CN109813424B - Flexible up-conversion green light sensor for living body and preparation method thereof - Google Patents
Flexible up-conversion green light sensor for living body and preparation method thereof Download PDFInfo
- Publication number
- CN109813424B CN109813424B CN201910082128.XA CN201910082128A CN109813424B CN 109813424 B CN109813424 B CN 109813424B CN 201910082128 A CN201910082128 A CN 201910082128A CN 109813424 B CN109813424 B CN 109813424B
- Authority
- CN
- China
- Prior art keywords
- green light
- conversion
- flexible
- preparing
- light sensor
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a flexible up-conversion green light sensor for a living body and a preparation method thereof, wherein the method comprises the following steps: 1) preparing and characterizing a green light emission upconversion micron rod doped with rare earth erbium element; 2) preparing a flexible up-conversion green light sensor: (1) pre-laying a layer of polyester film on a glass sheet, preparing polydimethylsiloxane precursors with different proportions of 10: 1-7: 1, mixing with rare earth erbium element-doped green light emission up-conversion micrometer rods with the weight of 10-100 mg/ml, vacuumizing for 30-40 min under the negative pressure of 0.03-0.05 MPa, and uniformly spin-coating the mixture on the polyester film; (2) after the liquid forms a film with the thickness of 0.2mm to 3mm, curing the film for 30min to 60min at the high temperature of 80 ℃ in vacuum; (3) after the cooling, the pressing is carried out to avoid the generation of bubbles. The flexible up-conversion green light sensor for living bodies prepared by the invention has the area of 25mm2～1cm2Under the excitation of 980nm near-infrared light, the fluorescent material can emit bright green light with the wavelength of 540nm, can be embedded in subcutaneous tissues of living animals, and has higher green light conversion efficiency; has low biological toxicity.
Description
Technical Field
The invention belongs to the technical field of biotechnology and materials, and particularly relates to a flexible up-conversion green light sensor for a living body and a preparation method thereof.
Background
The up-conversion luminescent material is a material which absorbs long-wavelength light and emits short-wavelength light, and has long excitation light wavelength (980nm) and good tissue penetrability, so that the up-conversion luminescent material is widely applied to disease treatment, signal path regulation and the like of living bodies. The application modes of the up-conversion material in living bodies mainly comprise a local injection mode and a tail vein injection mode, but the two modes have limitations. First, the upconverting material component is a rare earth metal, and its safety for application to a living body needs to be carefully considered. The biological toxicity is usually reduced by complex surface modification methods, such as citric acid surface modification, polyethylene glycol coated surface and the like, while excessive modification of the up-conversion material can affect the photon yield and greatly weaken the luminous efficiency; second, the up-conversion is gradually metabolized in vivo through long-term blood circulation or body fluid circulation, and a common method is multiple injections, which has a high demand for the amount of up-conversion and causes a large metabolic burden on the living body. Therefore, an up-conversion light sensing method which is simple in preparation method, low in price and completely nontoxic to living bodies is developed, and the up-conversion light sensing method is more conveniently applied to subsequent biochemical researches and the like.
Disclosure of Invention
The invention provides a flexible up-conversion green light sensor for living bodies and a preparation method thereof, aiming at overcoming the defects of the prior art, and having the advantages of high luminous efficiency and high biological safety.
The technical scheme of the invention is a preparation method of a flexible up-conversion green light sensor for living bodies, which comprises the following steps:
1) preparing and characterizing a green light emission upconversion micron rod doped with rare earth erbium element;
2) and preparing the flexible upconversion green light sensor for the living body.
The preparation of the green light emission up-conversion micron rod doped with the rare earth erbium element in the step 1) comprises the following specific steps:
(1) 1.25g of sodium hydroxide and 8mL of double distilled water are sequentially added into a round-bottom flask, stirring is carried out at 300rpm for 10min until the solution is clear and transparent, 25mL of absolute ethyl alcohol and oleic acid with the same volume are sequentially added dropwise while stirring, and after stirring is carried out at 300rpm for 30min at room temperature, the solution in the flask is uniform and stable;
(2) taking yttrium nitrate hexahydrate (YCl)3·6H2O), ytterbium nitrate hexahydrate (YbCl)3·6H2O), erbium nitrate hexahydrate (ErCl)3·6H2O) is evenly mixed according to the proportion of 40:10:1-42:10:1 and stirred for 10min at room temperature at 800 rpm;
(3) adding 2.5ml of 2M ammonium fluoride solution, stirring at 800rpm for 30min, transferring the reaction system into a high-temperature reaction kettle, and reacting at 180 ℃ for 12 h; after the reaction is finished, naturally cooling to room temperature, ultrasonically suspending the obtained white precipitate by using equal volume of ethanol, centrifuging at 5000rpm for 10min, and repeating for 5 times; transferring the mixture into 2M hydrochloric acid solution, performing ultrasonic treatment for 5min, and cleaning with double distilled water for 5 times; the obtained transparent liquid is the monodisperse stable green light emission up-conversion fluorescent micrometer rod.
