CN120504629A - Quinoline group modified aromatic compound, preparation method thereof and application thereof in pH responsive fiber membrane - Google Patents
Quinoline group modified aromatic compound, preparation method thereof and application thereof in pH responsive fiber membraneInfo
- Publication number
- CN120504629A CN120504629A CN202510565258.4A CN202510565258A CN120504629A CN 120504629 A CN120504629 A CN 120504629A CN 202510565258 A CN202510565258 A CN 202510565258A CN 120504629 A CN120504629 A CN 120504629A
- Authority
- CN
- China
- Prior art keywords
- aromatic compound
- modified aromatic
- acid
- quinoline group
- quinoline
- 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.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
Abstract
本发明公开了一种喹啉基团修饰的芳香化合物及其制备方法与在pH响应型纤维膜应用。该化合物具有如下结构式：式中，R选自喹啉基。本发明方案结构化合物具有独特的分子结构，且喹啉基团结构具有多样性和灵活性，因此，本发明方案化合物结构设计灵活，具有优异的荧光性能和良好的结构稳定性，同时，本发明方案的化合物具有pH响应特性。将其制备成纤维膜后，化合物分子与酸碱蒸气等待测物质之间接触效率显著提高，对pH具有极高的灵敏响应度。
The present invention discloses a quinoline group-modified aromatic compound, its preparation method, and its application in pH-responsive fiber membranes. The compound has the following structural formula: Wherein R is selected from a quinoline group. The structural compounds of the present invention possess unique molecular structures, and the quinoline group structure offers diversity and flexibility. Therefore, the structural design of the compounds of the present invention is flexible, with excellent fluorescence properties and good structural stability. Furthermore, the compounds of the present invention exhibit pH-responsive properties. When prepared into a fiber membrane, the contact efficiency between the compound molecules and the acid, base, vapor, or other test substances is significantly improved, resulting in an extremely high sensitivity to pH.
Description
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to a quinoline group modified aromatic compound, a preparation method thereof and application thereof in pH response type fiber membranes.
Background
In the field of crossing chemistry and material science, fiber film materials have become a hot spot for functional material research due to their unique two-dimensional nanostructure features (such as high specific surface area, adjustable porosity and surface modification). The material has irreplaceable application value in the fields of environmental management (high-efficiency filtration and separation), biological medicine (targeted drug delivery, tissue engineering scaffold) and advanced sensing, etc. Although the traditional polymer fiber membrane (such as polypropylene and polytetrafluoroethylene) has a mature industrial application foundation, the surface chemical inertness and the functional singleness of the traditional polymer fiber membrane severely restrict the performance breakthrough in the front fields of precision sensing, living body imaging and the like. Especially when the molecular level interaction scene is involved, the existing materials have technical bottlenecks of response delay, low signal transduction efficiency and the like, and the strict requirements of an intelligent material system on real-time monitoring and dynamic feedback are difficult to meet.
In the field of molecular optical detection, aggregation-induced emission (AIE) materials based on multi-aromatic ring structures exhibit significant advantages in the construction of multiple stimulus-responsive fluorescent probes due to their unique Intramolecular Charge Transfer (ICT) effects. However, the conventional AIE probe has two major core challenges in practical application, namely that firstly, the strong intermolecular pi-pi stacking effect in a solid state/condensed state causes the energy dissipation of an excited state to remarkably reduce the fluorescence quantum yield, and secondly, the contact dynamics of the probe molecule and a target analyte (such as acid/alkaline vapor) are limited by a diffusion mass transfer process, so that the response time constant is generally greater than 30 seconds, and the real-time monitoring requirement cannot be met. Although the aggregation quenching effect can be partially relieved by molecular engineering means (such as introducing a rigid twisted structure and increasing steric hindrance), no technical scheme has been available for synchronously solving the contradictory relationship between fluorescence efficiency and response rate.
Therefore, the development of a novel fiber membrane-fluorescent probe composite system with high sensitivity response and rapid dynamic characteristics has great strategic significance for breaking through the technical bottleneck of the existing sensing materials and pushing the intelligent materials to be applied in the fields of environmental monitoring, biomedical diagnosis and the like.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the quinoline group modified aromatic compound with a novel structure, which has obvious fluorescence intensity when applied to a fiber membrane and can quickly generate obvious contrast change when the pH value changes.
