CN113201857A - Temperature-sensitive composite nanofiber film and preparation method and application thereof - Google Patents
Temperature-sensitive composite nanofiber film and preparation method and application thereof Download PDFInfo
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- CN113201857A CN113201857A CN202110470872.4A CN202110470872A CN113201857A CN 113201857 A CN113201857 A CN 113201857A CN 202110470872 A CN202110470872 A CN 202110470872A CN 113201857 A CN113201857 A CN 113201857A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent 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
- D01F6/52—Monocomponent 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 of polymers of unsaturated carboxylic acids or unsaturated esters
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract
The invention discloses a temperature-sensitive composite nanofiber membrane, which consists of blue fluorescent functional micromolecules, red fluorescent micromolecules and a temperature-sensitive polymer matrix; the blue fluorescent functional micromolecule is 9- (pyrene-1-yl) -9H-carbazole; the red fluorescent micromolecules are perylene diimide derivatives; the temperature-sensitive polymer matrix is any one of poly N-isopropyl acrylamide, poly N-ethyl acrylamide, poly- [ 2- (N, N-dimethylamino) ] methacrylate and poly N, N-diethyl acrylamide. The invention creatively utilizes the temperature sensitivity of the material to realize the ultra-high sensitivity visual detection of the TNT steam, and simultaneously effectively eliminates the interference of the water vapor in the environment. In addition, the film disclosed by the invention is low in manufacturing cost, simple and rapid in preparation and application operation, high in visualization degree, and capable of being used for real-time detection of the field environment at any time.
Description
Technical Field
The invention discloses a low-cost temperature-sensitive composite nanofiber film and a preparation method thereof, and application of the low-cost temperature-sensitive composite nanofiber film in efficient and high-selectivity visual detection of nitro explosive vapor, and relates to the field of detection of nitro explosives by a fluorescence sensor.
Background
Nitro explosives are substances widely applied to military and civil blasting engineering at present, and the substances can pollute soil or water contacted with the substances in a short-term or long-term exposure process, further have harmful effects on human health, cause symptoms such as headache, weakness, anemia, respiratory system diseases, skin discomfort and liver damage to the contacted people, and cause cancers in severe cases. Therefore, the method has very important significance for detecting the nitro explosives.
At present, trace detection of nitro explosives is put into practical application, but low-cost and high-sensitivity visual detection and anti-interference of nitro explosive gas still need to be researched. The difficulty of the gas detection technology is that many interfering gases such as water vapor, toluene, wine and cigarettes exist in complex industrial scenes, chemical laboratories and living environments, so that a high-selectivity, low-cost and high-sensitivity visual sensor has a very important significance for actual detection in complex air environments.
Among the many interfering gases, water vapor is unavoidable and ubiquitous, and when nitro-explosives are stored, the water vapor content in the storage environment of nitro-explosives is always in the medium range, considering that the possibility of accidental explosion is greatly increased in the extremely dry environment with extremely low water vapor content, and the effective and safe use of explosives is affected in the high-humidity environment with extremely high water vapor content. Under the above circumstances, scientists have attempted to avoid false alarms due to water vapor interference when using fluorescence sensors to detect nitro explosives. For this reason, array-based fluorescence sensors have received much attention because they can distinguish many harmful substances, such as DNT, NB, and other nitro explosives, etc., in the field. However, such sensors also suffer from a number of drawbacks. For example, the production costs are high, the production process and the data analysis process are complicated, and the reusability is not always achieved in the detection of corrosive gases.
In summary, from the requirement of safety detection in daily life environment, a visual fluorescence sensor for detecting nitro explosive gas, which is low in cost, high in selectivity, simple, easy to use, sensitive and portable, is urgently needed.
Disclosure of Invention
In view of the above-mentioned defects in the prior art, the present invention aims to provide a low-cost temperature-sensitive composite nanofiber membrane, a preparation method thereof, and an application thereof in the visual detection of nitro-explosive vapor, which are specifically as follows.
A temperature-sensitive composite nanofiber membrane is composed of blue fluorescent functional micromolecules, red fluorescent micromolecules and a temperature-sensitive polymer matrix;
the blue fluorescent functional micromolecule is 9- (pyrene-1-yl) -9H-carbazole;
the red fluorescent micromolecule is a perylene diimide derivative with a general structural formula
Wherein R is1And R2The same or different at the time of occurrence, both being one of a hydrogen atom or an alkyl group;
the temperature-sensitive polymer matrix is any one of poly N-isopropyl acrylamide, poly N-ethyl acrylamide, poly- [ 2- (N, N-dimethylamino) ] methacrylate and poly N, N-diethyl acrylamide.