The preparation method of the flexible up-conversion green light sensor in the step 2) comprises the following specific steps:
(1) pre-laying a layer of polyester film on a glass sheet, preparing polydimethylsiloxane precursors with different proportions of 10: 1-7: 1, mixing with rare earth erbium element-doped green light emission up-conversion micrometer rods with the weight of 10-100 mg/ml, vacuumizing for 30-40 min under the negative pressure of 0.03-0.05 MPa, and uniformly spin-coating the mixture on the polyester film;
(2) after the liquid forms a film with the thickness of 0.2mm to 3mm, curing the film for 30min to 60min at the high temperature of 80 ℃ in vacuum;
(3) after the cooling, a layer of polyester film is laid on the top layer, and the top layer is compressed to avoid bubbles.
It is a second object of the present invention to provide a flexible up-conversion green sensor for living bodies using the above method, having an area of 25mm2～1cm2And the thickness is 0.2 mm-3 mm.
Advantageous effects
1. The flexible up-conversion green light sensor for living bodies prepared by the invention has the area of 25mm2～1cm2Under the excitation of 980nm near-infrared light, the fluorescent material can emit bright green light with the wavelength of 540nm, can be embedded in subcutaneous tissues of living animals, and has higher green light conversion efficiency; has low biological toxicity.
2. The diameter of the prepared rare earth erbium element doped green light emission up-conversion micron rod is 1-2 mu m, and the emission wavelength under the excitation of 980nm wavelength near infrared light is 540 nm.
3. The area of the prepared flexible up-conversion green light sensor is 25mm2～1cm2And the thickness is 0.2 mm-3 mm.
4. The prepared flexible up-conversion green light sensor can be embedded in a living nude mouse, has higher biological safety and luminous efficiency, and can be used for living body light conversion.
5. The invention encapsulates the up-conversion micron rods into the polydimethylsiloxane flexible substrate, avoids the direct contact of up-conversion and cells, and omits a series of complicated material transformation steps while ensuring the photon yield; meanwhile, in order to prevent the in vivo leakage of the up-conversion particles, the polyester film is encapsulated in the outer layer, so that the up-conversion particles have higher biological safety. Has a high scientific research application prospect in the fields of biotechnology and materials such as optogenetics and the like.
Drawings
FIG. 1 is a diagram of a synthetic path and a real object of a prepared flexible up-conversion green light sensor for living bodies.
Fig. 2 is a low-power transmission electron micrograph of a prepared rare earth erbium element doped green light emission up-conversion micron rod.
Fig. 3 is a luminescence spectrum of a green emission up-conversion nanorod doped with rare earth erbium prepared.
Detailed Description
The invention is further illustrated by the following specific examples and the accompanying drawings. The examples are intended to better enable those skilled in the art to better understand the present invention and are not intended to limit the present invention in any way.
Example 1
Preparation of flexible up-conversion green light sensor for living body
Pre-laying a layer of polyester film on a glass sheet, preparing a 10:1 polydimethylsiloxane precursor, mixing with a rare earth erbium element-doped green light emission up-conversion micrometer rod of 10mg/ml, vacuumizing for 30min at a negative pressure of 0.03MPa to remove bubbles, uniformly spin-coating the mixture on the polyester film, after the liquid is formed into a film of 0.2mm, curing at 80 ℃ for 30min in vacuum at high temperature, and after the liquid is cooled, laying a layer of polyester film on the top layer to avoid bubbles (figure 1).
Example 2
Preparation of flexible up-conversion green light sensor for living body
Pre-laying a layer of polyester film on a glass sheet, preparing a polydimethylsiloxane precursor with a ratio of 9:1, mixing a rare earth erbium element-doped green light emission up-conversion micrometer rod of 10mg/ml, vacuumizing for 40min at a negative pressure of 0.03MPa to remove bubbles, uniformly spin-coating the mixture on the polyester film, after the liquid is formed into a film of 1mm, curing at a high temperature of 80 ℃ in vacuum for 40min, and after cooling, laying a layer of polyester film on the top layer to avoid bubbles.
