CN113629183A - Phenylalanine dipeptide-based co-self-assembly product and preparation method and application thereof - Google Patents

Phenylalanine dipeptide-based co-self-assembly product and preparation method and application thereof Download PDF

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CN113629183A
CN113629183A CN202110713017.1A CN202110713017A CN113629183A CN 113629183 A CN113629183 A CN 113629183A CN 202110713017 A CN202110713017 A CN 202110713017A CN 113629183 A CN113629183 A CN 113629183A
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dipeptide
phenylalanine
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assembly product
mixed solution
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CN113629183B (en
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杨如森
袁慧
胡文
张娇娇
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Xidian University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/01Manufacture or treatment
    • H10N30/09Forming piezoelectric or electrostrictive materials
    • H10N30/098Forming organic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02NELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N2/00Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
    • H02N2/18Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention relates to a phenylalanine dipeptide-based co-self-assembly product, a preparation method and application thereof, wherein the method comprises the following steps of 1: preparing a mixed solution of phenylalanine dipeptide and dipeptide; step 2: and immersing the substrate into the mixed solution, and then lifting the substrate upwards from the solution along a direction vertical to the horizontal liquid level at a preset speed until the substrate is completely separated from the mixed solution, wherein a phenylalanine dipeptide-based co-self-assembled array is formed at a three-phase interface of a gas phase, a liquid phase and a solid phase in the lifting process. The method can synthesize the ordered phenylalanine dipeptide based co-self-assembly array in a large scale, and in the assembly process, the phenylalanine dipeptide based co-self-assembly products with different dipeptide ratios can be obtained by regulating the ratio of the phenylalanine dipeptide and the dipeptide in the mixed solution, so that the piezoelectric property of the phenylalanine dipeptide based co-self-assembly product can be regulated and controlled, and a piezoelectric constant regulation and control strategy which is simple and feasible and has low equipment cost is provided.

Description

Phenylalanine dipeptide-based co-self-assembly product and preparation method and application thereof
Technical Field
The invention belongs to the technical field of crossing of biological micro-nano structure materials and electrons, and particularly relates to a phenylalanine dipeptide-based co-self-assembly product and a preparation method and application thereof.
Background
In recent years, more and more biomaterials have been found to have piezoelectric properties, such as bone, proteins, cellulose, bacteriophages, amino acids, polypeptides and the like. The biological materials benefit from the advantages of piezoelectric property, biocompatibility, certain specific surface area and the like, and have great application prospects in the fields of biomedicine, genetic engineering, drug therapy, supercapacitors, nano generators, sensors and the like.
Phenylalanine dipeptide (FF) is a piezoelectric biological peptide material, is easy to prepare, has diversified appearances, can be functionalized, and has excellent piezoelectric and optical properties, so that the phenylalanine dipeptide (FF) is favored by researchers. FF molecules can self-assemble into nano/micro tubes, nano/micro wires, nano/micro fibers, micro pillars and micro flowers and other structures around water molecules in solution through hydrogen bonds, pi-pi stacking, van der waals and electrostatic interactions. FF self-assembled in solution has a non-centrosymmetric hexagonal crystal structure (P6)1) In-plane piezoelectric constant d thereof15>60pm/V, out-of-plane piezoelectric constant d33About 9.9 pm/V.
Despite the research efforts of researchers on the synthesis and piezoelectric properties of FFs, the synthesis and piezoelectric properties of ordered large-scale arrays are still limited. Research finds that an array with uniform polarization direction can be obtained by applying an electric field in the FF synthesis process, and the piezoelectric constant of the array is improved, but the FF array needs to be synthesized in a strong electric field, and the FF array with controllable piezoelectric characteristics and morphology cannot be synthesized in a natural environment.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a phenylalanine dipeptide-based co-self-assembly product, and a preparation method and application thereof. The technical problem to be solved by the invention is realized by the following technical scheme:
the invention provides a preparation method of a phenylalanine dipeptide-based co-self-assembly product, which comprises the following steps:
step 1: preparing a mixed solution of phenylalanine dipeptide and dipeptide;
step 2: immersing a substrate into the mixed solution, then pulling the substrate upwards from the solution along a direction vertical to a horizontal liquid level at a preset speed until the substrate is completely separated from the mixed solution, and forming a phenylalanine dipeptide-based co-self-assembled array at a three-phase interface of a gas phase, a liquid phase and a solid phase in the pulling process;
alternatively, step 2': naturally evaporating and crystallizing the mixed solution in a container to obtain phenylalanine dipeptide-based co-self-assembly powder;
the phenylalanine dipeptide-based co-self-assembly product with different dipeptide ratios is obtained by regulating the ratio of phenylalanine dipeptide and dipeptide in the mixed solution, so that the piezoelectric property of the phenylalanine dipeptide-based co-self-assembly product can be regulated.
