CN113465769B - Preparation method of double-emission nano fluorescent thermometer - Google Patents
Preparation method of double-emission nano fluorescent thermometer Download PDFInfo
- Publication number
- CN113465769B CN113465769B CN202110760520.2A CN202110760520A CN113465769B CN 113465769 B CN113465769 B CN 113465769B CN 202110760520 A CN202110760520 A CN 202110760520A CN 113465769 B CN113465769 B CN 113465769B
- Authority
- CN
- China
- Prior art keywords
- solution
- fluorescent
- steps
- preparing
- fluorescent nano
- 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.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A preparation method and application of a double-emission fluorescent nano thermometer relate to a preparation method and application of a temperature nano sensor. The method comprises the following steps: 1. stirring sodium polymethacrylate and silver nitrate in a magnetic stirrer, magnetically stirring, adjusting pH, and irradiating under an ultraviolet lamp to obtain a solution A; 2. adding a certain amount of chitosan into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging the obtained turbid liquid to obtain a solution B; 3. the solution A and the solution B are mixed and stirred to obtain the solution C, namely the double-emission carbonized polymer dot-silver nanocluster composite fluorescent thermometer material.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a double-emission fluorescent nano thermometer and a preparation method thereof.
Background
Temperature is one of seven basic physical quantities expressing a certain chemical or physical phenomenon, and plays a very important role in human life, scientific research and industrial production. Therefore, temperature detection, particularly high-precision temperature detection, plays an indispensable role in life, learning, production and research. An optical temperature sensor has the advantages of non-contact sensing, high heat resistance, wide temperature range, no influence on the original temperature, high response speed and the like, and is attracting more and more attention, and in recent years, fluorescent carbon dots are attracting attention of researchers as temperature sensors.
Due to their widespread use (electronics, biology, medical diagnostics) of fluorescent thermometers, accurate measurement of them is increasingly important. To date, some promising local temperature sensing materials are being designed, including scanning probe microscopy, raman spectroscopy, and fluorescence-based measurements, with fluorescence-based nanosensors receiving particular attention due to their fast response, high spatial resolution, and safety for remote processing. In fact, some fluorescent nanomaterials using semiconductor quantum dots, organic dyes, fluorescent polymers have been reported for temperature detection.
Intracellular temperature plays an important role in many biological events, as temperature determines the kinetics and reactivity of a large number of biomolecules within a cell. Thus, accurate measurement of cell temperature and its changes within the cell may be helpful in the development of cell biology and biomedicine. For this reason, intracellular temperature sensing using fluorescent materials is a potentially useful tool for real-time and in vivo monitoring of important cellular analytes. In recent years, a large number of fluorescent probes have been developed for measuring temperatures, such as fluorescent dyes, fluorescent polymer nanoparticles, semiconductor quantum dots, carbon dots, and metal nanoclusters. Fluorescent carbon nanodots are becoming a new star in the family of carbon-based nanomaterials, and are attracting more and more attention because of their excellent advantages of easy preparation and functionalization, no/low toxicity, high light stability, etc. These unique properties make them prominent in a wide variety of applications such as drug delivery, biological imaging, and optical sensing. Recently, carbon dot based fluorescent nano-thermometers have been implemented for spatially resolved temperature measurement of living cells.
Temperature plays a critical role in biological reactions and functions. They also provide dual functions of imaging and temperature sensing. Many promising fluorescent nanomaterials, such as semiconductor quantum dot metal nanoclusters, carbon nanomaterials and rare earth doped nanoparticles, have been successfully applied to nanothermometers for biological and medical diagnostics. However, these single-emission fluorescent nanothermometers do not accurately reflect changes in local temperature and temperature gradients at the nanoscale or sub-nanoscale due to poor chemical stability in complex environments. This inherent limitation encourages the development of new fluorescent nanothermometers. In contrast, the sensitivity and stability of the dual luminescence fluorescent nano thermometer have great development prospects.
Disclosure of Invention
The invention aims to provide a preparation method of a temperature-sensitive controllable double-emission nano fluorescent thermometer with fluorescent property.
