CN114874341A - Fluorescent nanoparticle with AIE characteristic, bionic nano composite hydrogel actuator, preparation method and application - Google Patents
Fluorescent nanoparticle with AIE characteristic, bionic nano composite hydrogel actuator, preparation method and application Download PDFInfo
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Abstract
The invention discloses a fluorescent nanoparticle with AIE characteristics, a bionic nano composite hydrogel actuator, a preparation method and application. The invention provides a fluorescent nanoparticle with aggregation-induced emission (AIE) characteristics, which is prepared from TPE-pyo fluorescent molecules and cellulose nanocrystals under the action of a catalyst. Based on the conjugated donor-acceptor (D-A) structure of the fluorescent nanoparticles, the change of a microenvironment can be sensitively sensed, so that the dynamic motion of the fluorescent nanoparticles in the hydrogel forming process can be tracked; visualizing the static distribution of the fluorescent nanoparticles in the hydrogel; and monitoring the process of bending motion of the nano composite hydrogel under thermal stimulation and the phase transition behavior. The fluorescent nanoparticles with AIE characteristics and the related application method thereof are expected to promote the application of the fluorescence technology in the fields of artificial muscles, intelligent actuation and bionic nano composite materials.
Description
Technical Field
The invention relates to a fluorescent nanoparticle with AIE (advanced Electron emission) characteristics, a bionic nano-composite hydrogel actuator, a preparation method and application, and belongs to the technical field of fluorescent nano-composite materials.
Background
The hydrogel driver is a novel intelligent material capable of generating reversible deformation or volume change to external stimuli (light, heat, chemistry, electricity and the like). As a class of soft and wet materials similar to biological tissues, the hydrogel driver has great potential application value in the fields of soft robots, artificial muscles, tissue engineering and the like. The addition of nanoparticles to hydrogel systems to induce asymmetric network structures is an effective method.
In order to realize the construction of an asymmetric hydrogel network, the distribution condition of nanoparticles in a high-molecular matrix is very important to be accurately regulated and controlled. However, conventional testing methods such as Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Atomic Force Microscope (AFM), etc. require complicated sample preparation processes such as crushing, cutting, vacuum drying, etc., which inevitably causes the internal structure of the material to be damaged, thereby causing information distortion, and especially when the material is a hydrogel, i.e., a "wet and soft" material, it becomes more difficult to observe the distribution of the nanoparticles. Moreover, the test window of the conventional test is small, and difficult to represent the structural information of the macroscopic material. Therefore, a testing method which is simple to operate, non-destructive and available in a wet state is needed to research the distribution information of the nanoparticles in the hydrogel system, and the rapid development of the hydrogel driver is promoted.
The fluorescence technology has the advantages of high resolution, no damage, good biocompatibility and the like, and is concerned by a lot in the fields of chemical and biological sensing, biological imaging, catalysis, new energy materials and the like. However, the conventional fluorescent dyes such as rhodamine B and fluorescein have high quantum yield in a solution state, and in a solid state and an Aggregation state, due to the close packing of molecules, the luminescence property is greatly reduced, even no luminescence occurs, that is, Aggregation induced Quenching (ACQ) occurs, which greatly limits the application of the fluorescence technology in the field of material science. Until 2001, the Aggregation-Induced Emission (AIE) phenomenon was discovered by Down's loyalist. The AIE molecules with highly twisted propeller-like conformation can effectively inhibit the intermolecular pi-pi stacking in an aggregation state, prevent the dissipation of excited state energy through a non-radiative decay channel, and emit light strongly in the aggregation state. In addition, AIE molecules are extremely sensitive to microenvironments according to the Restriction of Intramolecular Movement (RIM) mechanism, and have been successfully used in the study of various microenvironments. Therefore, if the AIE molecules are modified on the nanoparticles and are introduced into the hydrogel system, the visual research of the nanoparticles in the hydrogel system is hopeful to be realized, so that the relationship between the internal structure and the macroscopic property of the hydrogel is further explored, and the development of a hydrogel driver in a plurality of fields is promoted.