In one embodiment of the invention, the dipeptide is a phenylalanine-tryptophan dipeptide, a cyclic phenylalanine-tryptophan dipeptide, or N-fluorenylmethoxycarbonyldiphenylalanine;
the solvent of the mixed solution is hexafluoroisopropanol aqueous solution, methanol aqueous solution, ethanol aqueous solution, acetone aqueous solution, isopropanol aqueous solution, acetonitrile aqueous solution or acetic acid aqueous solution.
In one embodiment of the present invention, the step 1 comprises:
step 11: weighing phenylalanine dipeptide and dipeptide according to a preset proportion;
step 12: preparing a solvent of the mixed solution;
step 13: and dissolving the weighed phenylalanine dipeptide and dipeptide into a solvent to reach a preset concentration, and uniformly dispersing the phenylalanine dipeptide and dipeptide into the solvent by using an ultrasonic machine to obtain the mixed solution.
In one embodiment of the present invention, in the step 11, the mass ratio of the phenylalanine dipeptide to the dipeptide is 0% to 40% of the dipeptides (phenylalanine dipeptide + dipeptide).
In one embodiment of the present invention, the phenylalanine dipeptide and dipeptide are dissolved in the solvent at a concentration of 5mg/mL to 15 mg/mL.
In one embodiment of the invention, the substrate comprises a silicon wafer, a glass sheet, a polyimide film, a polytetrafluoroethylene film, a polyester film, a metal-covered silicon wafer, a metal-covered glass sheet, a metal-covered polyimide film, a metal-covered polytetrafluoroethylene film or a metal-covered polyester film, wherein the metal is one of gold, silver, magnesium, molybdenum, nickel or copper.
In one embodiment of the present invention, in the step 2, the substrate is pulled at a rate of 5 to 20 μm/min.
In one embodiment of the invention, the preparation temperature of the phenylalanine dipeptide-based co-self-assembly product is 5-60 ℃.
The invention provides a phenylalanine dipeptide-based co-self-assembly product prepared according to the preparation method of any one of the embodiments.
The invention provides application of the phenylalanine dipeptide-based co-self-assembly product in a piezoelectric nano generator.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the phenylalanine dipeptide based co-self-assembly product can synthesize an ordered phenylalanine dipeptide based co-self-assembly array in a large scale, and in the assembly process, the phenylalanine dipeptide based co-self-assembly products with different dipeptide ratios can be obtained by regulating the ratio of the phenylalanine dipeptide and the dipeptide in the mixed solution, so that the piezoelectric property of the phenylalanine dipeptide based co-self-assembly product can be regulated, and a piezoelectric constant regulation strategy which is simple, feasible and low in equipment cost is provided.
2. According to the preparation method of the phenylalanine dipeptide-based co-self-assembly product, in the co-self-assembly process, when the content of dipeptide is low, the crystallization capacity of the co-self-assembly depends on the content of dipeptide; when the dipeptide monomer content is higher, the crystallization capacity of the co-self-assembly body depends on the content of the matrix phenylalanine dipeptide, so that the phenylalanine dipeptide-based fiber co-self-assembly products with different shapes and array densities can be obtained by regulating and controlling different dipeptide contents in the mixed solution.