The preparation method of the double-emission nano fluorescent thermometer is characterized by comprising the following steps of:
1. dissolving a silver source raw material and a polymerization monomer in deionized water, performing ultrasonic dissolution at room temperature, stirring in a magnetic stirrer, performing magnetic stirring, adjusting pH, and then irradiating under an ultraviolet lamp to obtain a solution A, wherein the volume ratio of the molar quantity of the silver source raw material to the deionized water is (25) mmol: (3) mL; the volume ratio of the molar quantity of the polymerized monomer raw material to deionized water is (1000) mmol: (33) mL;
2. adding chitosan into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging the obtained turbid liquid to obtain a solution B;
3. and (3) mixing the solution A obtained in the step (A) with the solution B obtained in the step (B) and stirring to obtain a solution C, namely the double-emission carbonized polymer dot-silver nanocluster composite fluorescent thermometer material.
In the first step, the silver source raw material is silver nitrate, and the polymerized monomer is sodium polymethacrylate.
Further, in the first step, the stirring speed of the magnetic stirrer is 600-800 r/min.
Further, in the first step, the pH value is 6.
Further, in the first step, the irradiation wavelength of the ultraviolet lamp is 365 and nm, and the time is 40 minutes.
Further, the hydrothermal reaction temperature in the second step is 180 ℃ and the time is 7 hours.
Further, the centrifugation rate in the second step is 8000r/min.
Further, the stirring time in the third step is 10 minutes.
The method is used for preparing the double-emission nano fluorescent thermometer.
The principle of the invention is as follows:
in recent years, photoluminescent nanocomposites have received extensive attention for their sensitivity and selective response to external stimuli and have shown great potential for use in thermal sensors, drug delivery, biological probes, and chemical sensors, among others. However, these single-emission fluorescent nanothermometers do not accurately reflect changes in local temperature and temperature gradients at the nanoscale or sub-nanoscale due to poor chemical stability in complex environments. This inherent limitation encourages the development of new fluorescent nanothermometers. In contrast, the sensitivity and stability of the dual luminescence fluorescent nano thermometer have great development prospects.
The fluorescent nano thermometer of the invention is in orange water solution state under natural light, and the fluorescent nano sensor under 365 and nm ultraviolet light shows pink fluorescence. The fluorescence intensity is sensitive along with the temperature change, and has good reciprocability to the temperature.
The invention has the beneficial effects that:
1. the preparation method of the double-emission nano fluorescent thermometer provided by the invention is simple, low in cost and easy for mass preparation, and special equipment is not needed in the preparation process. The controllability is strong, and the repeatability is good. 2. Has dual response performance of fluorescence property and temperature sensitivity, namely, has reversible change along with the increase or decrease of the ambient temperature. 3. The temperature response range of the linear change of the fluorescence property of the prepared nano fluorescence thermometer is 20-85 ℃, and the nano fluorescence thermometer with excellent property is prepared.
Drawings
FIG. 1 is a fluorescence excitation spectrum and a fluorescence emission spectrum of the fluorescent nanothermometer prepared in example 1;
FIG. 2 is a graph showing fluorescence change at 20℃to 85℃of the fluorescent nanothermometer prepared in example 1;
FIG. 3 is a graph showing the linear change of the maximum fluorescence intensity with ambient temperature of the fluorescent nanothermometer prepared in example 1;
FIG. 4 is the heating and cooling cycle fluorescence intensity at the maximum fluorescence intensity of the fluorescent nanothermometer prepared in example 1.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the double-emission fluorescent nano thermometer is characterized by comprising the following steps of:
1. dissolving a silver source raw material and a polymerization monomer in deionized water, performing ultrasonic dissolution at room temperature, stirring in a magnetic stirrer, performing magnetic stirring, adjusting pH, and then irradiating under an ultraviolet lamp to obtain a solution A, wherein the volume ratio of the molar quantity of the silver source raw material to the deionized water is (25) mmol: (3) mL; the volume ratio of the molar quantity of the polymerized monomer raw material to deionized water is (1000) mmol: (33) mL;
2. adding chitosan into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging the obtained turbid liquid to obtain a solution B;
3. and (3) mixing the solution A obtained in the step (A) with the solution B obtained in the step (B) and stirring to obtain a solution C, namely the double-emission carbonized polymer dot-silver nanocluster composite fluorescent thermometer material.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: in the first step, the silver source raw material is silver nitrate, and the polymerized monomer is sodium polymethacrylate. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: in the first step, the stirring speed of the magnetic stirrer is 600-800 r/min. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: and in the first step, the pH value is 6. The other is the same as in one of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the irradiation wavelength of the ultraviolet lamp in the first step is 365 and nm, and the time is 40 minutes. The others are the same as in one to one fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: in the first step, the volume ratio of the mol of the silver source raw material to deionized water is (25) mmol: (3) mL; the volume ratio of the molar quantity of the polymerized monomer raw material to deionized water is (1000) mmol: (33) mL. The others are the same as in one of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: and in the second step, the hydrothermal reaction temperature is 180 ℃ and the time is 7 hours. The others are the same as in one of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and in the second step, the centrifugal speed is 8000r/min. The other is the same as in one of the first to seventh embodiments.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the stirring time in the third step is 10 minutes. The others are the same as in one to eight embodiments.