Disclosure of Invention
The technical problem solved by the invention is as follows: the characteristics of the hydrogel are difficult to be represented due to the reasons of the softness and the humidity, the low conductivity, the low contrast ratio of the nano particles and the polymer matrix and the like, and the technical problems of difficulty in realizing dynamic real-time detection and the like are solved.
In order to solve the technical problems, the invention provides a fluorescent nanoparticle with AIE characteristics, which has a chemical structural formula shown in formula I:
the fluorescent nanoparticles emit yellow light, the solid emission wavelength is 518nm, and the liquid dispersion system emission wavelength is 520-532 nm.
The invention also provides a preparation method of the fluorescent nanoparticle with the AIE characteristic, which comprises the following steps:
step 1: fully drying the cellulose nanocrystals, and dispersing the cellulose nanocrystals into dichloromethane to obtain a CNC dispersion liquid;
step 2: respectively dissolving TPE-pyo fluorescent molecules shown in a formula II and a catalyst 4-dimethylaminopyridine into dichloromethane to obtain corresponding TPE-pyo solution and catalyst solution;
and step 3: adding the TPE-pyo solution into the CNC dispersion liquid, adding a catalyst solution, uniformly mixing, and carrying out magnetic stirring to react;
and 4, step 4: after the reaction is finished, sequentially filtering, washing and drying the obtained product to obtain fluorescent nano particle TPE-CNC with AIE characteristics, wherein the chemical structure of the fluorescent nano particle TPE-CNC is shown as a formula I;
preferably, the cellulose nanocrystal in the step 1 has a diameter of 20-30nm, a length of 200-300nm and an aspect ratio of about 10; the concentration of the CNC dispersion liquid is 1-5 wt%; the concentrations of the TPE-pyo solution and the catalyst solution in the step 2 are respectively as follows: 0.5-2 mg/mL, 0.001-0.008M.
Preferably, the mass ratio of the TPE-pyo in the TPE-pyo solution to the cellulose nanocrystals in the CNC solution in the step shown is 0.075-0.1: 1.
the invention also provides application of the fluorescent nanoparticles with AIE characteristics.
Preferably, the application comprises the application in the preparation of the bionic nanocomposite hydrogel actuator, and/or the application in the visual monitoring of the forming process of the bionic nanocomposite hydrogel actuator, and/or the application in the visual detection of the internal structure of the bionic nanocomposite hydrogel actuator, and/or the application in the visual monitoring of the thermal stimulation response of the bionic nanocomposite hydrogel actuator.
Preferably, the method comprises the step of visually monitoring the forming process of the bionic nanocomposite hydrogel actuator during the process of preparing the bionic nanocomposite hydrogel actuator.
Preferably, the method further comprises the step of visually detecting the internal structure and the thermal stimulation response behavior of the prepared bionic nanocomposite hydrogel actuator.
The invention also provides a bionic nano composite hydrogel actuator, which is a composite hydrogel fiber formed by the polymerization of the fluorescent nano particles shown in the formula I, N-isopropyl acrylamide, N' -methylene bisacrylamide and polyethylene glycol monomethyl ether methacrylate through photo-initiated free radicals, and the emission wavelength of the composite hydrogel fiber is 482 nm.