3. The phenylalanine dipeptide-based co-self-assembly product has different optical properties due to the dipeptide and the phenylalanine dipeptide, can realize the regulation and control of fluorescence luminous intensity and emission wavelength position through co-self-assembly, and has great potential in organic photoelectric application.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a flow chart of a method for preparing a phenylalanine dipeptide-based co-self-assembly product according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing a phenylalanine dipeptide-based co-self-assembly product according to an embodiment of the present invention;
FIG. 3 is an SEM image of a phenylalanine dipeptide-based co-self-assembly product provided by an embodiment of the present invention;
FIG. 4 is a statistical graph of the array coverage area of phenylalanine dipeptide based co-self-assembly products provided by the present invention;
FIG. 5 is an XRD pattern of a phenylalanine dipeptide based co-self assembly product provided by an embodiment of the present invention;
FIG. 6 is a fluorescence spectrum of a phenylalanine dipeptide-based co-self-assembly product provided by an embodiment of the present invention;
FIG. 7 is a statistical plot of the maximum measured effective piezoelectric constant of a phenylalanine dipeptidyl co-self-assembly product provided by an embodiment of the present invention;
FIG. 8 is a graph of voltage and current output of a nano-generator assembled by phenylalanine dipeptide based co-self-assembly products provided by an embodiment of the invention;
fig. 9 is a statistical graph of comparative output numbers of the voltage of the nano-generator according to the embodiment of the present invention.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, a phenylalanine dipeptide-based co-self-assembly product, a preparation method thereof and applications thereof according to the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
The foregoing and other technical matters, features and effects of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings. The technical means and effects of the present invention adopted to achieve the predetermined purpose can be more deeply and specifically understood through the description of the specific embodiments, however, the attached drawings are provided for reference and description only and are not used for limiting the technical scheme of the present invention.
Example one
Referring to fig. 1 and 2, fig. 1 is a flow chart illustrating a method for preparing a phenylalanine dipeptide-based co-self-assembly product according to an embodiment of the present invention; FIG. 2 is a schematic flow chart of a preparation method of a phenylalanine dipeptide-based co-self-assembly product provided by an embodiment of the invention. As shown in the figure, the preparation method of the phenylalanine dipeptide-based co-self-assembly product in this embodiment includes: the method comprises the following steps:
step 1: preparing a mixed solution of phenylalanine dipeptide (FF) and dipeptide;
alternatively, the dipeptide is a phenylalanine-tryptophan dipeptide (FW), a cyclic phenylalanine-tryptophan dipeptide (Cyclo-FW), or an N-fluorenylmethoxycarbonyldiphenylalanine (Fmoc-FF).
The solvent of the mixed solution is hexafluoroisopropanol aqueous solution, methanol aqueous solution, ethanol aqueous solution, acetone aqueous solution, isopropanol aqueous solution, acetonitrile aqueous solution or acetic acid aqueous solution.
Specifically, step 1 comprises:
step 11: weighing phenylalanine dipeptide and dipeptide according to a preset proportion;
step 12: preparing a solvent of the mixed solution;
step 13: dissolving the weighed phenylalanine dipeptide and dipeptide into a solvent to reach a preset concentration, and uniformly dispersing the phenylalanine dipeptide and dipeptide into the solvent by using an ultrasonic machine to obtain a mixed solution.
In the present embodiment, in step 11, the mass ratio of the phenylalanine dipeptide to the dipeptide is 0% to 40% as the dipeptides (phenylalanine dipeptide + dipeptide). The concentration of the phenylalanine dipeptide and the dipeptide dissolved in the solvent is 5 mg/mL-15 mg/mL.
When the solvent of the mixed solution is prepared, the volume ratio of hexafluoroisopropanol, methanol, ethanol, acetone, isopropanol, acetonitrile or acetic acid to water is 10:1 to 1: 1.
Step 2: immersing the substrate into the mixed solution, then lifting the substrate upwards from the solution along the direction vertical to the horizontal liquid level at a preset speed until the substrate is completely separated from the mixed solution, and forming a phenylalanine dipeptidyl self-assembly array at the three-phase interface of a gas phase, a liquid phase and a solid phase in the lifting process;
optionally, the substrate comprises a silicon wafer, a glass sheet, a polyimide film, a polytetrafluoroethylene film, a polyester film, a metal-covered silicon wafer, a metal-covered glass sheet, a metal-covered polyimide film, a metal-covered polytetrafluoroethylene film, or a metal-covered polyester film, wherein the metal is one of gold, silver, magnesium, molybdenum, nickel, or copper.
By covering the substrate with a metal, the growth of various substrates can be applied.
In this example, in step 2, the substrate is pulled at a rate of 5 to 20 μm/min.