The following examples of the present invention are described in detail, and are provided by taking the technical scheme of the present invention as a premise, and the detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Example 1:
1. weighing 0.01274 g, dissolving silver nitrate in 3mL deionized water, dissolving 1 mL sodium polymethacrylate in 3.3 mL deionized water, adding 500 uL sodium polymethacrylate solution into silver nitrate solution, dissolving at room temperature under 100W ultrasonic waves, and stirring in a stirrer to form uniform mixed solution. Adjusting the pH to 6, and then irradiating for 40 minutes under an ultraviolet lamp with the wavelength of 365 and nm to obtain a silver nanocluster solution;
2. weighing 0.2. 0.2 g chitosan, dissolving in 20 mL deionized water, loading into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging the obtained turbid liquid to obtain chitosan carbon quantum dot solution;
3. and (3) adding the chitosan carbon quantum dot solution obtained in the step (II) into the silver nanocluster solution obtained in the step (I), and stirring for 10 minutes by a magnetic stirrer to obtain the double-emission carbonized polymer dot-silver nanocluster nano composite fluorescent nano thermometer material.
FIG. 1 is a fluorescence excitation spectrum and a fluorescence emission spectrum of the fluorescent nanothermometer prepared in example 1, with fluorescence excitation peaks at 334 nm and fluorescence emission peaks at 401 nm and 609 nm. The fluorescent nano thermometer under natural illumination is in an orange water solution state, and the fluorescent nano sensor under 365 and nm ultraviolet illumination is in pink fluorescence.
FIG. 2 is a graph showing the fluorescence spectrum of the fluorescent nanothermometer prepared in example 1 at 25℃to 85 ℃. The fluorescence intensity at 401 and nm gradually decreases with the gradual increase of the temperature, and the fluorescence intensity at different temperatures is obviously distinguished.
FIG. 3 is a graph showing the linear change of the maximum fluorescence intensity with the ambient temperature of the fluorescent nano-thermometer prepared in example 1, which shows that the sensitivity of the fluorescence intensity with the temperature change can be quantitatively applied as the fluorescent nano-thermometer.
FIG. 4 is a reversible reciprocation curve of maximum fluorescence intensity of the fluorescent nanothermometer prepared in example 1 with the change of ambient temperature, showing that the fluorescent nanothermometer according to the present invention has very good cyclic reciprocation performance with temperature.
Claims (8)
1. The preparation method of the double-emission fluorescent nano thermometer is characterized by comprising the following steps of: 1. dissolving silver nitrate serving as a silver source raw material and sodium polymethacrylate serving as a polymerization monomer into deionized water, performing ultrasonic dissolution at room temperature, stirring in a magnetic stirrer, performing magnetic stirring, adjusting pH, and irradiating under an ultraviolet lamp to obtain a solution A, wherein the volume ratio of the molar quantity of the silver source raw material to the deionized water is 25mmol:3mL; the volume ratio of the molar quantity of the polymerized monomer raw material to deionized water is 1000mmol:33mL; 2. adding chitosan into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging the obtained turbid liquid to obtain a solution B; 3. and (3) mixing the solution A obtained in the step (A) with the solution B obtained in the step (B) and stirring to obtain a solution C, namely the double-emission carbonized polymer dot-silver nanocluster composite fluorescent thermometer material.