Preferably, the forming process or the thermal stimulation response behavior of the composite hydrogel fiber is visually monitored by a fluorescence detection instrument or tool; the internal structure of the composite hydrogel fiber is visually characterized by a fluorescence detection instrument or tool. Specifically, the dynamic motion of the nanoparticles in the composite hydrogel forming process is tracked through a fluorescence spectrum and a fluorescence microscope; monitoring the dynamic forming process of the hydrogel and visualizing the static distribution of the fluorescent nanoparticles in the hydrogel by a fluorescence microscope and a laser confocal microscope; the process of the spiral motion and the hydrogel phase transformation of the nanocomposite hydrogel actuator under thermal stimulation is monitored through fluorescence shooting and fluorescence spectroscopy.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a fluorescent nanoparticle with aggregation-induced emission (AIE) characteristics, which can sensitively sense the change of a microenvironment based on a conjugated donor-acceptor (D-A) structure of the fluorescent nanoparticle, thereby realizing the tracking of the dynamic motion of the fluorescent nanoparticle in the hydrogel forming process; visualizing the static distribution of the fluorescent nanoparticles in the hydrogel; monitoring the process and phase transition behavior of the nano composite hydrogel which generates bending motion under thermal stimulation;
(2) the method for labeling the cellulose nanocrystals by the aggregation-induced emission molecules has the advantages that the reaction conditions are normal-temperature magnetic stirring, water and oxygen removal is not needed, the process is simple and easy to implement, the fluorescence labeling effect is obvious, the quantum yield of the obtained fluorescent nanoparticles is from 4.7% of solid state to 7.3% of water dispersion to 16.0% of hydrogel, the typical AIE characteristic is shown, and the method can be used for the research of various systems;
(3) the fluorescent nanoparticles have obvious TICT effect, the emission wavelength is from 532nm in aqueous dispersion to 482nm in hydrogel, the color change is obvious, and the fluorescent nanoparticles can be used for detecting the change of a microenvironment; the aggregation-induced emission molecules have no biological toxicity, and the cellulose nanocrystal is a common biological material, so that the application of a fluorescence detection technology in the field of nano composite hydrogel is greatly promoted;
(4) when the fluorescent nanoparticles with the AIE characteristic provided by the invention are used for visually monitoring the internal structure of the CNC nano composite hydrogel actuator in the forming process, the complex sample treatment of the traditional testing method is avoided, the network structure of the hydrogel is protected from being damaged, the detection result is accurate, the resolution ratio is less than 100 mu m, the real-time visual monitoring can be realized, and the data feedback time is less than 500 ms;
(5) the fluorescent nanoparticles with the AIE characteristic provided by the invention can be used for visually monitoring the thermal stimulation response process of the CNC nano composite hydrogel actuator, can feed back the internal network structure in the hydrogel actuation process in real time, and can be directly observed by naked eyes; meanwhile, the fluorescence intensity test can detect the lower critical transition temperature (LCST) and the deformation temperature (T) in the hydrogel deformation process df ) The sample is not damaged, and the detection can be repeated for more than 50 times;
(6) the fluorescent nanoparticles with the AIE characteristic provided by the invention can be used for representing the internal structure of CNC (computerized numerical control) nano composite hydrogel, does not need complex sample preparation, has high sensitivity and high resolution, is lossless, can realize real-time observation, and is expected to promote the application of a fluorescence technology in the fields of artificial muscle, intelligent actuation and bionic nano composite materials.
Drawings
FIG. 1 shows the synthesis process of fluorescent nanoparticle TPE-CNC and the photophysical properties of the obtained fluorescent nanoparticles; wherein a is that TPE-pyo fluorescent molecules are grafted to CNC (computerized numerical control) nano particles through a click reaction, b is that fluorescence spectra represent that the obtained fluorescent nano particles emit strong yellow fluorescence in a solid state and a water dispersion system, c is that thin-layer chromatography (TLC) proves that the TPE-pyo fluorescent molecules are in covalent connection with the CNC nano particles, and d is that the fluorescence intensity of the TPE-CNC fluorescent nano particle water dispersion is in a linear relation with the concentration;
FIG. 2 is a graph of the particle size change before and after CNC nanoparticle grafting; wherein a is an atomic force microscope picture before grafting, b is an atomic force microscope picture after grafting, c is the particle size distribution of the CNC nano particles and the TPE-CNC fluorescent nano particles, and d is the diameter of the CNC nano particles and the TPE-CNC fluorescent nano particles calculated by a molecular theory;
