CN112708955A - Temperature-sensitive fluorescent nanofiber and preparation method and application thereof - Google Patents

Temperature-sensitive fluorescent nanofiber and preparation method and application thereof Download PDF

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Publication number
CN112708955A
CN112708955A CN202110073395.8A CN202110073395A CN112708955A CN 112708955 A CN112708955 A CN 112708955A CN 202110073395 A CN202110073395 A CN 202110073395A CN 112708955 A CN112708955 A CN 112708955A
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China
Prior art keywords
solution
spinning
temperature
fluorescent
sensitive fluorescent
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CN202110073395.8A
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Chinese (zh)
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代昭
马越
郭文娟
刘巍
龙孝诚
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

Abstract

The invention belongs to the technical field of fiber materials, and particularly provides a temperature-sensitive fluorescent nanofiber as well as a preparation method and application thereof. The invention uses electrostatic spinning technology to prepare fluorescent fiber, which comprises the following steps: the method comprises the following steps: selecting protein as a template agent and a reducing agent, mixing a protein solution and a chloroauric acid solution according to a certain proportion, and then adding a sodium hydroxide solution to prepare a gold nanocluster solution. Step two: and (3) blending the gold nanocluster solution prepared in the step one and polymer powder, placing the mixture into secondary water, stirring to prepare a spinning solution, and standing and defoaming for later use. Step three: and (4) sucking the spinning solution prepared in the step two into an injector, spinning on electrostatic spinning equipment, and preparing uniform and continuous fluorescent fibers by changing process parameters. The fluorescent nanofiber is widely applied to the fields of fluorescence anti-counterfeiting, environment detection, biological medicine and the like at present. The fluorescent fiber prepared by mixing the fluorescent material and the polymer has the advantages of uniformity, no beads, good appearance, simple and convenient preparation process and excellent fluorescent characteristic and temperature sensitivity.