Preferably, the diameter of the fiber forming the temperature-sensitive composite nanofiber membrane is 200 nm-350 nm.
Preferably, the temperature-sensitive composite nanofiber membrane has hydrophobicity above a critical solution temperature.
Preferably, when R is1Or R2When the alkyl is alkyl, the alkyl chain is a straight chain or branched chain of C1-C12.
A preparation method of a temperature-sensitive composite nanofiber membrane is used for preparing the temperature-sensitive composite nanofiber membrane, and comprises the following steps:
s1, adding 9- (pyrene-1-yl) -9H-carbazole, perylene diimide derivatives and temperature sensitive polymer matrix into an organic solvent, and violently stirring at room temperature to obtain uniform electrospinning liquid;
and S2, feeding the uniform electrospinning solution into an electrostatic spinning device, and preparing the temperature-sensitive composite nanofiber membrane by using an electrostatic spinning technology.
Preferably, the organic solvent in S1 is N, N-dimethylformamide or chloroform.
Preferably, the mass ratio of the 9- (pyrene-1-yl) -9H-carbazole, the perylene diimide derivative and the temperature-sensitive polymer matrix in the S1 is (3-5): (6-9): 327.
preferably, the mass concentration of the temperature-sensitive polymer matrix is 15 wt%.
Preferably, the process conditions of the electrospinning process in S2 include: the temperature is 25 ℃, the humidity is 35%, the RH voltage is 5 kV-15 kV, the distance between a needle head of the electrostatic spinning device and a receiver is 10 cm-20 cm, the inner diameter of the needle head is 0.5mm, the solution flow rate is 0.12 muL/s, the spinning time is 3min, and the finished product is stored in a dry environment.
The application of the temperature-sensitive composite nanofiber membrane is characterized in that: the temperature-sensitive composite nanofiber membrane is applied to the visual detection of nitro explosive vapor.
Compared with the prior art, the invention has the advantages that:
the temperature-sensitive composite nanofiber membrane provided by the invention is low in manufacturing cost, simple and rapid in preparation and application operation, high in visualization degree and good in selectivity, and can be used for real-time detection of a field environment at any time.
Specifically, the nanofibers in the temperature-sensitive composite nanofiber film of the present invention are hydrophobic above the critical solution temperature and thus are not disturbed by water vapor. The temperature-sensitive composite nanofiber membrane has extremely high detection sensitivity on nitro explosive steam at 50 ℃, and can generate very obvious fluorescent color change after being exposed in TNT steam with higher saturated vapor pressure for only about 20s, wherein the fluorescent color is changed from bluish purple to pink purple, the quenching efficiency is about 20%, the fluorescent color is changed into red after 20min, and the quenching efficiency is 92%. The invention can simply know the existence of the nitro explosive gas within tens of seconds through visual observation, and has no fluorescent response to common interferents in the air, such as water vapor, toluene, wine, cigarettes and the like.
In addition, the invention can also be used as a reference basis for subsequent research, and has reference value and deployment significance for searching and preparing related materials by researchers in the industry in the future.
The following detailed description of the embodiments of the present invention is provided in connection with the accompanying drawings to make the technical solutions of the present invention easier to understand and master.
Drawings
FIG. 1 is a scanning electron microscope image of a temperature-sensitive composite nanofiber film prepared in example 1;
fig. 2 is a fluorescence spectrum of the temperature-sensitive composite nanofiber film prepared in example 1 (λ ex =340 nm);
FIG. 3 is a contact angle of the temperature-sensitive composite nanofiber membrane prepared in example 3 at a temperature of 50 ℃;
FIG. 4 is a fluorescence spectrum of the temperature-sensitive composite nanofiber membrane prepared in example 3 before and after being exposed to TNT vapor at a temperature of 50 ℃ for 20 s;
FIG. 5 is a fluorescence spectrum of the temperature-sensitive composite nanofiber membrane prepared in example 3 before and after being exposed to TNT vapor at a temperature of 50 ℃ for 20 min;
FIG. 6 is a visual fluorescence picture of the temperature-sensitive composite nanofiber membrane prepared in example 3 in TNT vapor at 50 ℃ for 20s and 20 min;
FIG. 7 is a graph of quenching efficiency of the temperature-sensitive composite nanofiber film prepared in example 3 when exposed to water vapor and TNT vapor at 50 ℃ for 20s and 20min respectively to generate fluorescence color separation.