FIG. 3 shows the change of fluorescence color and luminescence intensity of TPE-CNC in different micro environments during the preparation process of the bionic nano-composite hydrogel actuator, wherein the fluorescence color of the TPE-CNC gradually changes from yellow to blue and the luminescence intensity continuously increases as the system changes from water to a hydrogel precursor with higher viscosity and then to polymerization is completed to form hydrogel; wherein, a is a schematic diagram of the preparation process and the luminescence change, and b is a fluorescence spectrum characterization result;
FIG. 4 is a graph showing the monitoring of the sedimentation process of nanoparticles during the hydrogel formation process by fluorescence spectroscopy, wherein the fluorescence intensity is observed to increase and then decrease as time goes on, and finally the equilibrium state is reached in 320 min;
FIG. 5 is a graph showing the detection of gradient structures in hydrogel by fluorescence spectroscopy, where the height interval of the positions I-X is 1mm from top to bottom, the gradual increase of fluorescence intensity along the direction of gravity can be observed, and the excitation wavelength is 370 nm; wherein, a is a fluorescence spectrogram, and b is a fluorescence intensity gradient change curve;
FIG. 6 is a Scanning Electron Microscope (SEM) image showing the relationship between the nanoparticle distribution and the hydrogel network, i.e., the gel network density is high in the region where the nanoparticles are distributed more, by using a fluorescence microscope to track the gel forming process and a laser confocal microscope to observe the nanoparticle distribution in the gel; wherein a is a picture of the nano composite hydrogel driver in the forming process, which is shot in real time by a fluorescence microscope; b is the distribution of the fluorescent nanoparticles in the hydrogel visually observed by a laser confocal microscope, c is the network structure of the hydrogel observed by using SEM, and d is an enlarged view of c;
FIG. 7 is a graph showing the visual monitoring of the actuation process of a hydrogel actuator by fluorescence imaging, wherein the hydrogel fiber is subjected to asymmetric bending deformation under 60 ℃ thermal initiation, and the fluorescence intensity of the inner side of the crimped fiber is higher than that of the outer side under the irradiation of an ultraviolet lamp (365nm), which indicates that more fluorescent nanoparticles TPE-CNC are arranged inside the crimped fiber, so that the hydrogel fiber is bent; wherein, a is a picture of the hydrogel fiber under natural light and a schematic diagram of an internal network structure, and b is a fluorescent picture for monitoring the hydrogel fiber under an ultraviolet lamp to generate asymmetric bending deformation;
FIG. 8 shows the change of internal network structure during the thermal stimulation response of hydrogel measured by temperature-variable fluorescence spectroscopy, where LCST and T of hydrogel are measured at 32 ℃ and 49 ℃ respectively df 。
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
In one embodiment of the invention, fluorescent nanoparticles are designed and synthesized, wherein fluorescent molecules are Tetraphenylethylene (TPE) derivatives TPE-pyo with activated alkynyl, the nanoparticles are biomass Cellulose Nanocrystals (CNC), the mass ratio of TPE-pyo: CNC is 0.075-0.1, and the molar concentration of DMAP is 0.002-0.008M. TPE and CNC are covalently connected through click reaction, so that the fluorescent material has AIE characteristics and strong fluorescence emission in powder state, water dispersion system and hydrogel composite system.
The fluorescent nanoparticles have a D-A structure, and have sensitive response to a microenvironment: the luminescent color of the fluorescent nanoparticles changes from yellow (532nm) to blue (482nm) as the polarity of the microenvironment increases due to the Twisted Intramolecular Charge Transfer (TICT) effect; due to the effect of the Restriction of Intermolecular Movement (RIM), the luminous intensity of the fluorescent nanoparticles is continuously increased along with the increase of the microenvironment hardness.
In one embodiment of the present invention, the proposed nanocomposite hydrogel actuator is a hydrogel capable of generating stimulus-responsive motion formed by adding CNC nanoparticles to a hydrogel precursor and initiating polymerization by an initiator. The hydrogel system is a typical temperature-sensitive hydrogel, a cross-linked network is formed by PNIAM, Bis and PEGMEMA, and the network density is adjusted by CNC nanoparticles in the cross-linked network.
According to the invention, the dynamic motion and the static distribution of the fluorescent nanoparticles in the hydrogel composite system can be tracked by the fluorescent labeled nanoparticles.
The invention monitors the continuous sedimentation of the nano particles under the action of gravity in the gel forming process through fluorescence spectroscopy in one embodiment, and finally, a concentration gradient is formed in the hydrogel along the gravity direction.