Description

Temperature-sensitive fluorescent nanofiber and preparation method and application thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of fiber materials, and relates to a preparation method and application of temperature-sensitive fluorescent nanofiber.
[ background of the invention ]
The fluorescent nanofiber refers to a linear material with the diameter reaching the nanometer level and long length. The fluorescent fiber is also called as a safety fiber, can emit different colors under different excitation light sources, and can recover the color of the fiber after the light disappears. Fibers emitting different colors under the excitation of infrared light are called infrared fluorescent fibers, and functional fibers emitting different colors under the excitation of ultraviolet light are ultraviolet fluorescent fibers. The fluorescent fiber is widely applied to the fields of biosensors, photoelectric materials, package anti-counterfeiting and the like due to the excellent fluorescent characteristic of the fluorescent fiber.
At present, the preparation method of the fluorescent fiber mainly comprises a melt spinning method, an electrostatic spinning method, a dyeing method, a surface coating method and a chemical modification method. Most of the fluorescent materials commonly used by people are rare earth materials and fluorescent dyes, but the method for preparing the fluorescent fibers by using the rare earth materials is complicated, and the fluorescent fibers prepared by using the fluorescent dyes pollute the environment, so that in order to comply with the trend of green development, the inventor provides a preparation method of the fluorescent nanofibers with simple preparation process, low cost, low carbon and environmental protection, so as to overcome the defects in the existing fluorescent fiber preparation.
[ summary of the invention ]
Problems to be solved
The invention aims to provide a preparation method of temperature-sensitive fluorescent nanofiber. The invention provides a method for preparing a fluorescent fiber by blending polymer powder and gold nanoclusters to prepare a spinning solution and adopting an electrostatic spinning technology. The method can prepare the fluorescent fiber with large area and low cost, and the preparation process is simple, so that the process of synthesizing the fluorescent fiber is greatly simplified.
(II) technical scheme
The technical scheme provided by the invention is as follows: a temperature-sensitive fluorescent fiber comprises a high molecular polymer and a fluorescent material, wherein the high molecular polymer can be one or a combination of more of polyacrylamide, polyvinyl alcohol and polyvinyl butyral, the mass fraction of polymer powder in the total mass of a solution is 1-3 wt%, and the mass ratio of a gold nanocluster solution to secondary water is 5: 14.6. The fluorescent fiber has fluorescent characteristic and temperature-sensitive characteristic, and the luminescent characteristic and the temperature-sensitive characteristic come from fluorescent material gold nanoclusters.
(III) advantageous effects
Compared with the prior art, the temperature-sensitive fluorescent nanofiber prepared by adopting the electrostatic spinning technology has the advantages of simple and convenient preparation process, lower cost, low price and easy obtainment, the prepared temperature-sensitive fluorescent nanofiber has smooth surface and uniform diameter distribution, the size is between 200 plus materials and 500nm, excellent red fluorescence performance can be displayed under an ultraviolet lamp, different color changes can be displayed under different temperatures, and the temperature-sensitive fluorescent nanofiber has huge potential in the application aspects of fluorescent anti-counterfeiting, environmental monitoring, biological medicine and the like due to the double functions of fluorescent imaging and temperature induction.
(IV) specific reaction process
The invention comprises the following steps:
the method comprises the following steps: selecting protein as a template agent and a reducing agent, mixing a protein solution and a chloroauric acid solution according to a certain proportion, and then adding a gold nanocluster solution prepared from a sodium hydroxide solution;
step two: mixing the gold nanocluster solution prepared in the step one with polymer powder, placing the mixture into secondary water, stirring to prepare a spinning stock solution, and standing and defoaming for later use;
step three: and (4) sucking the spinning solution prepared in the step two into an injector, spinning on electrostatic spinning equipment, and preparing uniform and continuous fluorescent fibers by changing process parameters.
In a preferred embodiment, the protein in the first step is bovine serum albumin or chicken protein; in the chloroauric acid solution in the first step, the ratio of the chloroauric acid solution to the protein solution is 2: 1, 1: 1 and 1: 2; in the second step, the mass fraction of the polymer powder in the total mass of the solution is 1-3 wt%; the mass ratio of the gold nanocluster solution to the secondary water in the second step is 5: 14.6; the spinning solution in the second step is stirred for 14 hours at room temperature; in the third step of electrostatic spinning, the spinning voltage is 10-16kv, the spinning speed is 0.02-0.04mm/min, and the distance between the needle head and the spinning collecting device is 25-29 cm.
In a preferred embodiment, the protein in the first step is preferably bovine serum albumin, and the ratio of the chloroauric acid solution to the protein solution is preferably 1: 1.
In a preferred embodiment, the polymer in step two is preferably polyacrylamide, and the mass fraction thereof is preferably 2 wt%. In a preferred embodiment, the spinning voltage in the third step is preferably 13kv, the spinning speed is preferably 0.03mm/min, and the distance between the needle and the spinning collecting device is preferably 27 cm.
[ description of the drawings ]
FIG. 1 is an SEM image of temperature-sensitive fluorescent nanofibers prepared in example 1 provided by the present invention;
fig. 2 is a fluorescence microscope optical image of the temperature-sensitive fluorescent nanofiber prepared in example 1.
[ detailed description ] embodiments
Example 1:
(1) mixing a protein solution and a chloroauric acid solution according to a certain proportion by taking protein as a template agent and a reducing agent, and then adding a sodium hydroxide solution to prepare a gold nanocluster solution; the method comprises the following specific steps: mixing bovine hemoglobin with secondary water to prepare a bovine hemoglobin solution with the concentration of 50 mg/ml; preparing 10Mm chloroauric acid solution from chloroauric acid, adding 10Ml chloroauric acid solution into 10Ml bovine hemoglobin solution under vigorous stirring, dropping 1Ml 1M sodium hydroxide solution after two minutes, and finally vigorously stirring at 37 ℃ for 12 hours to prepare the gold nano-cluster solution.
(2) Mixing the gold nanocluster solution prepared in the step (1) with polymer powder, placing the mixture into secondary water, stirring to prepare a spinning solution, and standing and defoaming for later use; the method comprises the following specific steps: dissolving 2 wt% of polyacrylamide powder in 14.6g of secondary water, then adding 5g of gold nanocluster solution, stirring vigorously for 14 hours under magnetic stirring, and finally standing and defoaming for later use.
(3) Sucking the spinning solution prepared in the step (2) into an injector, spinning on electrostatic spinning equipment, and preparing uniform and continuous fluorescent fibers by changing process parameters; the method comprises the following specific steps: and (3) standing and defoaming the spinning solution prepared in the step (2), extracting 8ml of the spinning solution by using an injector, fixing a needle head on the injector, placing the injector on an injection pump for fixing, applying positive high pressure on the needle head, and covering an aluminum foil on a receiving device for fixing. And (3) carrying out electrostatic spinning to prepare the fluorescent nanofiber by adjusting the spinning voltage to be 13kv, the spinning speed to be 0.03mm/min and the receiving distance to be 27cm under the conditions of room temperature and humidity of about 20-40%.
Example 2:
(1) mixing a protein solution and a chloroauric acid solution according to a certain proportion by taking protein as a template agent and a reducing agent, and then adding a sodium hydroxide solution to prepare a gold nanocluster solution; the method comprises the following specific steps: mixing bovine hemoglobin with secondary water to prepare a bovine hemoglobin solution with the concentration of 50 mg/ml; preparing 5Mm chloroauric acid solution from chloroauric acid, adding 20Ml chloroauric acid solution into 10Ml bovine hemoglobin solution under vigorous stirring, dropping 1Ml 1M sodium hydroxide solution after two minutes, and vigorously stirring at 37 deg.C for 12 hours to obtain gold nanocluster solution.
(2) Mixing the gold nanocluster solution prepared in the step (1) with polymer powder, placing the mixture into secondary water, stirring to prepare a spinning solution, and standing and defoaming for later use; the method comprises the following specific steps: dissolving 1 wt% of polyacrylamide in 14.6g of secondary water, then adding 5g of gold nanocluster solution, stirring vigorously for 14 hours under magnetic stirring, and finally standing and defoaming for later use.
(3) Sucking the spinning solution prepared in the step (2) into an injector, spinning on electrostatic spinning equipment, and preparing uniform and continuous fluorescent fibers by changing process parameters; the method comprises the following specific steps: and (3) standing and defoaming the spinning solution prepared in the step (2), extracting 8ml of the spinning solution by using an injector, fixing a needle head on the injector, placing the injector on an injection pump for fixing, applying positive high pressure on the needle head, and covering an aluminum foil on a receiving device for fixing. Under the conditions of room temperature and humidity of about 20% -40%, the spinning voltage is adjusted to 10kv, the spinning speed is 0.02mm/min, and the receiving distance is 25cm to carry out electrostatic spinning to prepare the fluorescent nanofiber.
Example 3:
(1) mixing a protein solution and a chloroauric acid solution according to a certain proportion by taking protein as a template agent and a reducing agent, and then adding a sodium hydroxide solution to prepare a gold nanocluster solution; the method comprises the following specific steps: mixing bovine hemoglobin with secondary water to prepare a bovine hemoglobin solution with the concentration of 50 mg/ml; preparing 20Mm chloroauric acid solution from chloroauric acid, adding 10Ml chloroauric acid solution into 20Ml bovine hemoglobin solution under vigorous stirring, dropping 1Ml 1M sodium hydroxide solution after two minutes, and vigorously stirring at 37 deg.C for 12 hours to obtain gold nanocluster solution.
(2) Mixing the gold nanocluster solution prepared in the step (1) with polymer powder, placing the mixture into secondary water, stirring to prepare a spinning solution, and standing and defoaming for later use; the method comprises the following specific steps: dissolving 3 wt% of polyacrylamide in 14.6g of secondary water, then adding 5g of gold nanocluster solution, stirring vigorously for 14 hours under magnetic stirring, and finally standing and defoaming for later use.
(3) Sucking the spinning solution prepared in the step (2) into an injector, spinning on electrostatic spinning equipment, and preparing uniform and continuous fluorescent fibers by changing process parameters; the method comprises the following specific steps: and (3) standing and defoaming the spinning solution prepared in the step (2), extracting 8ml of the spinning solution by using an injector, fixing a needle head on the injector, placing the injector on an injection pump for fixing, applying positive high pressure on the needle head, and covering an aluminum foil on a receiving device for fixing. And (3) carrying out electrostatic spinning to prepare the fluorescent nanofiber by adjusting the spinning voltage to be 16kv, the spinning speed to be 0.04mm/min and the receiving distance to be 29cm under the conditions of room temperature and humidity of about 20-40%.
The foregoing description is of the preferred embodiment of the present invention and is not intended to limit the scope of the invention. All equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.