Detailed Description
The invention provides a temperature-sensitive composite nanofiber membrane which is low in manufacturing cost, simple and rapid in preparation and application operation, high in visualization degree and good in selectivity, and can be used for real-time detection of TNT in an on-site environment at any time. The specific scheme is as follows.
A temperature-sensitive composite nanofiber membrane, the diameter of the fiber forming the temperature-sensitive composite nanofiber membrane is 200 nm-350 nm, and the temperature-sensitive composite nanofiber membrane has hydrophobicity above the critical solution temperature. Due to the hydrophobic characteristic, the colorimetric method cannot be interfered by water vapor in the air, and meanwhile, the colorimetric method accelerates the detection sensitivity.
The temperature-sensitive composite nanofiber membrane consists of blue fluorescent functional micromolecules, red fluorescent micromolecules and a temperature-sensitive polymer matrix;
wherein the blue fluorescent functional micromolecule is 9- (pyrene-1-yl) -9H-carbazole (PyCz).
The red fluorescent micromolecule is perylene diimide derivative (PTCDI-C)x) The general formula of the structure is
Wherein R is1And R2The same or different at the time of occurrence, both being one of a hydrogen atom or an alkyl group; when R is1Or R2When the alkyl is alkyl, the alkyl chain is a straight chain or branched chain of C1-C12.
The temperature-sensitive polymer matrix is any one of poly N-isopropyl acrylamide (PNIPAM), poly N-ethyl acrylamide (PNEA), poly- [ 2- (N, N-dimethylamino) ] methacrylate (PDMAEMA) and poly N, N-diethyl acrylamide (PDEA).
The invention also discloses a preparation method of the temperature-sensitive composite nanofiber membrane, which is used for preparing the temperature-sensitive composite nanofiber membrane and comprises the following steps:
s1, adding 9- (pyrene-1-yl) -9H-carbazole, perylene diimide derivative and temperature sensitive polymer matrix into an organic solvent, and violently stirring at room temperature to obtain uniform electrospinning solution.
9- (pyrene-1-yl) -9H-carbazole perylene diimide derivatives as described hereinAnd the mass ratio of the temperature-sensitive polymer matrix to the temperature-sensitive polymer matrix is (3-5): (6-9): 327; the mass concentration of the temperature-sensitive polymer matrix is 15 wt%. The organic solvent is N, N-Dimethylformamide (DMF) or chloroform (CHCl)3）。
And S2, feeding the uniform electrospinning solution into an electrostatic spinning device, and preparing the temperature-sensitive composite nanofiber membrane by using an electrostatic spinning technology.
The process conditions of the electrospinning process described herein include: the temperature is 25 ℃, the humidity is 35%, the RH voltage is 5 kV-15 kV, the distance between a needle head of the electrostatic spinning device and a receiver is 10 cm-20 cm, the inner diameter of the needle head is 0.5mm, the solution flow rate is 0.12 muL/s, the spinning time is 3min, and the finished product is stored in a dry environment.
The invention also discloses an application of the temperature-sensitive composite nanofiber membrane, and the temperature-sensitive composite nanofiber membrane is applied to the visual detection of nitro explosive vapor by using the temperature-sensitive composite nanofiber membrane.
The detection method of the temperature-sensitive composite nanofiber film at the temperature of 50 ℃ is as follows: a trace amount of analyte (1.5 mg solid) was placed in an alumina crucible (5 mm. times.5 mm. times.3 mm), and sealed in a screw-cap quartz cell (1 cm. times.1 cm. times.3.5 cm) at 25 ℃ for 24 hours to reach a saturated vapor pressure. The quartz plate with the deposited nanofiber film and the blank quartz cell were placed on a 50 ℃ heating plate and heated for 15min until the test environment temperature reached about 50 ℃. Setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360-720 nm. And then placing the quartz plate in a quartz pool sealed with nitro explosive gas and heated for 15min for a period of time, setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360 nm-720 nm.
To demonstrate the effectiveness of the above approach, three specific examples are provided herein as references.
Example 1
4mg of PyCz, 8mg of PTCDI-Cx and 327mg of PNIPAM were weighed out and dissolved in 2mL of DMF and stirred at 23 ℃ to form a 15wt% homogeneous electrospinning solution.
