CN111299605A - Controllable preparation of gold nanoclusters wrapped by papain - Google Patents
Controllable preparation of gold nanoclusters wrapped by papain Download PDFInfo
- Publication number
- CN111299605A CN111299605A CN202010195702.5A CN202010195702A CN111299605A CN 111299605 A CN111299605 A CN 111299605A CN 202010195702 A CN202010195702 A CN 202010195702A CN 111299605 A CN111299605 A CN 111299605A
- Authority
- CN
- China
- Prior art keywords
- gold nanoclusters
- papain
- gold
- adjusting
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention relates to a controllable preparation method of gold nanoclusters wrapped by papain, belonging to the field of nanotechnology; the papain is taken as a template, and the influence of the change of the pH value on the optical performance of the gold nanoclusters in the reaction process is explored; by controlling the reaction pH, temperature and time, the gold nanoclusters capable of emitting green, blue and yellow fluorescence and having the particle size of about 1 nm are respectively synthesized; the synthetic method is simple and green, and the synthesized gold nanocluster has good optical stability, strong photobleaching resistance, strong catalytic performance and electrochemiluminescence performance, and can be used as a good photochemical and electrochemical signal probe or catalyst.
Description
Technical Field
The invention belongs to the field of nanotechnology.
Background
The gold nanocluster is composed of several to hundreds of gold atoms, the particle size is usually less than 2nm, and the continuous state density is decomposed into discrete energy levels due to the fact that the size is close to the Fermi wavelength of electrons, so that the gold nanocluster can generate electron transitions in a metal core, including interband electron transitions between a d band and an sp band and intraband electron transitions between the highest occupied orbit and the lowest unoccupied orbit of the sp band, and has obvious quantum size effect.
The template method is used as a gold nanocluster synthesis method widely applied at present, has the characteristics of simple, convenient and quick operation process, environmental protection and the like, and is a preparation method with great development potential. The method is a method for finally forming the metal nano-cluster by selecting a proper material capable of protecting and stabilizing the metal nano-cluster as a template, gradually reducing gold ions into gold atoms in the preparation process, and continuously accumulating and wrapping the gold atoms in a cavity structure formed by template molecules. The choice of template is critical, the template material has many functional groups that can interact with metal ions, and therefore proteins are usually chosen as templates in the synthesis of metal nanoclusters.
However, in the synthesis process, the complex structure of many proteins and many amino acid types can not effectively control the complexing ability and reducing ability of the reaction system, for example, the fluorescence wavelength of gold nanoclusters synthesized by using the currently common bovine serum albumin, pepsin, transferrin and the like as templates is almost larger than 700 nm, and the optical stability is poor, because the action of active amino acids such as cysteine, tyrosine and tryptophan cannot be clearly defined, and many proteins are expensive, it is very important to find a protein template with a clear structure and low cost.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a controllable preparation method of a gold nanocluster wrapped by papain, the selected papain is cysteine protease, is a single peptide chain consisting of 212 amino acid residues, has an average molecular weight of 23000, contains tyrosine (Y), tryptophan (W), histidine (H) and other amino acid residues rich in amino groups and carboxyl in an amino acid sequence, has a small molecular weight, a simple peptide chain structure and clear amino acid residue quantity and types, effectively realizes the control of the optical performance of a product by controlling the reaction pH, temperature and time, and provides certain reference significance for the selection of template proteins in the gold nanocluster synthesized by a template method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. a controllable preparation method of gold nanoclusters wrapped by papain is characterized by comprising the following steps:
placing 1-5 mL of papain aqueous solution (40-60 mg/mL) and 1-5 mL of chloroauric acid aqueous solution (5-10 mM) in a 50 mL round-bottom flask for mixing, and stirring for 3-5 min; adjusting the pH value of the solution by using hydrochloric acid (1M) and sodium hydroxide (1M) aqueous solution, and reacting in a constant-temperature shaking box to obtain gold nanoclusters capable of emitting green, blue and red fluorescence;
2. the controllable preparation method of papain-coated gold nanoclusters as claimed in claim 1, wherein the gold nanoclusters with red fluorescence are prepared by the following steps:
adjusting the pH value of the solution to 9-10 by using a sodium hydroxide (1M) aqueous solution, and adjusting the pH value to 37oC, shaking at constant temperature for 2-5 h, and centrifuging (4000 rpm) for 20 min after finishing, wherein the supernatant is a target product;
3. the controllable preparation method of papain-coated gold nanoclusters as claimed in claim 1, wherein the gold nanoclusters with green fluorescence are prepared by the following steps:
adjusting the pH value to 0.2-1.2 by using a hydrochloric acid (1M) aqueous solution, incubating at the constant temperature of 37 ℃ for 60-96 h, and centrifuging (4000 rpm) for 20 min after completion, wherein the supernatant is a target product;
4. the controllable preparation method of papain-coated gold nanoclusters as claimed in claim 1, wherein the gold nanoclusters with blue fluorescence are prepared by the following steps:
adjusting the pH value to 4-6 by using a sodium hydroxide (1M) aqueous solution, shaking at a constant temperature of 25 ℃ for 18-24 h, and centrifuging (4000 rpm) for 20 min after completion, wherein the supernatant is the target product.