In one embodiment of the invention, by a fluorescence microscope, the asymmetric flow of the nanoparticles due to the marangoni effect in the gel forming process is observed; the fluorescent nanoparticles form an eccentric circle-shaped concentration gradient on the cross section of the hydrogel fiber under the observation of a laser confocal microscope; the scanning electron microscope observes that the eccentric circle concentration gradient of the nano particles leads to a crescent network structure of the hydrogel.
In the invention, the internal structure of the nano-composite hydrogel fiber actuator is expressed by the fluorescence intensity of the nano-particles, the fluorescence intensity is high in a region with high network density, and the fluorescence intensity is low in a region with low network density.
The nano composite hydrogel actuator prepared by the invention can rapidly respond to thermal stimulation and generate asymmetric bending, and in one embodiment, the asymmetric structure in the fiber in the response process can be visualized through fluorescence imaging.
The invention further analyzes and obtains the relation between the distribution of the nano particles and the micro network structure and the macro actuating performance of the gel by tracing the nano particles through fluorescence.
In the following examples, cellulose nanocrystals (diameter 20-30nm, length 200-300nm) were obtained from the Karsch technology (Science K), N-isopropylacrylamide (98%) was obtained from TCI Chiese (Shanghai) chemical industry Co., Ltd., N, N' -methylenebisacrylamide (99%), polyethylene glycol monomethyl ether methacrylate (M) n ＝500g mol -1 ) And the photoinitiator alpha, alpha-diethoxyacetophenone was purchased from Aladdin reagent (Shanghai) Co., Ltd, and the TPE-pyo fluorescent molecule was purchased from Medidyme biomedical Co., Ltd, Shanghai.
Example 1 design and Synthesis of fluorescent nanoparticles TPE-CNC
The method comprises the following steps of grafting TPE-pyo fluorescent molecules onto CNC through a click reaction to synthesize fluorescent nano TPE-CNC, as shown in FIG. 1a, specifically comprising the following steps:
(1) preparing a solution: 10-30mg of TPE-pyo fluorescent molecule (alkyne-TPE) is dissolved in 10-30mL of CH 2 Cl 2 Dispersing 0.1-0.4g Cellulose Nanocrystalline (CNC) in 10-90mL CH in solvent 2 Cl 2 Dissolving DMAP (4-dimethylaminopyridine) in CH by ultrasonic treatment for 10-40min 2 Cl 2 To obtain a solution of 20 mg/mL; wherein, the TPE-pyo fluorescent molecule and the CNC chemical structural formula are shown as follows:
(2) mixing the prepared 0.5-4mL DMAP solution with the TPE-pyo solution, dropwise adding the CNC suspension while stirring, and stirring at room temperature for 12h for full reaction;
(3) filtering the TPE-CNC product after the reaction is finished, and using a large amount of CH 2 Cl 2 Continuously washing until the filtrate has no fluorescence, vacuum drying at room temperature for 48h to obtain TPE-CNC fluorescent nanoparticles which emit strong yellow fluorescence in solid and water-dispersed systems, as shown in figure 1b, thin-layer chromatography (TLC) proves that the AIE molecules and the CNC nanoparticles are covalently linked, as shown in figure 1cAs shown, the fluorescence intensity of the aqueous dispersion of fluorescent nanoparticles was linearly related to the concentration, as shown in FIG. 1 d.
FIG. 2 shows the particle size change before and after CNC nanoparticle grafting, and the diameter of TPE-CNC is increased by 3nm compared with CNC, which is consistent with the calculation result of molecular theory.
Example 2 preparation of biomimetic nanocomposite hydrogel actuators
Introducing TPE-CNC fluorescent nanoparticles into a composite hydrogel system to prepare a biomimetic nanocomposite hydrogel actuator (TPE-CNC nanocomposite hydrogel fiber), comprising:
0.02-0.06g of TPE-CNC was dispersed in 2mL of H 2 And O, performing ultrasonic treatment for 3min, adding 0.1-0.3g N-isopropyl acrylamide (NIPAM), 0.001-0.004g N, N' -methylene bisacrylamide (Bis), 10-40 mu L of polyethylene glycol monoethyl ether methacrylate (PEGMEMA) and 2-6 mu L of photoinitiator DEAP, and stirring at room temperature in the dark for 10-60 min. And (3) pouring the solution into a fiber mold, and polymerizing for 10-60min by ultraviolet initiation to obtain the TPE-CNC nano composite hydrogel fiber. Fig. 3 shows that in the preparation process, the TPE-CNC is in different microenvironments, the fluorescence color and the luminescence intensity change, and the fluorescence color of the TPE-CNC is gradually changed from yellow to blue, and the luminescence intensity is continuously increased along with the system from water to the hydrogel precursor with higher viscosity and then to the hydrogel precursor after polymerization is completed.