The invention also provides a preparation method of the compound.
The invention also provides application of the compound.
According to one aspect of the present invention, there is provided a quinoline group-modified aromatic compound having the following structural formula:
Wherein R is selected from one of the following structures:
The quinoline group modified aromatic compound has at least the following beneficial effects that the compound has a unique molecular structure and the quinoline group structure has diversity and flexibility, so that the compound has flexible structural design, excellent fluorescence performance and good structural stability, and meanwhile, the compound has pH response characteristics. After the fiber membrane is prepared, the contact efficiency between the compound molecules and substances to be tested such as acid and alkali vapors is obviously improved, and the fiber membrane has extremely high sensitivity response to pH.
According to another aspect of the present invention, there is also provided a method for preparing the above quinoline group-modified aromatic compound, comprising the steps of:
Reacting 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile with a quinolinecarboxaldehyde derivative to produce the quinolinecarboxyl-modified aromatic compound.
In some embodiments of the invention, the quinolinecarboxaldehyde derivative has a formula selected from one of the following formulas:
In some embodiments of the invention, the reaction conditions of 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile with a quinolinecarboxaldehyde derivative include at least one of the following conditions:
1) The reaction system is in a solution state, and the used solvent comprises an alcohol solvent or an aromatic hydrocarbon solvent (such as benzene, toluene and other aromatic hydrocarbon solvents azeotropy carry water to promote the reaction to be complete);
2) The reaction is carried out under the catalysis of a catalyst, the catalyst comprises a basic substance, and the basic substance comprises at least one of primary amine and salts thereof, secondary amine and salts thereof, tertiary amine and salts thereof, inorganic base, weak acid salt, combination of Lewis acid and tertiary amine or basic ion resin;
3) The reaction temperature is 85-95 ℃ and the reaction time is 12-36 h;
4) The molar ratio of the 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile to the quinolinecarboxaldehyde derivative is 1:0.9-1.2.
In some embodiments of the invention, the reaction conditions of 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile with a quinolinecarboxaldehyde derivative include at least one of the following conditions:
1) The reaction system is in a solution state, and the used solvent is ethanol;
2) The reaction is carried out under the catalysis of a catalyst, wherein the catalyst comprises tetrabutylammonium hydroxide (TBAH), sodium hydroxide, sodium carbonate, potassium fluoride, aluminum phosphate, diammonium hydrogen phosphate, tiCl 4/Py or TiCl 4/Et3 N;
3) The reaction temperature is 90+/-2 ℃ and the reaction time is 24+/-2 hours;
4) The molar ratio of the 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile to the quinolinecarboxaldehyde derivative is 1:1-1.1.
According to a further aspect of the present invention there is also provided the use of the above quinoline group-modified aromatic compound, a fibrous product comprising a polymer and the above quinoline group-modified aromatic compound as a starting material for the preparation of the fibrous product.
In some embodiments of the invention, the polymer comprises at least one of polyurethane, polylactic acid (PLA), cellulose Acetate (CA), and Polystyrene (PS). The polymer compound having spinnability may be used.
In some embodiments of the invention, the fibrous article comprises a fibrous material or a fibrous membrane.
According to a further aspect of the present invention, there is also provided another use of the above quinoline group-modified aromatic compound for the preparation of a pH-responsive fibrous article.
According to a further aspect of the present invention, there is also provided a method for preparing a fibrous material, comprising the steps of:
And (3) taking an electrostatic spinning solution, and forming filaments under the action of high-voltage static electricity, wherein the electrostatic spinning solution contains a polymer and the quinoline group modified aromatic compound.
In some embodiments of the present invention, the voltage of the electrostatic action is 5-30 kv.
In some embodiments of the present invention, the voltage of the electrostatic action is 10 to 25kv.
In some embodiments of the invention, the voltage of the electrostatic action is 15-20 kV.
In some embodiments of the present invention, the voltage of the electrostatic action is 16-18 kv. Such as 17kV.
In some embodiments of the present invention, the working distance of the filament is 10-15 cm under the action of high-voltage static electricity.
