CN116656344B - Preparation method of fluorescent nanocluster for humidity sensor - Google Patents
Preparation method of fluorescent nanocluster for humidity sensor Download PDFInfo
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- CN116656344B CN116656344B CN202310532532.9A CN202310532532A CN116656344B CN 116656344 B CN116656344 B CN 116656344B CN 202310532532 A CN202310532532 A CN 202310532532A CN 116656344 B CN116656344 B CN 116656344B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 19
- 108010024636 Glutathione Proteins 0.000 claims abstract description 9
- 229960003180 glutathione Drugs 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000002776 aggregation Effects 0.000 abstract description 9
- 238000004220 aggregation Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 4
- 235000013399 edible fruits Nutrition 0.000 abstract description 4
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 235000013311 vegetables Nutrition 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a preparation method of a fluorescent nanocluster for a humidity sensor, and belongs to the field of nanomaterial synthesis. According to the method, a simple solid state grinding method is adopted, so that silver (I) nitrate and a thiol group in glutathione are coordinated to form a silver (I) -thioacid complex, and then trace water is added to realize aggregation of the complex to generate a nanocluster with strong fluorescence. The strong fluorescent nanocluster is synthesized by utilizing water molecule induction aggregation, so that the humidity sensor can be prepared and used for detecting the content of water molecules in the environment. The non-fluorescent nanoclusters are converted into fluorescent nanoclusters when present in an aqueous environment, and can be used for detecting the surface layers of biological materials such as fruits, vegetables and the like. For example, the moisture content of the waxed and non-waxed fruit surfaces is different. This can be easily detected by changing their fluorescence intensity from non-fluorescent nanoclusters to fluorescent nanoclusters. Compared with the prior art, the fluorescent nanocluster prepared by the method has a simpler synthesis process, and is simultaneously suitable for various metal ions and alloy nanoclusters. The preparation method has the advantages of easily available raw materials, simple preparation process, easiness in realizing rapid and efficient mass production and the like, reduces the use of the raw materials, has zero pollution and no toxicity, is environment-friendly, and can be popularized to practical application on a large scale.
Description
Technical Field
The invention belongs to the field of nano material synthesis, and in particular relates to a method for preparing a nano cluster with a fluorescence enhancement effect by adopting a solid state grinding method and inducing the nano cluster to aggregate through water molecules, which can be used for preparing a humidity sensor and detecting the content of water molecules in the environment.
Background
Over the past few decades, ultra-small luminescent metal nanoclusters composed of several to hundreds of metal atoms have emerged as an emerging functional material in the field of view of the public. Because of its strong fluorescence effect, large stokes shift, good biocompatibility and excellent photo-thermal stability, metal nanoclusters are widely used in the fields of catalysis, energy conversion, medical health, electronics, photonics, and the like. In general, for most nanoclusters having a fluorescence effect, fluorescence is reduced or quenched after the solid nanoclusters are aggregated to the maximum extent, which may seriously affect the use of the solid nanoclusters in real life. Therefore, the realization of the fluorescence enhancement effect of the solid nanoclusters is of great research significance. In the previous research, the solution is used for synthesizing the nanocluster polymer, then the weak polar solvent, metal ions or heating and other means are used for inducing aggregation to realize fluorescence enhancement, and the method has the advantages of complex synthesis process, long time consumption and high raw material consumption; in our research, a solid state milling method is used to synthesize nanocluster polymers, then a strong polar aqueous solvent is used to induce aggregation to realize fluorescence enhancement, no other solvent is needed in the synthesis process, raw material consumption is reduced, the synthesis process is fast and efficient, and the method can be used to prepare humidity sensors and is used for detecting the content of water molecules in the environment. The non-fluorescent nanoclusters are converted into fluorescent nanoclusters when present in an aqueous environment, and can be used for detecting the surface layers of biological materials such as fruits, vegetables and the like. For example, the moisture content of the waxed and non-waxed fruit surfaces is different. This can be easily detected by changing their fluorescence intensity from non-fluorescent nanoclusters to fluorescent nanoclusters. Compared with the traditional method, the method is simpler, easy to synthesize and high in yield, and has important guiding significance for further researching the fluorescent nanocluster and the practical application thereof.
Disclosure of Invention
[ problem to be solved ]
The invention aims to develop a universal simple synthesis method for preparing nanoclusters with fluorescence enhancement effect, preparing humidity sensors and using the nanoclusters for detecting the content of water molecules in the environment. The method has mild synthesis conditions, simple synthesis process, easy realization of rapid and efficient mass production, and wider applicability to various metal ions and alloy nanoclusters.