Claims (9)

1. A temperature-sensitive fluorescent nanofiber is characterized in that the diameter of the fiber is uniformly distributed, the size of the fiber is between 200 and 500nm, and the temperature-sensitive fluorescent nanofiber has excellent fluorescent characteristics and temperature sensitivity.
2. The temperature-sensitive fluorescent nanofiber according to claim 1, wherein the high molecular polymer is one or a combination of several of polyacrylamide, polyvinyl alcohol and polyvinyl butyral.
3. The temperature-sensitive fluorescent nanofiber according to claim 2, wherein the polymer is selected from one or two of polyacrylamide or polyvinyl alcohol.
4. The preparation method of the temperature-sensitive fluorescent nanofiber according to claim 1, wherein the temperature-sensitive fluorescent nanofiber is prepared by blending a gold nanocluster and a high molecular polymer and performing electrostatic spinning, and comprises the following steps:
the method comprises the following steps: selecting protein as a template agent and a reducing agent, mixing a protein solution and a chloroauric acid solution according to a certain proportion, and then adding a sodium hydroxide solution to prepare a gold nanocluster solution;
step two: mixing the gold nanocluster solution prepared in the step one with polymer powder, placing the mixture into secondary water, stirring to prepare a spinning stock solution, and standing and defoaming for later use;
step three: and (4) sucking the spinning solution prepared in the step two into an injector, and spinning on electrostatic spinning equipment to prepare uniform and continuous fluorescent fibers.
5. The preparation method of the temperature-sensitive fluorescent nanofiber according to claim 4, wherein the protein in the first step is bovine serum albumin or chicken protein; the ratio of the chloroauric acid solution to the protein solution in the first step is 2: 1, 1: 1 and 1: 2; in the second step, the mass fraction of the polymer powder in the total mass of the solution is 1-3 wt%; the mass ratio of the gold nanocluster solution to the secondary water in the second step is 5: 14.6; the spinning solution in the second step is stirred for 14 hours at room temperature; in the third step of electrostatic spinning, the spinning voltage is 10-16kv, the spinning speed is 0.02-0.04mm/min, and the distance between the needle head and the spinning collecting device is 25-29 cm.
6. The preparation method of the temperature-sensitive fluorescent nanofiber according to claim 5, wherein in the first step, the protein is preferably bovine serum albumin, and the ratio of the chloroauric acid solution to the protein solution is preferably 1: 1.
7. The temperature-sensitive fluorescent nanofiber according to claim 5, wherein the polymer in the second step is preferably polyacrylamide, and the mass fraction of the polymer is preferably 2 wt%.
8. The preparation method of the temperature-sensitive fluorescent nanofiber according to claim 5, wherein the spinning voltage in the third step is preferably 13kv, the spinning speed is preferably 0.03mm/min, and the distance between the needle and the spinning collection device is preferably 27 cm.
9. The application of the temperature-sensitive fluorescent nanofiber as claimed in claims 1-8, wherein the temperature-sensitive nanocomposite fluorescent fiber can be applied to the fields of fluorescence anti-counterfeiting, environmental monitoring, biological medicine and the like.
CN202110073395.8A 2021-01-20 2021-01-20 Temperature-sensitive fluorescent nanofiber and preparation method and application thereof Pending CN112708955A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114645377A (en) * 2022-03-17 2022-06-21 广东工业大学 Electrostatic spinning composite film of polyvinyl alcohol and bovine serum albumin and preparation method thereof
CN114855366A (en) * 2022-05-20 2022-08-05 齐齐哈尔大学 Preparation method of polyvinyl alcohol/gold nanocluster photoluminescent film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232083A (en) * 2014-08-29 2014-12-24 东华大学 Preparation method of flexible inorganic fluorescent fibrous membrane
CN106245129A (en) * 2016-08-19 2016-12-21 Tcl集团股份有限公司 A kind of nano luminescent fiber and preparation method thereof
CN106381555A (en) * 2016-08-26 2017-02-08 华南理工大学 Composite fiber containing aggregation-induced luminescent molecules, preparation method thereof and application thereof
CN108796661A (en) * 2018-06-14 2018-11-13 中原工学院 A kind of electrostatic spinning preparation method of platinum doping fluorescent nanofiber
CN109371568A (en) * 2018-11-16 2019-02-22 江苏科技大学 The preparation method of fluorescent nano-fiber film based on acrylic based emulsion
CN110055619A (en) * 2019-05-07 2019-07-26 湖北大学 The preparation method and application of nano combined fluorescent fiber

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232083A (en) * 2014-08-29 2014-12-24 东华大学 Preparation method of flexible inorganic fluorescent fibrous membrane
CN106245129A (en) * 2016-08-19 2016-12-21 Tcl集团股份有限公司 A kind of nano luminescent fiber and preparation method thereof
CN106381555A (en) * 2016-08-26 2017-02-08 华南理工大学 Composite fiber containing aggregation-induced luminescent molecules, preparation method thereof and application thereof
CN108796661A (en) * 2018-06-14 2018-11-13 中原工学院 A kind of electrostatic spinning preparation method of platinum doping fluorescent nanofiber
CN109371568A (en) * 2018-11-16 2019-02-22 江苏科技大学 The preparation method of fluorescent nano-fiber film based on acrylic based emulsion
CN110055619A (en) * 2019-05-07 2019-07-26 湖北大学 The preparation method and application of nano combined fluorescent fiber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114645377A (en) * 2022-03-17 2022-06-21 广东工业大学 Electrostatic spinning composite film of polyvinyl alcohol and bovine serum albumin and preparation method thereof
CN114855366A (en) * 2022-05-20 2022-08-05 齐齐哈尔大学 Preparation method of polyvinyl alcohol/gold nanocluster photoluminescent film

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Application publication date: 20210427