In some embodiments of the invention, the working distance of the filaments under high-voltage electrostatic action is 13+ -1 cm.
According to still another aspect of the present invention, there is also provided a method for preparing a fibrous membrane, comprising the steps of:
The fiber material prepared by the preparation method is interwoven to form a fiber membrane.
In some embodiments of the invention, the method of making comprises the step of depositing the fibrous material into a film. Electrospinning techniques draw a polymer solution or melt into nano-to micro-sized fibers by a high voltage electric field (typically 5-30 kV) and deposit the film. The process begins with the formation of a charged taylor cone at the spinneret, the jet undergoes severe stretching and whip instability under the force of an electric field, the solvent rapidly volatilizes to solidify the fibers, and finally a porous reticulated film is deposited by a static or dynamic collector (e.g., a rotating drum).
According to a further aspect of the invention, the use of the quinoline group-modified aromatic compounds described above or the fibrous products described above in acid-base detection, environmental monitoring, industrial control is also presented.
In some embodiments of the invention, the industrial control comprises anti-counterfeiting or textile detection. The method can be applied to various industrial controls which are directly or indirectly related to pH and need quick response, and can be applied to other industrial controls, especially industrial control processes which need quick response, based on the property that the quinoline group has multiple responses.
The fiber material provided by the invention has excellent fluorescence performance, not only has obvious fluorescence intensity, but also can generate obvious contrast change of fluorescence color in a very short time when the acid-base environment is changed. The characteristic enables the fiber membrane to have extremely high sensitivity and accuracy in the acid-base detection field. More remarkable, the response speed of the fiber membrane to acid-base environment is extremely high, the fiber membrane can react in a short period of 1 second, and powerful technical support is provided for real-time monitoring and rapid judgment. Therefore, the fiber membrane of the invention has great potential application value in the fields of acid-base detection, environment monitoring, anti-counterfeiting, textile detection, industrial control requiring quick response and the like, and provides an innovative solution for the development of related industries.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
In the description of the inventionRepresenting the ligation site.
Drawings
FIG. 1 is a 1 H NMR spectrum of a quinoline group-modified aromatic compound obtained in example 1 of the present invention.
FIG. 2 is a 1 H NMR spectrum of a quinoline group-modified aromatic compound obtained in example 2 of the present invention.
FIG. 3 is a 1 H NMR spectrum of a quinoline group-modified aromatic compound obtained in example 3 according to the present invention.
FIG. 4 is a 1 H NMR spectrum of a quinoline group-modified aromatic compound obtained in example 4 of the present invention.
FIG. 5 is a graph showing the results of the characterization of pure PLA at a magnification of 10k by SEM with respect to a fiber film prepared in example 8 of the present invention using TPABCNnQU (n=2, 3, 4), (a) pure PLA, (b) PLA-TPABCN2QU, (c) PLA-TPABCN3QU, and (d) PLA-TPANCN4QU.
FIG. 6 is a graph showing the results of the characterization of pure PLA at a magnification of 10k by SEM with respect to a fibrous film prepared using TPABCNnQU (n=5, 6,7 or 8) in example 8 of the present invention, (a) PLA-TPABCN QU, (b) PLA-TPABCN QU, (c) PLA-TPABCN7QU, and (d) PLA-TPANCN8QU.
FIG. 7 shows the PLA-TPABCN < 2 > QU acid stimulus response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL pattern, (b) XRD pattern of compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is original sample, O-HCl is acid-smoked sample, O-HCl-NH 3 is acid-smoked alkali-smoked sample.
FIG. 8 shows the PLA-TPABCN QU acid stimulus response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL profile, (b) XRD profile of the compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is the original sample, O-HCl is the acid-smoked sample, O-HCl-NH 3 is the acid-smoked alkali-smoked sample.
FIG. 9 shows the PLA-TPABCN4QU acid stimulus response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL pattern, (b) XRD pattern of the compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is the original sample, O-HCl is the acid-smoked sample, O-HCl-NH 3 is the acid-smoked alkali-smoked sample.
FIG. 10 shows the PLA-TPABCN QU acid stimulation response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL pattern, (b) XRD pattern of the compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is the original sample, O-HCl is the acid-smoked sample, O-HCl-NH 3 is the acid-smoked alkali-smoked sample.