Technical scheme
The invention adopts the following technical scheme:
according to the method, a solid state grinding method is utilized, so that a silver (I) -thioacid complex is formed by coordination of a silver (I) nitrate and a thiol group in glutathione, and then a trace amount of water is added to realize aggregation of the complex to generate a nano cluster with strong fluorescence. The invention provides a simple and universal method for preparing the nanocluster with fluorescence enhancement effect, which can be used for preparing a humidity sensor and detecting the content of water molecules in the environment, and the wide applicability is also applicable to various metal ions and alloy nanoclusters thereof.
A. Preparation of silver (I) -thioacid complexes
The weighed glutathione and silver nitrate are placed in a mortar, fully ground to obtain white powder, and no fluorescence is generated under the irradiation of an ultraviolet lamp.
B. Preparation of fluorescent nanoclusters
And C, adding a small amount of water into the white powder in the step A, rapidly grinding to a dry state to obtain white powder, and emitting bright yellow fluorescence under the irradiation of an ultraviolet lamp to obtain the fluorescent nanoclusters.
C. Detection of humidity in an environment
And (c) placing the nanoclusters in the step A under the condition of different humidity, and observing the reaction time required by the nanoclusters from non-fluorescence to fluorescence under the irradiation of an ultraviolet lamp.
In a further technical scheme of the invention, in the step A, the mass of the glutathione is 200mg; the mass of silver nitrate was 23mg and the inner diameter of the mortar was 70mm.
According to a further embodiment of the present invention, in the step B, the volume of the water is 20. Mu.L.
In the further technical scheme of the invention, in the step C, the humidity is respectively 50%,60%,70% and 80%; the corresponding reaction times were 78min,40min,30min and 15min, respectively.
The nanocluster obtained by the preparation method can generate bright yellow fluorescence through water molecule induced aggregation, and can be widely used for detecting the content of water molecules in the environment.
The present invention will be described in detail below.
A method for preparing a fluorescent nanocluster for a humidity sensor, comprising the steps of:
A. preparation of silver (I) -thioacid complexes
200mg of glutathione and 23mg of silver nitrate are weighed and placed in a mortar, and are sufficiently ground to obtain white powder, and no fluorescence is generated under the irradiation of an ultraviolet lamp.
In the invention, monovalent silver ions in silver nitrate and thiol groups in glutathione form silver (I) -thioacid complexes through coordination.
B. Preparation of fluorescent nanoclusters
And (C) adding 20 mu L of water into the white powder in the step (A), rapidly grinding to a dry state to obtain white powder, and emitting bright yellow fluorescence under the irradiation of an ultraviolet lamp to obtain the fluorescent nanoclusters.
In the present invention, water induces aggregation of the silver (I) -thioacid complex from non-fluorescent to bright yellow fluorescent.
C. Detection of humidity in an environment
Placing the fluorescent nanoclusters in the step A under the conditions of different humidity to be 50%,60%,70% and 80% respectively; the reaction time required for the nanoclusters to go from non-fluorescent to fluorescent was observed under uv lamp irradiation. The corresponding reaction times were 78min,40min,30min and 15min, respectively.
According to the invention, the humidity sensor can be prepared according to response time of the fluorescent nanoclusters to different humidities, and the content of water molecules in the environment is detected.
The nanocluster obtained by the preparation method can generate bright yellow fluorescence through water molecule induced aggregation, and can be widely used for detecting the content of water molecules in the environment.
[ advantageous effects ]
Compared with the prior art, the invention has the following beneficial effects:
compared with the prior art, the fluorescent nanocluster prepared by the method has a simpler synthesis process, and is simultaneously suitable for various metal ions and alloy nanoclusters. The nano clusters with strong fluorescence are synthesized through the induction and aggregation of water molecules, so that the humidity sensor can be prepared and used for detecting the content of water molecules in the environment. Has the advantages of easily available raw materials, simple preparation process, easy realization of rapid and efficient mass production, and the like.
The solid state grinding method used in the invention does not need other solvents, has advantages compared with the traditional solution synthesis, reduces the use of raw materials, has zero pollution and no toxicity, is environment-friendly, and can be popularized to practical application on a large scale.