Injecting the prepared electrospinning solution into a 2mL plastic syringe, connecting an opening end with a stainless steel needle with the inner diameter of 0.5mm as a spray head, connecting the spray head with a power supply anode, using an aluminum foil as a receiving screen, connecting the spray head with a power supply cathode, applying 10kV direct current voltage on the stainless steel needle with the inner diameter of 0.5mm, injecting the electrospinning solution at the flow rate of 0.12 mu L/s, carrying out electrospinning under the conditions that the distance between a receiver and the needle is 15cm, the relative air humidity is 35% and the temperature is 25 ℃, wherein the temperature-sensitive composite nanofiber film for the spectrum test is obtained by depositing fibers on a quartz plate in the electrospinning process.
A trace amount of analyte (1.5 mg solid) was placed in an alumina crucible (5 mm. times.5 mm. times.3 mm), and sealed in a screw-cap quartz cell (1 cm. times.1 cm. times.3.5 cm) at 25 ℃ for 24 hours to reach a saturated vapor pressure. The quartz plate with the deposited nanofiber film and the blank quartz cell were placed on a 50 ℃ heating plate and heated for 15min until the test environment temperature reached about 50 ℃. Setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360-720 nm. And then placing the quartz plate in a quartz pool sealed with nitro explosive gas and heated for 15min for a period of time, setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360 nm-720 nm.
FIG. 1 is a scanning electron microscope image of the temperature-sensitive composite nanofiber film prepared in this example, the thickness of the fibers constituting the film is uniform, and the diameter is 200nm to 350 nm.
FIG. 2 is a fluorescence spectrum of a temperature-sensitive composite nanofiber film prepared by doping PyCz and PTCDI-Cx in a polymer according to the present example, wherein the fluorescence spectrum (λ ex =340 nm) has emission peaks at 412nm and 650nm, and the film is blue-violet light.
Example 2
6.5mg of PyCz and 327mg of PNIPAM were weighed out and dissolved in 2mL of DMF and stirred at 23 ℃ to form a 15wt% homogeneous electrospinning solution.
Injecting the prepared electrospinning solution into a 2mL plastic syringe, connecting an opening end with a stainless steel needle with the inner diameter of 0.5mm as a spray head, connecting the spray head with a power supply anode, using an aluminum foil as a receiving screen, connecting the spray head with a power supply cathode, applying 10kV direct current voltage on the stainless steel needle with the inner diameter of 0.5mm, injecting the electrospinning solution at the flow rate of 0.12 mu L/s, carrying out electrospinning under the conditions that the distance between a receiver and the needle is 15cm, the relative air humidity is 35% and the temperature is 25 ℃, wherein the temperature-sensitive composite nanofiber film for the spectrum test is obtained by depositing fibers on a quartz plate in the electrospinning process.
A trace amount of analyte (1.5 mg solid) was placed in an alumina crucible (5 mm. times.5 mm. times.3 mm), and sealed in a screw-cap quartz cell (1 cm. times.1 cm. times.3.5 cm) at 25 ℃ for 24 hours to reach a saturated vapor pressure. The nanofiber-deposited quartz plate was placed in the quartz cell for testing. Setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360-550 nm. And then placing the quartz plate in a quartz pool sealed with nitro explosive gas and heated for 15min for a period of time, setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360 nm-550 nm.
The temperature-sensitive composite nanofiber prepared in the embodiment has obviously changed fluorescence color substances after being exposed in TNT steam for 20s at normal temperature, and only the fluorescence intensity of a film becomes dark after 20min, so that the temperature-sensitive composite nanofiber is known to be undoped with PTCDI-CxThe sensitivity of the temperature-sensitive composite nanofiber membrane for detecting TNT is low.
Example 3
6mg of PyCz, 14mg of PTCDI-Cx and 654mg of PNIPAM were weighed out and dissolved in 4mL of DMF and stirred at 23 ℃ to form a 15wt% homogeneous electrospinning solution.
Injecting the prepared electrospinning solution into a 2mL plastic syringe, connecting an opening end with a stainless steel needle with the inner diameter of 0.5mm as a spray head, connecting the spray head with a power supply anode, using an aluminum foil as a receiving screen, connecting the spray head with a power supply cathode, applying 10kV direct current voltage on the stainless steel needle with the inner diameter of 0.5mm, injecting the electrospinning solution at the flow rate of 0.12 mu L/s, carrying out electrospinning under the conditions that the distance between a receiver and the needle is 15cm, the relative air humidity is 35% and the temperature is 25 ℃, wherein the temperature-sensitive composite nanofiber film for the spectrum test is obtained by depositing fibers on a quartz plate in the electrospinning process.