It is noted that, in other embodiments, step 2' may be used instead of the czochralski method in step 2 to prepare a phenylalanine dipeptide-based co-self-assembly product, and specifically,
step 2': and naturally evaporating and crystallizing the mixed solution in a container to obtain the phenylalanine dipeptide-based co-self-assembly powder.
It should be noted that the sequence of the phenylalanine dipeptidyl self-assembly product obtained by the pulling method is better, and the sequence of the phenylalanine dipeptidyl self-assembly product prepared by natural evaporation is worse.
In the embodiment, the preparation temperature of the phenylalanine dipeptide-based co-self-assembly product is 5-60 ℃.
The preparation method of the phenylalanine dipeptide based co-self-assembly product can synthesize an ordered phenylalanine dipeptide based co-self-assembly array in a large scale, and in the assembly process, the phenylalanine dipeptide based co-self-assembly products with different dipeptide ratios can be obtained by regulating the ratio of the phenylalanine dipeptide to the dipeptide in the mixed solution, so that the piezoelectric property of the phenylalanine dipeptide based co-self-assembly product can be regulated, and a piezoelectric constant regulation strategy which is simple, feasible and low in equipment cost is provided.
The preparation method is simple and can be synthesized in natural environment, and in the process of co-self-assembly, when the content of dipeptide is low, the crystallization capacity of the co-self-assembly depends on the content of dipeptide; when the dipeptide monomer content is higher, the crystallization capacity of the co-self assembly body depends on the content of the matrix phenylalanine dipeptide, so that the phenylalanine dipeptide-based fiber co-self assembly products with different shapes and array densities can be obtained by regulating and controlling different dipeptide contents in the mixed solution
Further, the principle of preparing the phenylalanine-tryptophan dipeptide-based co-self-assembly product of this example will be described by taking phenylalanine-tryptophan dipeptide as an example of the dipeptide.
During self-assembly, FF molecules form hexamers around water molecules through hydrogen bonding, and the hexamers are stacked in the direction of the long axis of the structure through peptide backbone hydrogen bonding to van der Waals radius of about
Figure BDA0003133697300000071
The hydroxyl and carboxyl of the amino acid are surrounded in the channel, water molecules are inserted into the channel through hydrogen bonds to play a role in stabilizing the structure, and oxygen atoms in the water molecules and hydrogen atoms in FF molecules form hydrogen bonds to eliminate the strong influence of the electronic performance on the structure. These stacked hexamers cluster into a honeycomb structure, resulting in a nanofiber structure. As the FF monomer further accumulates, these nanofibers grow in lengthLarge to form micron-sized fibrous structures. Therefore, FF fibers are formed at a gas-liquid-solid three-phase interface in the pulling process, and an ordered fiber array is obtained. Due to the hydrophobic nature of the peptide material, one dipeptide tends to agglomerate and grow on the other dipeptide. Furthermore, FW has a molecular structure similar to FF and has charged groups, i.e., a hydroxyl group and a carboxyl group, and thus can be self-assembled together with FF.
Different co-self assemblies are obtained by regulating the proportion of different FW monomers and FF monomers, and due to the fact that FW contains indole rings and has larger molecular mass, the asymmetry of the crystal structure of FF is increased, and therefore the regulation of piezoelectric performance is achieved. Due to the different thermodynamics and kinetics of monomer self-assembly in different proportions, when the FW content is lower, the amount of crystal of the self-assembly depends on the amount of the FW monomer added; at high FW monomer content, the amount of co-self-assembly crystals depends on the amount of matrix FF monomer, and thus control of array arrangement density can be achieved. Thereby realizing double regulation and control of piezoelectric property and morphology.
Example two
In this example, the method for producing the phenylalanine dipeptide-based co-self-assembly product of example one will be described by taking phenylalanine-tryptophan dipeptide as the dipeptide and an aqueous hexafluoroisopropanol solution as the solvent of the mixed solution.
1. Preparing FF with FW content of 0, comprising the steps of:
1) 48mg of FF starting material was weighed into a beaker in an inert gas glove box.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 1 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 1.
4) The substrate was slowly pulled out at a speed of 10 μm/min perpendicular to the horizontal plane of the solution to obtain a horizontal FF array named FF.