Drawings
FIG. 1 is TEM characterization of red fluorescent gold nanoclusters prepared in example 2 of the present invention;
FIG. 2 is TEM characterization of green fluorescent gold nanoclusters prepared in example 3 of the present invention;
FIG. 3 is TEM characterization of blue fluorescent gold nanoclusters prepared in example 4 of the present invention;
FIG. 4 shows the fluorescence test results of three gold nanoclusters with three fluorescence wavelengths prepared in example 1 of the present invention.
Advantageous results of the invention
According to the invention, papain is used as a coating agent and a reducing agent for the first time, red light gold nanoclusters, green light gold nanoclusters and blue light gold nanoclusters with uniform sizes are synthesized by controlling and adjusting the pH, temperature and time of reaction, the influence of the reaction time, concentration and temperature on an experiment is researched, the method is simple and green, and the synthesized gold nanoclusters have good optical and electrical stability.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1.
The invention discloses a controllable preparation method of a gold nanocluster wrapped by papain, which comprises the following steps:
placing papain in water (5 mL, 40 mg/mL) and chloroauric acid in water (5 mL, 10 mM) in a 50 mL round-bottom flask, mixing and stirring for 5 min; adjusting the pH value of the solution by using hydrochloric acid (1M) and sodium hydroxide (1M) aqueous solution, and reacting in a constant-temperature shaking box to obtain gold nanoclusters capable of emitting green, blue and red fluorescence;
further, in order to obtain the gold nanocluster with red fluorescence, the preparation method comprises the following steps:
the pH of the solution was adjusted to 9 with aqueous sodium hydroxide (1M) and at 37oC, shaking at constant temperature for 2 h, and centrifuging (4000 rpm) for 20 min after finishing, wherein the supernatant is a target product;
further, in order to obtain the gold nanocluster with green fluorescence, the preparation method comprises the following steps:
adjusting pH to 1.2 with hydrochloric acid (1M) water solution, incubating at 37 deg.C for 96 hr, centrifuging (4000 rpm) for 20 min, and collecting supernatant as target product;
further, in order to obtain the gold nanocluster with blue fluorescence, the preparation method comprises the following steps:
adjusting pH to 6 with sodium hydroxide (1M) water solution, shaking at constant temperature of 25 deg.C for 24 hr, centrifuging (4000 rpm) for 20 min, and collecting supernatant as target product;
example 2.