Example 3
Preparation of flexible up-conversion green light sensor for living body
Pre-laying a layer of polyester film on a glass sheet, preparing a polydimethylsiloxane precursor with the proportion of 7:1, mixing 100mg/ml of rare earth erbium element doped green light emission upconversion micrometer rods, vacuumizing for 40min at the negative pressure of 0.03MPa to remove bubbles, uniformly spin-coating the mixture on the polyester film, curing at the high temperature of 80 ℃ for 60min in vacuum after the liquid is formed into a film of 3mm, and laying a layer of polyester film on the top layer after the liquid is cooled to avoid bubbles.
Example 4
Preparation of flexible up-conversion green light sensor for living body
Pre-laying a layer of polyester film on a glass sheet, preparing a polydimethylsiloxane precursor with the proportion of 7:1, mixing 100mg/ml of rare earth erbium element doped green light emission upconversion micrometer rods, vacuumizing for 40min under the negative pressure of 0.05MPa to remove bubbles, uniformly spin-coating the mixture on the polyester film, curing at the high temperature of 80 ℃ in vacuum for 60min after the liquid is formed into a film of 3mm, and laying a layer of polyester film on the top layer after the liquid is cooled to avoid bubbles.
Example 5
Preparation of green light emission up-conversion micron rod doped with rare earth erbium element
1.25g of sodium hydroxide and 8mL of double distilled water are sequentially added into a round-bottom flask, and the mixture is stirred at 300rpm for 10min until the solution is clear and transparent. 25mL of absolute ethanol and an equal volume of oleic acid were added dropwise in sequence with stirring. After stirring at 300rpm for 30min at room temperature, the solution in the flask was uniform and stable. Taking yttrium nitrate hexahydrate (YCl)3·6H2O), ytterbium nitrate hexahydrate (YbCl)3·6H2O), erbium nitrate hexahydrate (ErCl)3·6H2O) are evenly mixed according to the ratio of 40:10:1 and stirred for 10min at room temperature at 800 rpm. 2.5ml of 2M ammonium fluoride solution is added, the mixture is stirred for 30min at 800rpm, and the reaction system is transferred to a high-temperature reaction kettle and reacts for 12h at 180 ℃. After the reaction is finished, naturally cooling to room temperature, ultrasonically suspending the obtained white precipitate by using equal volume of ethanol, centrifuging at 5000rpm for 10min, and repeating for 5 times. Transferring the mixture to a concentration of 2MUltrasonic treating in hydrochloric acid solution for 5min, and washing with double distilled water for 5 times. The obtained transparent liquid is the monodisperse stable green light emission up-conversion fluorescent micrometer rod. (FIG. 2, FIG. 3)
Example 6
Preparation of green light emission up-conversion micron rod doped with rare earth erbium element
1.25g of sodium hydroxide and 8mL of double distilled water are sequentially added into a round-bottom flask, and the mixture is stirred at 300rpm for 10min until the solution is clear and transparent. 25mL of absolute ethanol and an equal volume of oleic acid were added dropwise in sequence with stirring. After stirring at 300rpm for 30min at room temperature, the solution in the flask was uniform and stable. Taking yttrium nitrate hexahydrate (YCl)3·6H2O), ytterbium nitrate hexahydrate (YbCl)3·6H2O), erbium nitrate hexahydrate (ErCl)3·6H2O) are evenly mixed according to the ratio of 41:10:1 and stirred for 10min at room temperature at 800 rpm. 2.5ml of 2M ammonium fluoride solution is added, the mixture is stirred for 30min at 800rpm, and the reaction system is transferred to a high-temperature reaction kettle and reacts for 12h at 180 ℃. After the reaction is finished, naturally cooling to room temperature, ultrasonically suspending the obtained white precipitate by using equal volume of ethanol, centrifuging at 5000rpm for 10min, and repeating for 5 times. The mixture was transferred to a 2M hydrochloric acid solution with sonication for 5min and washed again 5 times with double distilled water. The obtained transparent liquid is the monodisperse stable green light emission up-conversion fluorescent micrometer rod.