2. Preparing an FW/FF co-self-assembled array with the FW content of 5%, comprising the following steps of:
1) respectively weighing 45.6mg of FF and 2.4mg of FW raw materials in an inert gas glove box, and respectively putting the raw materials into a beaker, wherein the mass ratio of FW to FF is FW: (FF + FW) ═ 5%.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 2 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 2.
4) And slowly pulling the substrate out at a speed of 10 mu m/min in a direction vertical to the horizontal plane of the solution to obtain FW/FF co-self-assembled arrays with different proportional contents, which are named as 5% FW.
3. Preparing a FW/FF co-self-assembled array with the FW content of 10%, comprising the following steps of:
1) 43.2mg of FF and 4.8mg of FW raw materials are respectively weighed in an inert gas glove box and are respectively put into a beaker, so that the mass ratio of FW to FF is as follows: (FF + FW) ═ 10%.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 3 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 3.
4) And slowly pulling the substrate out at a speed of 10 mu m/min in a direction vertical to the horizontal plane of the solution to obtain FW/FF co-self-assembled arrays with different proportional contents, which are named as 10% FW.
4. Preparing a FW/FF co-self-assembled array with the FW content of 15%, and comprising the following steps of:
1) respectively weighing 40.8mg of FF and 7.2mg of FW raw materials in an inert gas glove box, and respectively putting the raw materials into a beaker, wherein the mass ratio of FW to FF is FW: (FF + FW) ═ 15%.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 4 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 4.
4) And slowly pulling the substrate out at a speed of 10 mu m/min in a direction vertical to the horizontal plane of the solution to obtain FW/FF co-self-assembled arrays with different proportional contents, wherein the FW/FF co-self-assembled arrays are named as 15% FW.
5. Preparing a FW/FF co-self-assembled array with the FW content of 20%, comprising the following steps of:
1) respectively weighing 38.4mg FF and 9.6mg FW raw materials in an inert gas glove box, and respectively putting the raw materials into a beaker, wherein the mass ratio of FW to FF is FW: (FF + FW) ═ 20%.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 5 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 5.
4) And slowly pulling the substrate out at a speed of 10 mu m/min in a direction vertical to the horizontal plane of the solution to obtain FW/FF co-self-assembled arrays with different proportional contents, which are named as 20% FW.
6. Preparing a FW/FF co-self-assembled array with the FW content of 300%, comprising the following steps of:
1) 33.6mg of FF and 14.4mg of FW raw materials are respectively weighed in an inert gas glove box and respectively placed in a beaker, so that the mass ratio of FW to FF is as follows: (FF + FW) 30%.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 6 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 6.
4) And slowly pulling the substrate out at a speed of 10 mu m/min in a direction vertical to the horizontal plane of the solution to obtain FW/FF co-self-assembled arrays with different proportional contents, which are named as 30% FW.
7. Preparing a FW/FF co-self-assembled array with the FW content of 40%, and comprising the following steps of:
1) respectively weighing 28.8mg FF and 19.2mg FW raw materials in an inert gas glove box, and respectively putting the raw materials into a beaker, wherein the mass ratio of FW to FF is FW: (FF + FW) ═ 40%.
2) The weighed raw materials are dissolved in a mixed solution of 4.5mL of hexafluoroisopropanol and 1.5mL of water to enable the concentration of the mixed solution to reach 8mg/mL, the obtained solution is named as No. 7 solution, and the solution is placed into an ultrasonic machine to be subjected to ultrasonic treatment for 5 minutes to enable the materials to be uniformly dispersed in the solution.
3) 1 silver-coated silicon wafer was immersed in solution No. 7.
4) And slowly pulling the substrate out at a speed of 10 mu m/min in a direction vertical to the horizontal plane of the solution to obtain FW/FF co-self-assembled arrays with different proportional contents, which are named as 40% FW.