2. The method for preparing the fluorescent nano thermometer according to claim 1, wherein the method comprises the following steps: in the first step, the ultrasonic power is 60-100W.
3. The method for preparing the fluorescent nano thermometer according to claim 2, wherein the method comprises the following steps: in the first step, the stirring speed of the magnetic stirrer is 600-800 r/min.
4. A method for preparing a fluorescent nano-thermometer according to claim 3, wherein: and in the first step, the pH value is 6.
5. The method for preparing the fluorescent nano thermometer according to claim 4, wherein the method comprises the following steps: the irradiation wavelength of the ultraviolet lamp in the first step is 365 and nm, and the time is 40 minutes.
6. The method for preparing the fluorescent nano thermometer according to claim 5, wherein the method comprises the following steps: and in the second step, the hydrothermal reaction temperature is 180 ℃ and the time is 7 hours.
7. The method for preparing the fluorescent nano thermometer according to claim 6, wherein the method comprises the following steps: and in the second step, the centrifugal speed is 8000r/min.
8. The method for preparing the fluorescent nano thermometer according to claim 7, wherein the method comprises the following steps: the stirring time in the third step is 10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760520.2A CN113465769B (en) | 2021-07-06 | 2021-07-06 | Preparation method of double-emission nano fluorescent thermometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760520.2A CN113465769B (en) | 2021-07-06 | 2021-07-06 | Preparation method of double-emission nano fluorescent thermometer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113465769A CN113465769A (en) | 2021-10-01 |
| CN113465769B true CN113465769B (en) | 2023-04-28 |
Family
ID=77878426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110760520.2A Active CN113465769B (en) | 2021-07-06 | 2021-07-06 | Preparation method of double-emission nano fluorescent thermometer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113465769B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726316A (en) * | 2014-01-02 | 2014-04-16 | 江苏联发纺织股份有限公司 | Preparation method of pH value and temperature response, photocuring and one-way wet permeability multifunctional finishing agent for woven fabrics |
| CN103878386A (en) * | 2014-03-28 | 2014-06-25 | 黑龙江大学 | Method for preparing fluorescent silver nano-clusters |
| CN104232075A (en) * | 2014-09-30 | 2014-12-24 | 郑州大学 | Novel thermochromic fluorescent thermometer material and preparation method thereof |
| CN107011527A (en) * | 2017-05-04 | 2017-08-04 | 长春工业大学 | A kind of preparation method and application of the silver nanoclusters of temperature-responsive/polyalcohol hydrogel composite |
| CN107225255A (en) * | 2017-05-31 | 2017-10-03 | 山西大学 | A kind of red fluorescence ag nano-cluster probe and its preparation method and application |
| CN107576418A (en) * | 2017-09-11 | 2018-01-12 | 中国科学院理化技术研究所 | A kind of fluorescence nano thermometer based on DNA nanostructure and preparation method thereof |
| CN108709657A (en) * | 2018-04-12 | 2018-10-26 | 中山大学 | A kind of bimodulus nano fluorescence thermometer and preparation method thereof |
| WO2020087835A1 (en) * | 2018-11-02 | 2020-05-07 | 青岛大学 | Method for preparing cymoxanil ratio fluorescence probe based on dual emission quantum dot/silver nanoparticle complex |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9274008B2 (en) * | 2012-11-28 | 2016-03-01 | Washington University | Nanothermometer, methods and uses therefor |
-
2021
- 2021-07-06 CN CN202110760520.2A patent/CN113465769B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726316A (en) * | 2014-01-02 | 2014-04-16 | 江苏联发纺织股份有限公司 | Preparation method of pH value and temperature response, photocuring and one-way wet permeability multifunctional finishing agent for woven fabrics |
| CN103878386A (en) * | 2014-03-28 | 2014-06-25 | 黑龙江大学 | Method for preparing fluorescent silver nano-clusters |
| CN104232075A (en) * | 2014-09-30 | 2014-12-24 | 郑州大学 | Novel thermochromic fluorescent thermometer material and preparation method thereof |