A trace amount of analyte (1.5 mg solid) was placed in an alumina crucible (5 mm. times.5 mm. times.3 mm), and placed in a screw-cap quartz cell (1 cm. times.1 cm. times.3.5 cm) and sealed in summer at a temperature of 25 ℃ for 24 hours to reach a saturated vapor pressure. The quartz plate with deposited nanofibers and the blank quartz cell were placed on a 50 ℃ heating plate and heated for 15min until the test environment temperature reached about 50 ℃. Setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360-720 nm. And then placing the quartz plate in a quartz pool sealed with nitro explosive gas and heated for 15min for a period of time, setting the excitation wavelength to be 340nm, and collecting the fluorescence curve of the temperature-sensitive composite nanofiber film at the position of 360 nm-720 nm.
Fig. 3 is a contact angle of the temperature-sensitive composite nanofiber film prepared in the embodiment at a temperature of 50 ℃, and it can be seen that the contact angle at the temperature is 128 °, the temperature-sensitive composite nanofiber film is hydrophobic at this time, and the fluorescence intensity of the temperature-sensitive composite nanofiber film is not changed at this time.
Fig. 4 is a fluorescence spectrum of the temperature-sensitive composite nanofiber film prepared in this example after being exposed to TNT vapor at 50 ℃ for 20 seconds, and it can be seen from the fluorescence spectrum that blue fluorescence is quenched by about 20% and red fluorescence intensity is not changed.
Fig. 5 is a fluorescence spectrum of the temperature-sensitive composite nanofiber film prepared in this example after being exposed to TNT vapor at 50 ℃ for 20min, and it can be seen from the fluorescence spectrum that blue fluorescence is quenched by about 92% and red fluorescence intensity is not changed.
FIG. 6 is a temperature sensitive composite nanofiber membrane 50 prepared in example 3oThe visible fluorescence pictures of 20s and 20min in TNT vapor under C show that the film changes from bluish purple to pink at 20s and red at 20 min.
Fig. 7 is a quenching efficiency graph of the temperature-sensitive composite nanofiber film prepared in this example when the film is exposed to water vapor and TNT vapor for 20s and 20min at a temperature of 50 ℃ to generate fluorescence color differentiation, and it can be seen from the graph that the quenching efficiency of blue light is 20% after the film is exposed to TNT vapor for 20s, at this time, the fluorescence color changes from blue-violet to pink, and the quenching efficiency of blue light is 92% after 20min, at this time, the fluorescence color is red.
Tests show that the temperature-sensitive composite nanofiber film has extremely high detection sensitivity on nitro explosive vapor at 50 ℃, and can generate very obvious fluorescent color change after being exposed in TNT vapor with higher saturated vapor pressure for only about 20s, wherein the fluorescent color is changed from blue-purple to pink, the quenching efficiency is about 20%, the fluorescent color is changed from blue-purple to red after 20min, and the quenching efficiency is 92%. The invention can detect nitro explosive gas simply and sensitively through visual observation, and has no fluorescence response to common interferents in the air such as water vapor, toluene, wine, cigarettes and the like.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Finally, it should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should integrate the description, and the technical solutions in the embodiments can be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (10)
1. A temperature-sensitive composite nanofiber membrane is characterized in that: the fluorescent material consists of blue fluorescent functional micromolecules, red fluorescent micromolecules and a temperature-sensitive polymer matrix;
the blue fluorescent functional micromolecule is 9- (pyrene-1-yl) -9H-carbazole;
the red fluorescent micromolecule is a perylene diimide derivative with a general structural formula
Wherein R is1And R2The same or different at the time of occurrence, both being one of a hydrogen atom or an alkyl group;
the temperature-sensitive polymer matrix is any one of poly N-isopropyl acrylamide, poly N-ethyl acrylamide, poly- [ 2- (N, N-dimethylamino) ] methacrylate and poly N, N-diethyl acrylamide.
2. The temperature-sensitive composite nanofiber membrane according to claim 1, wherein: the diameter of the fiber forming the temperature-sensitive composite nanofiber membrane is 200 nm-350 nm.
3. The temperature-sensitive composite nanofiber membrane according to claim 1, wherein: the temperature-sensitive composite nanofiber membrane has hydrophobicity above the critical dissolution temperature.