For various characterizations of the above example samples, please refer to fig. 3, fig. 3 is SEM images of phenylalanine dipeptidyl co-assembly products provided by the examples of the present invention, wherein (a) is SEM image of FF, (b) is SEM image of 5% FW, (c) is SEM image of 10% FW, (d) is SEM image of 15% FW, (e) is SEM image of 20% FW, (f) is SEM image of 30% FW, and (g) is SEM image of 40% FW. As shown in the figure, the morphology of the 7 products of this example was observed by Scanning Electron Microscopy (SEM), from which it can be seen that the pure FF arrays are orderly distributed on the substrate in the form of hexagonal fibers with a fiber diameter of about 5-25 microns. When 5% FW was added, the fiber density became dense and the diameter was reduced to 10-20 μm. As the FW content increases to 10% and 15%, the density of the fibers continues to increase, and the size of the fiber diameter also gradually decreases. When the FW content is increased to 20%, 30% and 40%, the structure of the fiber thereof is not significantly changed, but the fiber becomes sparse and the areal density thereof gradually decreases.
Referring to fig. 4, fig. 4 is a statistical graph of the coverage area of the array of phenylalanine dipeptidyl self-assembly products according to the present invention, and as shown in the figure, the coverage area of 7 products according to the present embodiment is counted, and it can be seen from the graph that the coverage area is gradually increased as the FW content is increased. When the FW content was 15%, the coverage area ratio thereof reached a maximum of 94.7%. As the FW content increases, the coverage area thereof gradually decreases, and when the FW content increases to 40%, the coverage area ratio thereof is only 42%. This is because, at low FW content, the crystallization of the co-assembled fibers depends on the amount of FW added. When the FW content is more than 15%, the crystallinity of the fiber thereof depends on the degree of crystallinity of self FF, and when the FF content is reduced, the amount of crystallinity is reduced.
Referring to fig. 5, fig. 5 is an XRD pattern of a phenylalanine dipeptide-based co-self-assembly product provided by an embodiment of the present invention, wherein (b) is a partial enlarged view of (a). As shown in the figure, the 7 products of this example were characterized by X-ray diffraction (XRD), and it can be seen that FF has a non-centrosymmetric hexagonal structure (P6)1) As the FW content increased, the diffraction peak of the self-assembled crystal shifted to the left, and when 40% of FW was added to the solution, the diffraction peak of the (7-10) crystal plane was shifted by 0.37 deg., because the interplanar spacing increased due to the addition of FW.
Referring to fig. 6, fig. 6 is a fluorescence spectrum of a phenylalanine dipeptide-based co-self-assembly product provided by an embodiment of the present invention, as shown in the figure, 7 products of the embodiment are further characterized by a fluorescence spectrum test, and it can be seen from the figure that pure FF has a main emission peak at 292nm and a secondary emission peak at 304nm when excited by a wavelength of 260 nm. When 5% FW was added, its emission peak wavelength shifted to 313nm, and the intensity of its peak increased because the indole ring in FW had a stronger emission peak and a longer emission wavelength. As the FW content increases, its diffraction peak continues to red-shift (red-shift indicates a phenomenon in which the wavelength of electromagnetic radiation of an object increases for some reason), but its peak intensity decreases because as FW is added, its asymmetry increases, defects increase, and movement of water molecules between its aromatic and indole rings is restricted.
Referring to fig. 7, fig. 7 is a statistical chart of maximum measured effective piezoelectric constants of phenylalanine dipeptide-based co-self-assembly products provided in the present embodiment, and due to the change of FF crystal structure caused by FW introduction, 7 products of the present embodiment were tested by piezoelectric force microscopeAs shown in the figure. The maximum value of the effective piezoelectric constant of the tested pure FF was 25.7pm V-1With the addition of FW, the piezoelectric constant thereof increases, since FW increases the non-centrosymmetry of the structure. When the FW content is 20%, the maximum piezoelectric constant is 35.5pm V-1
EXAMPLE III
The present embodiment provides a phenylalanine dipeptide-based co-self-assembly product, which is prepared according to the preparation method described in the first embodiment.
Example four
In this example, the application performance of the phenylalanine dipeptide-based co-self-assembly product in the second example in the piezoelectric nano generator was tested.
Referring to fig. 8, fig. 8 is a graph of current and voltage output of a nano-generator assembled by phenylalanine dipeptide based co-self-assembly products provided by the embodiment of the invention, and 7 products in the second embodiment are assembled into a piezoelectric nano-generator, and the output voltage and current statistical distribution graph thereof is shown, wherein (a) is a voltage statistical graph, and (b) is a current statistical graph. As shown in the figure, when a 47N cycle pressure was applied, the voltage and current output values of the FF-based nanogenerator were 1.2V and 12.3nA, respectively, and the output voltage and current thereof gradually increased as the FW content increased, and the voltage and current values of the 15% FW-based nanogenerator output were the highest, reaching 3.2V and 17.2 nA.