The invention discloses a controllable preparation method of a gold nanocluster wrapped by papain, which comprises the following steps:
placing papain in water (3 mL, 60 mg/mL) and chloroauric acid in water (5 mL, 10 mM) in a 50 mL round-bottom flask, mixing and stirring for 5 min; adjusting the pH value of the solution by using hydrochloric acid (1M) and sodium hydroxide (1M) aqueous solution, and reacting in a constant-temperature shaking box to obtain gold nanoclusters capable of emitting green, blue and red fluorescence;
further, in order to obtain the gold nanocluster with red fluorescence, the preparation method comprises the following steps:
the pH of the solution was adjusted to 10 with aqueous sodium hydroxide (1M) and at 37oC, shaking at constant temperature for 5 h, and centrifuging (4000 rpm) for 20 min after finishing, wherein the supernatant is a target product;
further, in order to obtain the gold nanocluster with green fluorescence, the preparation method comprises the following steps:
adjusting pH to 0.5 with hydrochloric acid (1M) water solution, incubating at 37 deg.C for 60 hr, centrifuging (4000 rpm) for 20 min, and collecting supernatant as target product;
further, in order to obtain the gold nanocluster with blue fluorescence, the preparation method comprises the following steps:
adjusting pH to 5.5 with sodium hydroxide (1M) water solution, shaking at constant temperature of 25 deg.C for 18 h, centrifuging (4000 rpm) for 20 min, and collecting supernatant as target product;
the above description is only the most preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A controllable preparation method of gold nanoclusters wrapped by papain is characterized by comprising the following steps:
placing 1-5 mL of papain aqueous solution (40-60 mg/mL) and 1-5 mL of chloroauric acid aqueous solution (5-10 mM) in a 50 mL round-bottom flask for mixing, and stirring for 3-5 min; adjusting the pH value of the solution by using hydrochloric acid (1M) and sodium hydroxide (1M) aqueous solution, and reacting in a constant-temperature shaking box to obtain gold nanoclusters capable of emitting green, blue and red fluorescence;
the controllable preparation method of papain-coated gold nanoclusters as claimed in claim 1, wherein the gold nanoclusters with red fluorescence are prepared by the following steps:
adjusting the pH value of the solution to 9-10 by using a sodium hydroxide (1M) aqueous solution, and adjusting the pH value to 37oC, shaking at constant temperature for 2-5 h, and centrifuging (4000 rpm) for 20 min after finishing, wherein the supernatant is a target product;
the controllable preparation method of papain-coated gold nanoclusters as claimed in claim 1, wherein the gold nanoclusters with green fluorescence are prepared by the following steps:
adjusting the pH value to 0.2-1.2 by using a hydrochloric acid (1M) aqueous solution, incubating at the constant temperature of 37 ℃ for 60-96 h, and centrifuging (4000 rpm) for 20 min after completion, wherein the supernatant is a target product;
the controllable preparation method of papain-coated gold nanoclusters as claimed in claim 1, wherein the gold nanoclusters with blue fluorescence are prepared by the following steps:
adjusting the pH value to 4-6 by using a sodium hydroxide (1M) aqueous solution, shaking at a constant temperature of 25 ℃ for 18-24 h, and centrifuging (4000 rpm) for 20 min after completion, wherein the supernatant is the target product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010195702.5A CN111299605A (en) | 2020-03-19 | 2020-03-19 | Controllable preparation of gold nanoclusters wrapped by papain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010195702.5A CN111299605A (en) | 2020-03-19 | 2020-03-19 | Controllable preparation of gold nanoclusters wrapped by papain |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111299605A true CN111299605A (en) | 2020-06-19 |
Family
ID=71151451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010195702.5A Pending CN111299605A (en) | 2020-03-19 | 2020-03-19 | Controllable preparation of gold nanoclusters wrapped by papain |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111299605A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925790A (en) * | 2020-08-17 | 2020-11-13 | 安徽师范大学 | Preparation method of fluorescent gold nanocluster and application of fluorescent gold nanocluster in ampicillin detection |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464780A (en) * | 2013-09-06 | 2013-12-25 | 湖南科技大学 | Preparation method of fluorescence gold nano clusters with stable chicken ovalbumin |
| CN106947471A (en) * | 2017-03-08 | 2017-07-14 | 吉林大学 | A kind of water miscible gold nanoclusters fluorescent material, preparation method and application |
| CN107552809A (en) * | 2017-08-28 | 2018-01-09 | 大连理工大学 | A kind of synthetic method of the color controllable fluorescence gold nanoclusters of silver regulation |
| CN108031857A (en) * | 2017-11-21 | 2018-05-15 | 东华大学 | A kind of preparation method for the gold nano cluster for sending out red fluorescence |