Example 7
Preparation of green light emission up-conversion micron rod doped with rare earth erbium element
1.25g of sodium hydroxide and 8mL of double distilled water are sequentially added into a round-bottom flask, and the mixture is stirred at 300rpm for 10min until the solution is clear and transparent. 25mL of absolute ethanol and an equal volume of oleic acid were added dropwise in sequence with stirring. After stirring at 300rpm for 30min at room temperature, the solution in the flask was uniform and stable. Taking yttrium nitrate hexahydrate (YCl)3·6H2O), ytterbium nitrate hexahydrate (YbCl)3·6H2O), erbium nitrate hexahydrate (ErCl)3·6H2O) are evenly mixed according to the proportion of 42:10:1 and stirred for 10min at room temperature at 800 rpm. 2.5ml of 2M ammonium fluoride solution is added, the mixture is stirred for 30min at 800rpm, and the reaction system is transferred to a high-temperature reaction kettle and reacts for 12h at 180 ℃. After the reaction is finished, naturallyAfter cooling to room temperature, the resulting white precipitate was ultrasonically suspended in an equal volume of ethanol, centrifuged at 5000rpm for 10min, and repeated 5 times. The mixture was transferred to a 2M hydrochloric acid solution with sonication for 5min and washed again 5 times with double distilled water. The obtained transparent liquid is the monodisperse stable green light emission up-conversion fluorescent micrometer rod.
Example 8
The flexible up-conversion green light sensor is implanted under the skin of a nude mouse
(1) In a clean bench, a flexible up-conversion green light sensor which is irradiated by ultraviolet light and sterilized overnight is cut into 25mm2Removing acute angles;
(2) after 10 percent chloral hydrate is used for intraperitoneal injection anesthesia on female 7-week-old BALB/c n mu de strain nude mice according to the weight, the skin surface is disinfected by iodophor;
(3) cutting a wound on the skin by using an operating scissors according to the size of the actual sensor, removing subcutaneous connective tendons, clamping the sensor by using forceps to plant the sensor in the gap between the skin and the fascia, and then performing surgical suture;
(3) the light sensing effect of the subcutaneous sensor can be observed after one week.
It should be understood that the embodiments and examples discussed herein are illustrative only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims.
Claims (2)
1. A method for preparing a flexible up-conversion green light sensor for a living body is characterized by comprising the following steps:
1) preparing and characterizing a green light emission upconversion micron rod doped with rare earth erbium element;
2) preparing a flexible up-conversion green light sensor;
the preparation of the green light emission up-conversion micron rod doped with the rare earth erbium element in the step 1) comprises the following specific steps:
(1) 1.25g of sodium hydroxide and 8mL of double distilled water are sequentially added into a round-bottom flask, stirring is carried out at 300rpm for 10min until the solution is clear and transparent, 25mL of absolute ethyl alcohol and oleic acid with the same volume are sequentially added dropwise while stirring, and after stirring is carried out at 300rpm for 30min at room temperature, the solution in the flask is uniform and stable;
(2) taking yttrium nitrate hexahydrate (YCl)3·6H2O), ytterbium nitrate hexahydrate (YbCl)3·6H2O), erbium nitrate hexahydrate (ErCl)3·6H2O) is evenly mixed according to the proportion of 40:10:1-42:10:1 and stirred for 10min at room temperature at 800 rpm;
(3) adding 2.5ml of 2M ammonium fluoride solution, stirring at 800rpm for 30min, transferring the reaction system into a high-temperature reaction kettle, and reacting at 180 ℃ for 12 h; after the reaction is finished, naturally cooling to room temperature, ultrasonically suspending the obtained white precipitate by using equal volume of ethanol, centrifuging at 5000rpm for 10min, and repeating for 5 times; transferring the mixture into 2M hydrochloric acid solution, performing ultrasonic treatment for 5min, and cleaning with double distilled water for 5 times; the obtained transparent liquid is a monodisperse stable green light emission up-conversion fluorescent micron rod;
the preparation method of the flexible up-conversion green light sensor in the step 2) comprises the following specific steps:
(1) pre-laying a layer of polyester film on a glass sheet, preparing polydimethylsiloxane precursors with different proportions of 10: 1-7: 1, mixing with rare earth erbium element-doped green light emission up-conversion micrometer rods with the weight of 10-100 mg/ml, vacuumizing for 30-40 min under the negative pressure of 0.03-0.05 MPa, and uniformly spin-coating the mixture on the polyester film;
(2) after the liquid forms a film with the thickness of 0.2mm to 3mm, curing the film for 30min to 60min at the high temperature of 80 ℃ in vacuum;
(3) after the cooling, a layer of polyester film is laid on the top layer, and the top layer is compressed to avoid bubbles.