FIG. 11 shows the PLA-TPABCN QU acid stimulus response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL pattern, (b) XRD pattern of the compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is the original sample, O-HCl is the acid-smoked sample, O-HCl-NH 3 is the acid-smoked alkali-smoked sample.
FIG. 12 shows the PLA-TPABCN QU acid stimulus response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL pattern, (b) XRD pattern of the compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is the original sample, O-HCl is the acid-smoked sample, O-HCl-NH 3 is the acid-smoked alkali-smoked sample.
FIG. 13 shows the PLA-TPABCN QU acid stimulus response test and fluorescence photograph (365 nm) obtained in example 8 of the present invention, (a) normalized PL pattern, (b) XRD pattern of the compound and micro-nanofiber membrane, (c) fluorescence photograph (365 nm) under external stimulus, O is the original sample, O-HCl is the acid-smoked sample, O-HCl-NH 3 is the acid-smoked alkali-smoked sample.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention. The test methods used in the examples are conventional methods unless otherwise specified, and the materials, reagents, etc. used, if otherwise specified, are commercially available. Unless otherwise indicated, the same parameter is the same in each embodiment. The following examples are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, reference to the term "some embodiments" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
Example 1
The present example provides a quinoline group modified aromatic compound having the structural formula:
Wherein R is
The preparation process comprises weighing 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile (0.5 g,1.39 mmol) into a three-necked flask, adding 20ml of absolute ethanol, stirring for dissolution, adjusting the temperature of a constant-temperature oil bath pot to 90 ℃ for condensation reflux, and taking TPABCN QU as an example. Quinoline-2-carbaldehyde (0.24 g,1.51 mmol) was added after complete dissolution, tetrabutylammonium hydroxide (TBAH) was added after clarification and reaction for 24 h. Suction filtration and washing of the filter residue with ethanol for 2 times gave a green solid powder (0.59 g, 85%).
The product obtained by the above operation is used for structural characterization, and the result is shown in fig. 1.
The specific data are as follows ：1H NMR(500MHz,DMSO-d6)δ8.66(s,1H),8.34(s,1H),7.94(s,1H),7.81(t,J＝8.4Hz,3H),7.44(s,1H),7.23–6.90(m,19H).
Example 2
This example provides a quinoline group-modified aromatic compound which differs from example 1 in that R is
The procedure was as in example 1 except that quinoline-2-carbaldehyde was replaced with quinoline-4-carbaldehyde to give an orange-yellow powder in 70% yield.
The product obtained by the above operation was subjected to structural characterization, and the result is shown in fig. 2.
Specific data are as follows ：1H NMR(500MHz,DMSO-d6)δ9.07(d,J＝4.5Hz,1H),8.81(s,1H),8.27(d,J＝8.5Hz,1H),8.14(d,J＝8.4Hz,1H),8.00(d,J＝8.5Hz,2H),7.93(d,J＝4.5Hz,1H),7.87(d,J＝8.3Hz,3H),7.72(d,J＝8.6Hz,3H),7.35(dd,J＝8.8,6.9Hz,4H),7.13–7.03(m,7H). example 3
This example provides a quinoline group-modified aromatic compound which differs from example 1 in that R is
The procedure was as in example 1 except that quinoline-2-carbaldehyde was replaced with quinoline-6-carbaldehyde to give a yellowish green powder with a yield of 78%.
The product obtained by the above operation was subjected to structural characterization, and the result is shown in fig. 3.
The specific data are as follows ：1H NMR(500MHz,DMSO-d6)δ8.99(s,1H),8.52(s,1H),8.47(d,J＝8.3Hz,1H),8.37–8.30(m,2H),8.16(d,J＝8.8Hz,1H),7.90(d,J＝8.5Hz,2H),7.83(d,J＝8.5Hz,2H),7.70(d,J＝8.6Hz,2H),7.63(dd,J＝8.3,4.2Hz,1H),7.35(t,J＝7.9Hz,4H),7.13–7.03(m,8H).