Drawings
FIG. 1 is a flow chart of a fluorescent nanocluster prepared by the method
FIG. 2 ultraviolet spectrum and fluorescence spectrum
FIG. 3 corresponding response time bar graph under different humidity conditions
Detailed Description
The invention is further illustrated and described below in connection with the following examples of the invention.
Fully grinding 200mg of glutathione and 23mg of silver nitrate in a mortar to obtain white powder, wherein the white powder does not fluoresce under the irradiation of an ultraviolet lamp; then, 20. Mu.L of water was added and the mixture was rapidly ground to a dry state to obtain a white powder, which was irradiated with an ultraviolet lamp to emit bright yellow fluorescence.
Humidity detection: 200mg of glutathione and 23mg of silver nitrate were sufficiently ground in a mortar to obtain a white powder, and the white powder was subjected to different humidity conditions, and the reaction time required from no fluorescence to occurrence of bright yellow fluorescence was observed under irradiation of an ultraviolet lamp.
Claims (4)
1. An application of fluorescent nanoclusters in detecting humidity in an environment, characterized in that: the fluorescent nanoclusters include the steps of:
A. preparation of silver (I) -thioacid complexes
Placing the weighed glutathione and silver nitrate into a mortar, fully grinding to obtain white powder, and keeping the white powder non-fluorescent under the irradiation of an ultraviolet lamp;
B. preparation of fluorescent nanoclusters
Adding a small amount of water into the white powder in the step A, rapidly grinding to a dry state to obtain white powder, and emitting bright yellow fluorescence under the irradiation of an ultraviolet lamp to obtain a fluorescent nanocluster;
C. detection of humidity in an environment
And (c) placing the nanoclusters in the step A under the condition of different humidity, and observing the reaction time required by the nanoclusters from non-fluorescence to fluorescence under the irradiation of an ultraviolet lamp.
2. The use according to claim 1, in step a, the mass of glutathione is 200mg; the mass of silver nitrate was 23mg and the inner diameter of the mortar was 70mm.
3. The use according to claim 1, wherein in step B the volume of water is 20 μl.
4. The use according to claim 1, wherein in step C the humidity is 50%,60%,70%,80%, respectively; the corresponding reaction times were 78min,40min,30min and 15min, respectively.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310532532.9A CN116656344B (en) | 2023-05-12 | 2023-05-12 | Preparation method of fluorescent nanocluster for humidity sensor |
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| CN202310532532.9A CN116656344B (en) | 2023-05-12 | 2023-05-12 | Preparation method of fluorescent nanocluster for humidity sensor |
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| CN116656344A CN116656344A (en) | 2023-08-29 |
| CN116656344B true CN116656344B (en) | 2024-04-12 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108489951A (en) * | 2018-04-20 | 2018-09-04 | 吉林大学 | Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection |
| CN114871443A (en) * | 2022-05-31 | 2022-08-09 | 电子科技大学 | Method for preparing gold nanocluster by solid-state grinding method |
| CN115283688A (en) * | 2022-07-04 | 2022-11-04 | 电子科技大学 | Method for preparing gold nanocluster by solid-phase dynamics control method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013156870A2 (en) * | 2012-04-17 | 2013-10-24 | Indian Institute Of Technology | Detection of quantity of water flow using quantum clusters |
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- 2023-05-12 CN CN202310532532.9A patent/CN116656344B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108489951A (en) * | 2018-04-20 | 2018-09-04 | 吉林大学 | Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection |
| CN114871443A (en) * | 2022-05-31 | 2022-08-09 | 电子科技大学 | Method for preparing gold nanocluster by solid-state grinding method |
| CN115283688A (en) * | 2022-07-04 | 2022-11-04 | 电子科技大学 | Method for preparing gold nanocluster by solid-phase dynamics control method |
Non-Patent Citations (3)
| Title |
|---|
| Ag9 Quantum Cluster through a Solid-State Route;Thumu Udaya B. Rao et al.;J. AM. CHEM. SOC.;20101029;第132卷;第16304-16307页 * |
| Gold cluster incorporated Rhenium disulfide: An efficient catalyst towards electrochemical and photoelectrochemical hydrogen evolution reaction;Aruna Vijayan et al.;Electrochimica Acta;20230223;第446卷;第142073页 * |
| 荧光手性银纳米簇的制备、表征及用于手性分子的检测研究;黄诚;中国优秀硕士学位论文全文 数据库 工程科技Ⅰ辑;20180315(第3期);B014-619 * |
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