Referring to fig. 9, fig. 9 is a statistical graph of voltage comparison output numbers of the nanogenerator according to the embodiment of the invention, and it can be seen that the voltage value of the piezoelectric nanogenerator assembled by 7 products in the second embodiment is higher than that of most amino acids and polypeptides.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (10)

1. A preparation method of a phenylalanine dipeptide-based co-self-assembly product is characterized by comprising the following steps:
step 1: preparing a mixed solution of phenylalanine dipeptide and dipeptide;
step 2: immersing a substrate into the mixed solution, then pulling the substrate upwards from the solution along a direction vertical to a horizontal liquid level at a preset speed until the substrate is completely separated from the mixed solution, and forming a phenylalanine dipeptide-based co-self-assembled array at a three-phase interface of a gas phase, a liquid phase and a solid phase in the pulling process;
alternatively, step 2': naturally evaporating and crystallizing the mixed solution in a container to obtain phenylalanine dipeptide-based co-self-assembly powder;
the phenylalanine dipeptide-based co-self-assembly product with different dipeptide ratios is obtained by regulating the ratio of phenylalanine dipeptide and dipeptide in the mixed solution, so that the piezoelectric property of the phenylalanine dipeptide-based co-self-assembly product can be regulated.
2. The method for preparing a phenylalanine dipeptide based co-self assembly product according to claim 1, wherein the dipeptide is a phenylalanine-tryptophan dipeptide, a cyclic phenylalanine-tryptophan dipeptide or N-fluorenylmethoxycarbonyldiphenylalanine;
the solvent of the mixed solution is hexafluoroisopropanol aqueous solution, methanol aqueous solution, ethanol aqueous solution, acetone aqueous solution, isopropanol aqueous solution, acetonitrile aqueous solution or acetic acid aqueous solution.
3. The method for preparing a phenylalanine dipeptidyl co-self-assembly product according to claim 2, wherein the step 1 comprises:
step 11: weighing phenylalanine dipeptide and dipeptide according to a preset proportion;
step 12: preparing a solvent of the mixed solution;
step 13: and dissolving the weighed phenylalanine dipeptide and dipeptide into a solvent to reach a preset concentration, and uniformly dispersing the phenylalanine dipeptide and dipeptide into the solvent by using an ultrasonic machine to obtain the mixed solution.
4. The method for preparing phenylalanine dipeptide based co-self-assembly product according to claim 3, wherein in the step 11, the mass ratio of phenylalanine dipeptide and dipeptide is that dipeptide [ phenylalanine dipeptide + dipeptide ] ═ 0% to 40%.
5. The method for preparing a phenylalanine dipeptide based co-self-assembly product according to claim 3, wherein the concentration of the phenylalanine dipeptide and the dipeptide dissolved in the solvent is 5mg/mL to 15 mg/mL.
6. The method for preparing a phenylalanine dipeptide based co-self assembly product according to claim 1, wherein the substrate comprises a silicon wafer, a glass sheet, a polyimide film, a polytetrafluoroethylene film, a polyester film, a metal-coated silicon wafer, a metal-coated glass sheet, a metal-coated polyimide film, a metal-coated polytetrafluoroethylene film, or a metal-coated polyester film, wherein the metal is one of gold, silver, magnesium, molybdenum, nickel, or copper.
7. The method for preparing a phenylalanine dipeptide based co-self assembly product according to claim 1, wherein in the step 2, the substrate is pulled at a rate of 5 to 20 μm/min.
8. The method for preparing a phenylalanine dipeptidyl co-self-assembly product according to claim 1, wherein the temperature at which the phenylalanine dipeptidyl co-self-assembly product is prepared is 5 to 60 ℃.
9. A phenylalanine dipeptidyl co-self-assembly product characterized by being prepared according to the preparation method of any one of claims 1 to 8.
10. Use of the phenylalanine dipeptide based co-self assembly product according to claim 9 in a piezoelectric nanogenerator.
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