Example 3 tracking of the dynamic motion and static distribution process of fluorescent nanoparticles during hydrogel preparation:
the TPE-CNC hydrogel precursor dispersion liquid is continuously scanned by a fluorescence spectrum detector (figure 4), the excitation wavelength is set to be 350-400nm, the scanning range is 400-800nm, and the slit is set to be 1 nm. The cuvette used was a 750 μ L microcuvette with an optical path of 2mm, and to ensure uniformity, the samples were mixed thoroughly before testing, testing was carried out at room temperature, and it was ensured that the fluorescence spectrometer and the samples were not disturbed. The testing time is more than or equal to 400min, the fluorescence intensity of the sample is firstly enhanced and then weakened along with the lapse of time, because the fluorescent nano particle TPE-CNC firstly generates aggregation among particles in a hydrogel dispersion system and then continuously generates sedimentation under the action of gravity, and meanwhile, the sedimentation of the particles reaches an equilibrium state under the combined action of Brownian motion and gravity, and the fluorescence intensity is not increased any more. Finally, the fluorescence intensity gradually increased in the direction of gravity, and the nanoparticles exhibited a gradient distribution, i.e., the concentration of nanoparticles gradually increased along the direction of gravity (fig. 5).
Example 4 monitoring the hydrogel formation process and observing the internal microstructure of the hydrogel:
the molding process of the nanocomposite hydrogel driver was monitored in real time by a fluorescence microscope (fig. 6a) of Nikon Eclipse Ni-U type, with a mercury lamp as excitation light source, 360nm wavelength, transmission mode. And a 365nm ultraviolet light source is arranged on the side of the objective table and is used for exciting the hydrogel precursor to generate free radical polymerization. And (3) observing the hydrogel polymerization process in real time by using CCD (charge coupled device) shooting, wherein the shooting time is longer than or equal to 30min, a 365nm ultraviolet light source is turned off and a 360nm mercury lamp light source is turned on during each shooting. As the polymerization process proceeds, the hydrogel and air interface continuously move to form an asymmetric interface shape. The distribution of fluorescent nanoparticles in the hydrogel was visualized by a confocal laser microscope (fig. 6b) of the type leia TCS SP5II, 405nm excitation, single channel. Before testing, the hydrogel is sliced, vertically cut into slices with the diameter less than or equal to 100 mu m along the radial direction of the fiber, soaked in deionized water, and kept in a hydrogel swelling state, so that the structure is not damaged. During testing, the sample is spread in a laser confocal culture dish and sealed, and the gradient distribution of the eccentric shaft of the fluorescent nanoparticles on the fiber section is observed. The same sample was freeze-dried and the hydrogel network structure was observed by SEM (fig. 6c, d), corresponding to the distribution of the nanoparticles, which are asymmetrically distributed to form a meniscus network structure.
Example 5 visualization of hydrogel actuator thermal stimulus responsive actuation process:
the hydrogel actuator thermal stimulus response actuation process was monitored visually by a homemade fluorescence imaging device (fig. 7) connected to a contact electronic thermometer ETS-D5 by an IKA hot plate HP 10, accurately controlled at 60 ℃, with an ultraviolet lamp fixed 10cm above the hot plate, and a canon EOS 80D imaging system fixed vertically 20cm above the hot plate. The hydrogel actuators were placed in deionized water for sufficient swelling for 48h before testing and fluorescence imaging was performed in a dark room. Turning on the ultraviolet lamp, turning on the camera, rapidly putting the sample into constant temperature water of 60 ℃, observing and recording the shape and fluorescence property change of the sample, and bending the hydrogel fiber to the side with strong fluorescence intensity (figure 7 b). The change of the internal micro-network structure in the hydrogel thermal stimulation response process was further monitored by fluorescence spectroscopy (fig. 8), which was equipped with a temperature control system, with the temperature increasing from 20 ℃ to 50 ℃ and scanning at 0.5 ℃ per liter. The decrease in fluorescence intensity before 32 ℃ (LCST) was observed with increasing temperature, indicating that the internal molecular chains of the hydrogel become hydrophobic from hydrophilic, begin to curl and coil, and the scattering effect increases; the fluorescence intensity begins to increase at 43 ℃, and the change rate is fastest at 49 ℃, which indicates that the gel collapses in an internal network and deforms at the moment, namely 49 ℃ is the deformation temperature of the hydrogel.