| CN109794617A (en) * | 2019-01-15 | 2019-05-24 | 南通纺织丝绸产业技术研究院 | The preparation of the gold nanoclusters of sericin package and fluorescence probe |
| CN110862820A (en) * | 2019-10-23 | 2020-03-06 | 云南大学 | Preparation method and application of cysteine-gold nanocluster |
-
2020
- 2020-03-19 CN CN202010195702.5A patent/CN111299605A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464780A (en) * | 2013-09-06 | 2013-12-25 | 湖南科技大学 | Preparation method of fluorescence gold nano clusters with stable chicken ovalbumin |
| CN106947471A (en) * | 2017-03-08 | 2017-07-14 | 吉林大学 | A kind of water miscible gold nanoclusters fluorescent material, preparation method and application |
| CN107552809A (en) * | 2017-08-28 | 2018-01-09 | 大连理工大学 | A kind of synthetic method of the color controllable fluorescence gold nanoclusters of silver regulation |
| CN108031857A (en) * | 2017-11-21 | 2018-05-15 | 东华大学 | A kind of preparation method for the gold nano cluster for sending out red fluorescence |
| CN109794617A (en) * | 2019-01-15 | 2019-05-24 | 南通纺织丝绸产业技术研究院 | The preparation of the gold nanoclusters of sericin package and fluorescence probe |
| CN110862820A (en) * | 2019-10-23 | 2020-03-06 | 云南大学 | Preparation method and application of cysteine-gold nanocluster |
Non-Patent Citations (2)
| Title |
|---|
| JUN PENG ET AL.: "Selective fluorescence quenching of papain–Au nanoclusters by self‐polymerization of dopamine", 《LUMINESCENCE》 * |
| LICHAO WANG ET AL.: "Fluorescent sensing of sulfide ions based on", 《NEW JOURNAL OF CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925790A (en) * | 2020-08-17 | 2020-11-13 | 安徽师范大学 | Preparation method of fluorescent gold nanocluster and application of fluorescent gold nanocluster in ampicillin detection |
| CN111925790B (en) * | 2020-08-17 | 2023-03-24 | 安徽师范大学 | Preparation method of fluorescent gold nanocluster and application of fluorescent gold nanocluster in ampicillin detection |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Heterogeneous catalysis by gold and gold-based bimetal nanoclusters | |
| Wu et al. | Sophisticated construction of Au islands on Pt–Ni: an ideal trimetallic nanoframe catalyst | |
| Jin et al. | Tri-icosahedral gold nanocluster [Au37 (PPh3) 10 (SC2H4Ph) 10X2]+: Linear assembly of icosahedral building blocks | |
| Wang et al. | Protein-directed synthesis of pH-responsive red fluorescent copper nanoclusters and their applications in cellular imaging and catalysis | |
| US9410950B2 (en) | Luminescent gold nanomaterial functionalized by N-(4-aminobutyl)-N-ethylisoluminol, preparation and application thereof | |
| CN103264987B (en) | Gold nanocluster preparation method and application thereof | |
| JP6364319B2 (en) | Atomic quantum cluster, method for producing the same, and method for using the same | |
| Hinterwirth et al. | Bioconjugation of trypsin onto gold nanoparticles: effect of surface chemistry on bioactivity | |
| EP1758678B1 (en) | Method for the production of platinum catalysts obtained by reducing in-situ formed platinum dioxide | |
| CA2537199C (en) | Precious metal colloid, precious metal microparticle, composition, and process for producing the precious metal microparticle | |
| Naveen et al. | Gold nanoclusters as electrocatalysts: Atomic level understanding from fundamentals to applications | |
| CN107470648B (en) | DNA functionalized gold nanocluster and preparation method thereof | |
| Zeng et al. | Aqueous synthesis of type-II CdTe/CdSe core–shell quantum dots for fluorescent probe labeling tumor cells | |
| CN109110819B (en) | Synthesis method of chiral manganese oxide nanoparticles | |
| Bhattacharjee et al. | Peptide-assisted synthesis of gold nanoparticles and their self-assembly | |
| KR20110127159A (en) | Encapsulated nanoparticles | |
| JPWO2003099708A1 (en) | Nanoparticle production method and nanoparticle produced by the production method | |
| WO1999001766A1 (en) | A metal particle, its preparation and use, and a material or device comprising the metal particle | |
| CA2589239C (en) | Stabilized inorganic nanoparticle, stabilized inorganic nanoparticle material, method for producing stabilized inorganic nanoparticle, and method for using stabilized inorganic nanoparticle | |
| CN110724156B (en) | Method for enhancing fluorescence intensity of copper nanocluster | |
| CN111299605A (en) | Controllable preparation of gold nanoclusters wrapped by papain | |
| CN112011333B (en) | Nitrogen-containing carbon quantum dot and preparation method thereof | |
| JPWO2009066548A1 (en) | Semiconductor nanoparticles, fluorescent labeling substances and molecular / cell imaging methods using them | |
| Balci et al. | Catalytic coating of virus particles with zinc oxide | |
| CN102847951B (en) | Process for preparing gold nano particles through reduction of chloroauric acid by catalase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200619 |
|
| RJ01 | Rejection of invention patent application after publication |