Example 4
This example provides a quinoline group-modified aromatic compound which differs from example 1 in that R is
The procedure was as in example 1 except that quinoline-2-carbaldehyde was replaced with quinoline-8-carbaldehyde to give a yellowish green powder with a yield of 83%.
The product obtained by the above operation was subjected to structural characterization, and the result is shown in fig. 4.
The specific data are as follows ：1H NMR(500MHz,DMSO-d6)δ9.05(s,1H),9.02(s,1H),8.54–8.47(m,2H),8.18(d,J＝8.9Hz,1H),7.89(d,J＝8.5Hz,2H),7.85(d,J＝8.5Hz,2H),7.81(t,J＝7.8Hz,1H),7.70(t,J＝8.7Hz,3H),7.38–7.31(m,4H),7.09(q,J＝7.6Hz,7H).
Example 5
This example provides a quinoline group-modified aromatic compound which differs from example 1 in that R is
The procedure was as in example 1 except that quinoline-2-carbaldehyde was replaced with quinoline-3-carbaldehyde to give a green powder in 75% yield.
The products obtained by the above operations are characterized by nuclear magnetism, and as a result, the target compounds are obtained (the reaction principle is similar to that of examples 1 to 4, and nuclear magnetism data are not shown one by one in order to avoid redundancy).
Example 6
This example provides a quinoline group-modified aromatic compound which differs from example 1 in that R is
The procedure was as in example 1 except that quinoline-2-carbaldehyde was replaced with quinoline-5-carbaldehyde to give a yellowish green powder with a yield of 79%.
The products obtained by the above operations are characterized by nuclear magnetism, and as a result, the target compounds are obtained (the reaction principle is similar to that of examples 1 to 4, and nuclear magnetism data are not shown one by one in order to avoid redundancy).
Example 7
This example provides a quinoline group-modified aromatic compound which differs from example 1 in that R is
The preparation process differs from example 1 in that quinoline-2-carbaldehyde is replaced by quinoline-5-carbaldehyde to give a yellowish green powder with a yield of 80%.
The products obtained by the above operations are characterized by nuclear magnetism, and as a result, the target compounds are obtained (the reaction principle is similar to that of examples 1 to 4, and nuclear magnetism data are not shown one by one in order to avoid redundancy).
Example 8
In this example, a fiber film was prepared, and the compound TPABCNnQU0.05g and 1g of Polymer (PLA) prepared in the above-mentioned examples 1 to 7 were dissolved in a mixed solution of 8.95gDMF/DCM (v/v=1/2) to prepare an electrostatic spinning solution. The solution was then loaded into a 10mL syringe, extruded through a spinneret at a rate of 1mL/h, spun under high voltage electrostatic forces and deposited into a film. Wherein the spinning voltage is 17kV, the working distance is 13cm, and the silicone paper is used as a grounding collector.
The microstructure of the fiber film (PLA-TPABCNnQU) prepared from pure PLA and the quinoline group-modified aromatic compound prepared in examples 1-7 is shown in FIGS. 5 and 6 by Scanning Electron Microscope (SEM). The surface of the prepared composite fiber film is even and smooth when being observed under a scanning electron microscope, and granular aggregates and beaded fibers are not observed, which shows that TPABCNnQU compounds have good compatibility with polylactic acid, and the addition of the compounds TPABCNnQU does not influence the spinning fiber forming performance of the polylactic acid.
Example 9
In this example, a fiber film was prepared, and the compound TPABCNnQU0.05g and 1g of the polymer (CA) prepared in the above examples 1 to 7 were dissolved in a mixed solution of 8.95gDMF/DCM (v/v=1/2) to prepare an electrostatic spinning solution. The solution was then loaded into a 10mL syringe, extruded through a spinneret at a rate of 1mL/h, spun under high voltage electrostatic forces and deposited into a film. Wherein the spinning voltage is 17kV, the working distance is 13cm, and the silicone paper is used as a grounding collector.
Example 10
In this example, a fiber film was prepared, and the compound TPABCNnQU0.05g and 1g of the polymer (polystyrene (PS)) prepared in the above examples 1 to 7 were dissolved in a mixed solution of 8.95gDMF/DCM (v/v=1/2) to prepare an electrostatic spinning solution. The solution was then loaded into a 10mL syringe, extruded through a spinneret at a rate of 1mL/h, spun under high voltage electrostatic forces and deposited into a film. Wherein the spinning voltage is 17kV, the working distance is 13cm, and the silicone paper is used as a grounding collector.