In conclusion, the invention is expected to promote the application of the fluorescence technology in the fields of artificial muscle, intelligent actuation and bionic nano composite materials.
Claims (10)
1. A fluorescent nanoparticle with AIE characteristics is characterized in that the chemical structural formula of the fluorescent nanoparticle is shown as a formula I:
the fluorescent nanoparticles emit yellow light, the solid emission wavelength is 518nm, and the liquid dispersion system emission wavelength is 520-532 nm.
2. The method of claim 1, wherein the steps of preparing fluorescent nanoparticles with AIE properties comprise:
step 1: fully drying the cellulose nanocrystals, and dispersing the cellulose nanocrystals into dichloromethane to obtain CNC dispersion;
step 2: respectively dissolving TPE-pyo fluorescent molecules shown in a formula II and a catalyst 4-dimethylaminopyridine into dichloromethane to obtain corresponding TPE-pyo solution and catalyst solution;
and step 3: adding the TPE-pyo solution into the CNC dispersion liquid, adding a catalyst solution, uniformly mixing, and carrying out magnetic stirring to react;
and 4, step 4: after the reaction is finished, sequentially filtering, washing and drying the obtained product to obtain fluorescent nano particle TPE-CNC with AIE characteristics, wherein the chemical structure of the fluorescent nano particle TPE-CNC is shown as a formula I;
3. the method as claimed in claim 2, wherein the diameter of the cellulose nanocrystal in step 1 is 20-30nm, and the length is 200-300 nm; the concentration of the CNC dispersion liquid is 1-5 wt%; the concentrations of the TPE-pyo solution and the catalyst solution in the step 2 are respectively as follows: 0.5-2 mg/mL, 0.001-0.008M.
4. The method of claim 2, wherein the mass ratio of TPE-pyo in TPE-pyo solution to cellulose nanocrystals in CNC solution in the step is 0.075-0.1: 1.
5. use of the fluorescent nanoparticle with AIE properties according to claim 1.
6. The use according to claim 5, comprising use in the manufacture of a biomimetic nanocomposite hydrogel actuator, and/or use in visually monitoring a molding process of a biomimetic nanocomposite hydrogel actuator, and/or use in visually detecting an internal structure of a biomimetic nanocomposite hydrogel actuator, and/or use in visually monitoring a thermal stimulus response of a biomimetic nanocomposite hydrogel actuator.
7. The use of claim 5 or 6, comprising simultaneously visually monitoring the shaping process of the biomimetic nanocomposite hydrogel actuator during the preparation thereof.
8. The use of claim 7, further comprising visually inspecting the internal structure and thermal stimulus response behavior of the fabricated biomimetic nanocomposite hydrogel actuator.
9. A bionic nano-composite hydrogel actuator is characterized in that the bionic nano-composite hydrogel actuator is a composite hydrogel fiber formed by photo-initiated free radical polymerization of fluorescent nano-particles shown in a formula I, N-isopropylacrylamide, N' -methylenebisacrylamide and polyethylene glycol monomethyl ether methacrylate, and the emission wavelength of the composite hydrogel fiber is 482 nm.
10. The biomimetic nanocomposite hydrogel actuator of claim 9, wherein the formation process or thermal stimulus response behavior of the composite hydrogel fibers is visually monitored by a fluorescence detection instrument or tool; the internal structure of the composite hydrogel fiber is visually characterized by a fluorescence detection instrument or tool.
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