particular to a kind of water-soluble Au
10The preparation method of nano-cluster molecules.
Background technology
Metal nanometer cluster has caused the research interest that the scientists of many ambits is very big, and is considered to have potential application as catalyst, light emitting diode etc. in various fields.Because the fermi level of metal is in the positive center that can be with, its relative energy level spacing is smaller, and the crystal of general nano-scale only shows the characteristic that plasma absorbs.But when the size of metal cluster is reduced to a certain degree, during as inferior nanometer level, cluster molecule can form differentiable band structure clearly, and this makes the metal cluster molecule may show the character of emission spectrum.Because gold nano-crystal is optimum for organism and has good biocompatibility, adopting luminous golden inferior nano-cluster molecules to be applied to field such as biology as marker will become possibility.
Though many seminars have developed the multiple method for preparing metal nanometer cluster, but preparation atomic level and monodispersed metal cluster molecule remain a challenge, and the nano-cluster molecules of most of method preparation needs further to purify and functionalization just may make it have water-soluble and biocompatibility.Biomolecule, as amino acid, polypeptide, protein, DNA, have accurate perfect chemical composition of nature and structure, often be applied to controlling the nucleation and the growth course of nanocrystal, perhaps be used as the synthetic controlled nanocrystal of shape of template-mediated.Importantly, biomolecule itself not only contains various functional groups, and has diversity structure, and this provides the possibility of carrying out selective absorption or keyed jointing with synthesis of nano crystal presoma, is controlling nanocrystal thus toward specific crystal face growth.For example, the researcher adopts DNA or oligomerization ribonucleic acid as support, has synthesized the ag nano-cluster that contains the specific atoms number.Participate in the prepared in reaction metal nanometer cluster with biomolecule and make the material preparation process become green non-poisonous, the nano material that obtains possesses excellent biological compatibility, provides good thinking for realizing the metal cluster molecule in the application of biological field.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of water-soluble Au is provided
10The preparation method of nano-cluster molecules.
Water-soluble Au
10The preparation method of nano-cluster molecules comprises the steps:
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.0033～0.2M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.0033～0.2M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 2～11, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Described water-soluble Au
10The histidine molecular composition on gold nuclear surface is examined and be coated on to the gold that nano-cluster molecules is made of 10 gold atoms, and the amino in the histidine molecule is chemically bonded to gold by strong N-Au and examines the surface.
The molecular structural formula of described histidine is:
The present invention compares the beneficial effect that has with existing technology:
1) histidine is induced and is generated Au
10Nano-cluster molecules is to prepare with Au for the first time in the world at present
10Nanocluster is the method for primary product, and it is 8.78% blue-green fluorescence that this cluster has fluorescence quantum efficiency, and fluorescence quantum efficiency is in higher level in the world;
2) Au
10The preparation process of nanocluster has the characteristics of stability and universality, and product is not subjected to reactant initial concentration ratio, solution acid alkalinity and Temperature Influence in the preparation process;
3) it is simple to prepare the method for water-soluble gold nano cluster, can make Au by single step reaction
10Nanocluster has greatly been simplified the preparation process of metal cluster, makes its mass preparation become possibility, has quickened its application in every field;
4) Au for preparing
10The nanocluster surface is coated by biomolecule, has improved the biocompatibility of nano material, makes its application at biological field become possibility.
Description of drawings
Fig. 1 is Au of the present invention
10The nanocluster ultraviolet-visible absorption spectroscopy;
Fig. 2 is Au of the present invention
10The nanocluster fluorescence spectrum;
Fig. 3 is Au of the present invention
10Nanocluster x-ray photoelectron power spectrum;
Fig. 4 (a) is Au of the present invention
10The nanocluster surface coats the mass spectrum of 2 histidines;
Fig. 4 (b) is Au of the present invention
10The nanocluster surface coats the mass spectrum of 6 histidines.
The specific embodiment
Water-soluble Au
10The preparation method of nano-cluster molecules comprises the steps:
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.0033～0.2M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.0033～0.2M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 2～11, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Described water-soluble Au
10The histidine molecular composition on gold nuclear surface is examined and be coated on to the gold that nano-cluster molecules is made of 10 gold atoms, and the amino in the histidine molecule is chemically bonded to gold by strong N-Au and examines the surface.
The molecular structural formula of described histidine is:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.0033M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.0033M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.01M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.01M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.05M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.05M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 4
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 5
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.2M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.2M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 6
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 2, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 7
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 11, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 8
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) potassium chloroaurate is soluble in water, stir, obtaining concentration is the potassium chloroaurate aqueous solution of 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the potassium chloroaurate aqueous solution that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 9
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.2M;
2) sodium chloraurate is soluble in water, stir, obtaining concentration is the sodium chloraurate aqueous solution of 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.2M joins in the sodium chloraurate aqueous solution that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 10
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and solution temperature is transferred to 0 ℃, leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 11
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and solution temperature is transferred to 25 ℃, leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Embodiment 12
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.1M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.1M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates Ph value to 7, fully mixes, and solution temperature is transferred to 60 ℃, leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
Claims (3)
1. water-soluble Au
10The preparation method of nano-cluster molecules is characterized in that comprising the steps:
1) histidine is soluble in water, stir, obtaining concentration is the histidine aqueous solution of 0.0033～0.2M;
2) gold chloride is soluble in water, stir, obtain the aqueous solution of chloraurate that concentration is 10mM;
3) 3mL concentration is that the histidine aqueous solution of 0.0033～0.2M joins in the aqueous solution of chloraurate that 1mL concentration is 10mM, regulates pH value to 2～11, fully mixes, and leaves standstill and reacts 1h, obtains water-soluble Au
10Nano-cluster molecules.
2. a kind of water-soluble Au according to claim 1
10The preparation method of nano-cluster molecules is characterized in that described water-soluble Au
10The histidine molecular composition on gold nuclear surface is examined and be coated on to the gold that nano-cluster molecules is made of 10 gold atoms, and the amino in the histidine molecule is chemically bonded to gold by strong N-Au and examines the surface.
3. a kind of water-soluble Au according to claim 1
10The preparation method of nano-cluster molecules is characterized in that the molecular structural formula of described histidine is:
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| CN103469331B (en) * | 2013-09-02 | 2016-02-24 | 福州麦克纳诺生物科技有限公司 | A kind of nano wire based on amino acid and metal hybrid and preparation method thereof |
| CN103920889B (en) * | 2014-04-03 | 2016-06-29 | 东南大学 | A kind of gold nanoclusters preparation method based on mercapto-polyglycol |
| CN104101584B (en) * | 2014-06-12 | 2017-04-05 | 东南大学 | Application of the gold nanoclusters as glutathione fluorescence probe |
| CN105344383B (en) * | 2015-12-11 | 2018-07-20 | 中国科学院上海高等研究院 | A kind of carrier TiO2And the preparation method and application thereof |
| WO2018024111A1 (en) * | 2016-08-05 | 2018-02-08 | 北京深见投资基金管理有限公司 | Substance containing gold cluster and preparation method and use thereof |
| CN110125432B (en) * | 2019-04-22 | 2021-07-27 | 山西大学 | Preparation method and application of green fluorescent copper nanocluster |
| CN113579243B (en) * | 2021-06-01 | 2023-08-01 | 广东省科学院健康医学研究所 | Honeysuckle nanometer flower and preparation method and application thereof |
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