4. The temperature-sensitive composite nanofiber membrane according to claim 1, wherein: when R is1Or R2When the alkyl is alkyl, the alkyl chain is a straight chain or branched chain of C1-C12.
5. A preparation method of a temperature-sensitive composite nanofiber membrane, which is used for preparing the temperature-sensitive composite nanofiber membrane as claimed in any one of claims 1-4, and is characterized by comprising the following steps:
s1, adding 9- (pyrene-1-yl) -9H-carbazole, perylene diimide derivatives and temperature sensitive polymer matrix into an organic solvent, and violently stirring at room temperature to obtain uniform electrospinning liquid;
and S2, feeding the uniform electrospinning solution into an electrostatic spinning device, and preparing the temperature-sensitive composite nanofiber membrane by using an electrostatic spinning technology.
6. The preparation method of the temperature-sensitive composite nanofiber membrane according to claim 5, characterized in that: the organic solvent in S1 is N, N-dimethylformamide or chloroform.
7. The preparation method of the temperature-sensitive composite nanofiber membrane according to claim 5, characterized in that: in the S1, the mass ratio of the 9- (pyrene-1-yl) -9H-carbazole to the perylene diimide derivative to the temperature-sensitive polymer matrix is (3-5): (6-9): 327.
8. the preparation method of the temperature-sensitive composite nanofiber membrane according to claim 5, characterized in that: the mass concentration of the temperature-sensitive polymer matrix is 15 wt%.
9. The preparation method of the temperature-sensitive composite nanofiber membrane as claimed in claim 5, wherein the process conditions of the electrospinning process in S2 include: the temperature is 25 ℃, the humidity is 35%, the RH voltage is 5 kV-15 kV, the distance between a needle head of the electrostatic spinning device and a receiver is 10 cm-20 cm, the inner diameter of the needle head is 0.5mm, the solution flow rate is 0.12 muL/s, the spinning time is 3min, and the finished product is stored in a dry environment.
10. The application of the temperature-sensitive composite nanofiber membrane, which is prepared by using the temperature-sensitive composite nanofiber membrane as claimed in any one of claims 1 to 4, is characterized in that: the temperature-sensitive composite nanofiber membrane is applied to the visual detection of nitro explosive vapor.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105136764A (en) * | 2015-09-14 | 2015-12-09 | 南京邮电大学 | Detection method of tetra-aryl ethene luminescent nanofiber for explosive |
| CN105133188A (en) * | 2015-07-31 | 2015-12-09 | 南京邮电大学 | Polymer nanometer fiber film doped with carbazole derivative and preparation method and application |
| WO2018044688A1 (en) * | 2016-08-29 | 2018-03-08 | Life Technologies Corporation | Fluorescent particles |
| CN108796825A (en) * | 2018-06-22 | 2018-11-13 | 南京邮电大学 | Detect the porous nano-fibre film and the preparation method and application thereof of wet environment explosive vapors |
| CN109023722A (en) * | 2018-06-26 | 2018-12-18 | 南京邮电大学 | The inexpensive composite fluorescence nano-fiber film and the preparation method and application thereof of highly selective detection TNT |
| CN110485062A (en) * | 2019-08-21 | 2019-11-22 | 南京邮电大学 | A kind of polychrome composite nano-fiber film and preparation method thereof |
-
2021
- 2021-04-29 CN CN202110470872.4A patent/CN113201857A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105133188A (en) * | 2015-07-31 | 2015-12-09 | 南京邮电大学 | Polymer nanometer fiber film doped with carbazole derivative and preparation method and application |
| CN105136764A (en) * | 2015-09-14 | 2015-12-09 | 南京邮电大学 | Detection method of tetra-aryl ethene luminescent nanofiber for explosive |
| WO2018044688A1 (en) * | 2016-08-29 | 2018-03-08 | Life Technologies Corporation | Fluorescent particles |
| CN108796825A (en) * | 2018-06-22 | 2018-11-13 | 南京邮电大学 | Detect the porous nano-fibre film and the preparation method and application thereof of wet environment explosive vapors |
| CN109023722A (en) * | 2018-06-26 | 2018-12-18 | 南京邮电大学 | The inexpensive composite fluorescence nano-fiber film and the preparation method and application thereof of highly selective detection TNT |
| CN110485062A (en) * | 2019-08-21 | 2019-11-22 | 南京邮电大学 | A kind of polychrome composite nano-fiber film and preparation method thereof |
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