The fibrous membrane materials prepared in examples 8 to 10 were subjected to pH response performance test, and the test results of the fibrous membrane materials prepared in example 8 are shown in fig. 7 to 13.
The test procedure was as follows:
And cutting the micro-nanofiber membrane prepared by the operation into square samples with the size of 1cm multiplied by 1cm, placing 1mL of concentrated hydrochloric acid into a 20mL sample bottle for fumigation for 5-10s, then performing fluorescence spectrum test, and subsequently placing 1mL of 20%wt ammonia water into the 20mL sample bottle for fumigation for 5-10 s.
As shown in FIG. 7, the fluorescence emission of PLA-TPABCN < 2 > QU micro-nanofiber membrane with the compound content of 1% has no obvious change after being fumigated by hydrochloric acid steam in the acid stimulus response experiment process, and the maximum emission wavelength of the micro-nanofiber membrane is red-shifted from 521nm to 523nm after being fumigated by the hydrochloric acid steam through a fluorescence spectrometer test, and the micro-nanofiber membrane is recovered to the initial maximum emission wavelength of 521nm in the fluorescence test after being fumigated by ammonia water steam. Although there is no obvious change to naked eyes, the product has good reversible performance. XRD test shows that the spinning solution is evenly dispersed in the micro-nano fiber membrane to form an amorphous state by blending with PLA, and the molecular conformation of the micro-nano fiber is fixed due to the preparation of the micro-nano fiber, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance.
As shown in FIG. 8, in the acid stimulus response experiment, PLA-TPABCN < 3 > QU micro-nano fiber film with the compound content of 1% is fumigated for about 3s by hydrochloric acid steam, the fluorescence color is changed from green to yellow-green, and the maximum emission wavelength of fluorescence is also red-shifted from 520nm to 527nm and red-shifted by 7nm. It was deprotonated using NH 3 vapor and its wavelength was restored to the original state. XRD test shows that the spinning solution is blended with PLA to be uniformly dispersed in the micro-nano fiber membrane to form an amorphous state, and the molecular conformation of the micro-nano fiber membrane tends to be fixed due to the preparation of the micro-nano fiber membrane, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance, which shows that the acid-base stimulus response performance of the PLA-TPABCNnQU micro-nano fiber membrane has good stability and reversibility.
As shown in FIG. 9, in the same process of the acid stimulus response experiment, PLA-TPABCN4QU micro-nanofiber membrane with the compound content of 1% is fumigated for about 3s by hydrochloric acid steam, the fluorescence color is changed from yellow to bright yellow, and the maximum emission wavelength of fluorescence is also red-shifted from 541nm to 552nm and red-shifted by 11nm. It was deprotonated using NH 3 vapor and its wavelength was restored to the original state. XRD test shows that the spinning solution is blended with PLA to be uniformly dispersed in the micro-nano fiber membrane to form an amorphous state, and the molecular conformation of the micro-nano fiber membrane tends to be fixed due to the preparation of the micro-nano fiber membrane, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance, which shows that the acid-base stimulus response performance of the PLA-TPABCNnQU micro-nano fiber membrane has good stability and reversibility.
As shown in FIG. 10, in the same experimental process of acid stimulus response, PLA-TPABCN QU micro-nanofiber membrane with 1% of compound content is fumigated for about 3s by hydrochloric acid vapor, the fluorescence color is changed from green to yellow-green, and the maximum emission wavelength of fluorescence is also red-shifted from 519nm to 547nm and 28nm. It was deprotonated using NH 3 vapor and its wavelength was restored to the original state. XRD test shows that the spinning solution is blended with PLA to be uniformly dispersed in the micro-nano fiber membrane to form an amorphous state, and the molecular conformation of the micro-nano fiber membrane tends to be fixed due to the preparation of the micro-nano fiber membrane, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance, which shows that the acid-base stimulus response performance of the PLA-TPABCNnQU micro-nano fiber membrane has good stability and reversibility.