| CN107011527A (en) * | 2017-05-04 | 2017-08-04 | 长春工业大学 | A kind of preparation method and application of the silver nanoclusters of temperature-responsive/polyalcohol hydrogel composite |
| CN107225255A (en) * | 2017-05-31 | 2017-10-03 | 山西大学 | A kind of red fluorescence ag nano-cluster probe and its preparation method and application |
| CN107576418A (en) * | 2017-09-11 | 2018-01-12 | 中国科学院理化技术研究所 | A kind of fluorescence nano thermometer based on DNA nanostructure and preparation method thereof |
| CN108709657A (en) * | 2018-04-12 | 2018-10-26 | 中山大学 | A kind of bimodulus nano fluorescence thermometer and preparation method thereof |
| WO2020087835A1 (en) * | 2018-11-02 | 2020-05-07 | 青岛大学 | Method for preparing cymoxanil ratio fluorescence probe based on dual emission quantum dot/silver nanoparticle complex |
Non-Patent Citations (1)
| Title |
|---|
| Xiran Shen.Thermo-responsive photoluminescent silver clusters/hydrogel nanocomposites for highly sensitive and selective detection of Cr(VI).Journal of Materials Chemistry C.2018,第2088-2094页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113465769A (en) | 2021-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Luminescent probes and sensors for temperature | |
| Shang et al. | Dual-mode upconversion nanoprobe enables broad-range thermometry from cryogenic to room temperature | |
| Kolesnikov et al. | Ratiometric optical thermometry based on emission and excitation spectra of YVO4: Eu3+ nanophosphors | |
| Hao et al. | Sensing using rare-earth-doped upconversion nanoparticles | |
| Li et al. | Investigation on the fluorescence intensity ratio sensing thermometry based on nonthermally coupled levels | |
| CN102798485B (en) | Temperature sensing method based on upconversion fluorescent powder | |
| Pang et al. | Fluorescent carbon dots sensor for highly sensitive detection of guanine | |
| Hasegawa et al. | Luminescent lanthanide coordination polymers with transformative energy transfer processes for physical and chemical sensing applications | |
| Radunz et al. | Evolution of size and optical properties of upconverting nanoparticles during high-temperature synthesis | |
| Ding et al. | A sensitive optic fiber sensor based on CdSe QDs fluorophore for nitric oxide detection | |
| Habibi et al. | 3D printed optofluidic biosensor: NaYF4: Yb3+, Er3+ upconversion nano-emitters for temperature sensing | |
| CN108896201A (en) | A kind of high-resolution organism thermometry of high sensitivity | |
| Hernandez et al. | High pressure responsive luminescence of flexible Eu3+ doped PVDF fibrous mats | |
| Zhou et al. | Novel optical thermometry strategy based on Gd3+ and defect-related luminescence of ZrO2: Gd3+ nanoparticles | |
| CN113465769B (en) | Preparation method of double-emission nano fluorescent thermometer | |
| Meng et al. | Core–Shell NaYF4: Yb3+/Tm3+@ NaGdF4: Ce3+/Eu3+ Nanoparticles for Upconversion and Downconversion Dual-Mode Fluorescence-Based Temperature Sensing | |
| Kumar et al. | Aspects of luminescence nanoprobes for thermometry: Progress and outlook | |
| Lioi et al. | Embedded optical nanosensors for monitoring the processing and performance of polymer matrix composites | |
| Wang et al. | Bandwidth-based flexible optical fiber thermometry based on sharp line emission regulation of Cr3+ ions | |
| CN108709657B (en) | Dual-mode nano fluorescence thermometer and preparation method thereof | |
| Saidi et al. | Temperature and Pressure Sensing Using an Optical Platform Based on Upconversion Luminescence in NaSrY (MoO4) 3 Codoped with Er3+ and Yb3+ Nanophosphors | |
| Li et al. | A dual-ratiometric optical thermometry based on Sr 2 LaF 7: Er 3+ crystal-implanted pliable fibers | |
| Knyazev et al. | Photostable temperature sensitive luminescent materials based on polystyrene doped by an anisometric Europium (III) complex | |
| Wang et al. | BaWO4: Ln3+ nanocrystals: Controllable synthesis, theoretical investigation on the substitution site, and bright upconversion luminescence as a sensor for glucose detection | |
| Zhang et al. | Ratiometric intracellular pH sensors based on nitrogen-doped graphene oxide quantum dots |
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 |