2. A flexible up-conversion green sensor for living bodies prepared by the method of claim 1, wherein the flexible up-conversion green sensor has an area of 25mm2～1cm2And the thickness is 0.2 mm-3 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910082128.XA CN109813424B (en) | 2019-01-28 | 2019-01-28 | Flexible up-conversion green light sensor for living body and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910082128.XA CN109813424B (en) | 2019-01-28 | 2019-01-28 | Flexible up-conversion green light sensor for living body and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109813424A CN109813424A (en) | 2019-05-28 |
| CN109813424B true CN109813424B (en) | 2021-01-15 |
Family
ID=66605511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910082128.XA Expired - Fee Related CN109813424B (en) | 2019-01-28 | 2019-01-28 | Flexible up-conversion green light sensor for living body and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109813424B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385448B (en) * | 2015-10-21 | 2017-07-11 | 哈尔滨工程大学 | The enhanced nucleocapsid up-conversion luminescence nano-carrier of feux rouges and preparation method |
| WO2017125951A1 (en) * | 2016-01-22 | 2017-07-27 | Council Of Scientific And Industrial Research | A lanthanum based upconverting microrods and application thereof |
| CN107041947B (en) * | 2016-02-05 | 2021-05-18 | 何玉龙 | Protective effect and application of FSTL1 in anti-fibrosis homeostatic regulation of tissues such as liver |
| CN105778916B (en) * | 2016-03-14 | 2019-02-26 | 哈尔滨工程大学 | The preparation of fluorescent liquid microballoon with Cellular tracking function and application method |
-
2019
- 2019-01-28 CN CN201910082128.XA patent/CN109813424B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN109813424A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wilhelm | Perspectives for upconverting nanoparticles | |
| Wang et al. | Large hollow cavity luminous nanoparticles with near-infrared persistent luminescence and tunable sizes for tumor afterglow imaging and chemo-/photodynamic therapies | |
| Li et al. | Near-infrared light activated persistent luminescence nanoparticles via upconversion | |
| Yu et al. | Lanthanide-doped near-infrared II luminescent nanoprobes for bioapplications | |
| Abdukayum et al. | Functional near infrared-emitting Cr3+/Pr3+ co-doped zinc gallogermanate persistent luminescent nanoparticles with superlong afterglow for in vivo targeted bioimaging | |
| Singh | Red and near infrared persistent luminescence nano-probes for bioimaging and targeting applications | |
| CN102031110A (en) | InP/ZnS core-shell structure quantum dot and preparation method thereof | |
| CN114836216B (en) | Rare earth nanocomposite capable of improving singlet oxygen generation, preparation method and application thereof | |
| CN109758589B (en) | Flexible up-conversion blue light sensor capable of regulating and controlling cryptochrome CRY2 protein allosteric in living body and preparation method thereof | |
| CN109675060B (en) | Flexible up-conversion red light sensor for living body and preparation method thereof | |
| CN112370535A (en) | Tumor microenvironment response type OFF-ON upconversion fluorescent probe and preparation method and application thereof | |
| CN109813424B (en) | Flexible up-conversion green light sensor for living body and preparation method thereof | |
| CN107033908A (en) | A kind of GdF3:Yb3+,Er3+The preparation method of upconversion fluorescence nano material | |
| CN116285949B (en) | Rare earth nano fluorescent material with core-shell structure and preparation method and application thereof | |
| CN110724517B (en) | Rare earth/chlorophyll composite probe and preparation method and application thereof | |
| CN115818621B (en) | Biomass-derived carbon nano particle with near infrared two-region light emission characteristic and preparation method and application thereof | |
| CN114292639B (en) | Multifunctional nano material based on aggregation-induced emission and MXenes, preparation method and application | |
| CN108192595B (en) | Magnetic-up-conversion nanoparticle aggregate and preparation method thereof | |
| CN114425092B (en) | MRI/NIR II dual-mode imaging spray contrast agent and preparation method and application thereof | |
| CN115895641A (en) | Short-wave infrared fluorescence emission rare earth nano material and preparation method thereof | |
| CN112877055B (en) | Holmium-based up-conversion nanomaterial and preparation method thereof | |
| CN113292988A (en) | Rare earth core-shell nano material and preparation method thereof | |
| Shang et al. | Bioimaging and prospects of night pearls‐based persistence phosphors in cancer diagnostics | |
| CN106674561B (en) | The preparation method of the gelatin-compounded conductive film of polypyrrole- | |
| CN107880886A (en) | One kind has magnetic fluorescence multi-functional nanometer material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210115 Termination date: 20220128 |