As shown in FIG. 11, in the same way, in the acid stimulus response experiment, PLA-TPABCN < 6 > QU micro-nano fiber film with the compound content of 1% is fumigated for about 3s by hydrochloric acid steam, the fluorescence color is changed from green to yellow, and the maximum emission wavelength of fluorescence is also red-shifted from 508nm to 567nm and 59nm. It was deprotonated using NH 3 vapor and its wavelength was restored to the original state. XRD test shows that the spinning solution is blended with PLA to be uniformly dispersed in the micro-nano fiber membrane to form an amorphous state, and the molecular conformation of the micro-nano fiber membrane tends to be fixed due to the preparation of the micro-nano fiber membrane, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance, which shows that the acid-base stimulus response performance of the PLA-TPABCNnQU micro-nano fiber membrane has good stability and reversibility.
As shown in FIG. 12, in the acid stimulus response experiment, PLA-TPABCN < 7 > QU micro-nano fiber film with the compound content of 1% is fumigated for about 3s by hydrochloric acid steam, the fluorescence color is changed from green to dark yellow, and the maximum emission wavelength of fluorescence is also red-shifted from 508nm to 591nm and red-shifted 83nm. It was deprotonated using NH 3 vapor and its wavelength was restored to the original state. XRD test shows that the spinning solution is blended with PLA to be uniformly dispersed in the micro-nano fiber membrane to form an amorphous state, and the molecular conformation of the micro-nano fiber membrane tends to be fixed due to the preparation of the micro-nano fiber membrane, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance, which shows that the acid-base stimulus response performance of the PLA-TPABCNnQU micro-nano fiber membrane has good stability and reversibility.
As shown in FIG. 13, in the acid stimulus response experiment process, the fluorescence emission of the PLA-TPABCN < 8 > QU micro-nano fiber film with the compound content of 1% is not obviously changed after being fumigated by hydrochloric acid steam, and the maximum emission wavelength of the micro-nano fiber film is red-shifted from 512nm to 514nm after being fumigated by the hydrochloric acid steam through a fluorescence spectrometer test, and the micro-nano fiber film is recovered to the original maximum emission wavelength of 512nm in the fluorescence test after being fumigated by ammonia water steam. Although there is no obvious change to naked eyes, the product has good reversible performance. XRD test shows that the spinning solution prepared by blending with PLA is uniformly dispersed in the micro-nano fiber membrane to form an amorphous state, and the molecular conformation of the micro-nano fiber membrane tends to be fixed due to the preparation of the micro-nano fiber membrane, so that the micro-nano fiber membrane has reversible acid-base stimulus response performance.
The properties of the fibrous membrane materials produced in examples 9 and 10 are similar and are not shown one by one to avoid redundancy.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A quinoline group modified aromatic compound is characterized by having the following structural formula:
Wherein R is selected from one of the following structures:
2. The method for producing a quinoline-group-modified aromatic compound according to claim 1, wherein the method comprises the steps of:
Reacting 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile with a quinolinecarboxaldehyde derivative to produce the quinolinecarboxyl-modified aromatic compound.
3. The process according to claim 2, wherein the reaction conditions of 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile with the quinolinecarboxaldehyde derivative comprise at least one of the following conditions:
1) The reaction system is in a solution state, and the used solvent comprises an alcohol solvent or an aromatic hydrocarbon solvent;
2) The reaction is carried out under the catalysis of a catalyst, the catalyst comprises a basic substance, and the basic substance comprises at least one of primary amine and salts thereof, secondary amine and salts thereof, tertiary amine and salts thereof, inorganic base, weak acid salt, combination of Lewis acid and tertiary amine or basic ion resin;
3) The reaction temperature is 85-95 ℃ and the reaction time is 12-36 h;
4) The molar ratio of the 2- (4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) acetonitrile to the quinolinecarboxaldehyde derivative is 1:0.9-1.2.
4. A fiber product, characterized in that the fiber product is prepared from a polymer and the quinoline group-modified aromatic compound according to claim 1.
5. The fibrous article of claim 4, wherein the polymer comprises at least one of polyurethane, polylactic acid, cellulose acetate, and polystyrene.
6. Use of a quinoline group-modified aromatic compound according to claim 1 for the preparation of a pH-responsive fibrous article.
7. A preparation method of a fiber material is characterized by comprising the following steps:
And (3) taking an electrostatic spinning solution, and forming filaments under the action of high-voltage static electricity, wherein the electrostatic spinning solution contains a polymer and the quinoline group modified aromatic compound as defined in claim 1.
8. A preparation method of a fiber membrane is characterized by comprising the following steps:
the fibrous material produced by the process of claim 7 interweaved to form a fibrous membrane.
9. Use of a quinoline-group-modified aromatic compound according to claim 1 or a fibrous product according to claim 4 or 5 for acid-base detection, environmental monitoring, industrial control.
10. The method according to claim 9, wherein the industrial control comprises anti-counterfeit or textile detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510565258.4A CN120504629A (en) | 2025-04-30 | 2025-04-30 | Quinoline group modified aromatic compound, preparation method thereof and application thereof in pH responsive fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510565258.4A CN120504629A (en) | 2025-04-30 | 2025-04-30 | Quinoline group modified aromatic compound, preparation method thereof and application thereof in pH responsive fiber membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN120504629A true CN120504629A (en) | 2025-08-19 |
Family
ID=96714805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202510565258.4A Pending CN120504629A (en) | 2025-04-30 | 2025-04-30 | Quinoline group modified aromatic compound, preparation method thereof and application thereof in pH responsive fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN120504629A (en) |
-
2025
- 2025-04-30 CN CN202510565258.4A patent/CN120504629A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | Tunable mechano-responsive organogels by ring-opening copolymerizations of N-carboxyanhydrides | |
| CN101910281A (en) | Polyolefin nanocomposites with functional ionic liquids and carbon nanofillers | |
| Guo et al. | Self-healing gels triggered by ultrasound with color-tunable emission based on ion recognition | |
| CN108456169B (en) | Gel factor, preparation method thereof, hydrogel, lanthanum metal hydrogel and application thereof | |
| CN106244142B (en) | Preparation method of fluorescent carbon quantum dot polymer hybrid material | |
| CN109456250B (en) | Thermally Activated Delayed Fluorescence (TADF) Nanoprobes and Their Preparation and Applications in Bioimaging | |
| Mao et al. | Solvent induced helical aggregation in the self-assembly of cholesterol tailed platinum complexes | |
| CN114315732A (en) | Fluorescent material and application thereof | |
| CN112441965A (en) | Preparation method of nano assembly with AIE effect | |
| CN101603213A (en) | Polyimide nano-fiber and preparation method thereof | |
| CN103237822A (en) | Novel acrylamide-ased mesoporous polymer and preparation method thereof | |
| CN114621159A (en) | Diazosulfide-based fluorescent material, fluorescent polymer, fluorescent nanoparticles, and preparation method and application thereof | |
| KR100779986B1 (en) | Manufacturing method of ultra fine fiber containing poly acetylene | |
| CN109535313A (en) | A kind of preparation method and applications of copolymer porous microsphere | |
| CN110746713B (en) | Colorimetric-fluorescent fiber membrane for detecting hypochlorite and preparation method thereof | |
| KR101429742B1 (en) | Polymeric fluorescent substance | |
| CN111303862A (en) | Dual-emission fluorescent temperature-sensitive polymer composite film and preparation method and application thereof | |
| CN120504629A (en) | Quinoline group modified aromatic compound, preparation method thereof and application thereof in pH responsive fiber membrane | |
| CN103201417B (en) | Porous electrospun fiber and preparation method thereof | |
| CN109970896A (en) | A method for constructing thermosensitive carbon nanotube composites based on carbon dot modification | |
| CN116396169B (en) | Compound containing bis-salicylaldehyde end group, polymer nanofiber and preparation method thereof | |
| JP5377265B2 (en) | Polymer / tartaric acid crystalline nanocomposite and method for producing the same | |
| CN111269369A (en) | Polyolefin diblock copolymer with dual responses to magnetism and temperature and preparation method thereof | |
| Ding et al. | Imidazolium cation mediated synthesis of polystyrene–polyaniline core–shell structures | |
| WO2012177021A2 (en) | Polymeric fluorescent material |
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 |