CN115323528B - Artificial muscle fiber with calcium ion response and preparation method thereof - Google Patents
Artificial muscle fiber with calcium ion response and preparation method thereof Download PDFInfo
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- CN115323528B CN115323528B CN202211006794.3A CN202211006794A CN115323528B CN 115323528 B CN115323528 B CN 115323528B CN 202211006794 A CN202211006794 A CN 202211006794A CN 115323528 B CN115323528 B CN 115323528B
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 218
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The invention relates to an artificial muscle fiber with calcium ion response and a preparation method thereof, wherein the artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer and the middle layer are polyelectrolyte, the outer layer is a polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; the specific preparation method of the invention comprises the following steps: sequentially immersing polyelectrolyte composite fibers into dopamine solution and deionized water to prepare artificial muscle fibers with calcium ion response; and (3) swelling the polyelectrolyte composite fiber in a dopamine solution, and then adding sodium periodate into the dopamine solution. The artificial muscle fiber with calcium ion response prepared by the invention can reversibly reach the circulation of 'calcium absorption' and 'calcium loss', and the tensile strength of the fiber is changed between 10-20 MPa and 100-120 MPa and the shrinkage rate of the fiber is stabilized between 30-40% in the process of 20 repeated circulation.
Description
Technical Field
The invention belongs to the technical field of artificial muscle fibers, and relates to an artificial muscle fiber with calcium ion response and a preparation method thereof.
Background
Artificial muscle refers to a class of materials that have the actions of stretching, contracting, rotating, etc. in response to external environmental stimuli (light, electricity, magnetism, heat, pH, etc.). The artificial muscle material is in important attention internationally in recent years, and the report of the national academy of sciences and sciences of China's academy of sciences and the literature and information center of China' 2020 research front indicates that the bionic muscle hydrogel in the field of chemistry and materials science is located at the ninth place of the hot spot of materials science, so that the bionic muscle material has important scientific and development significance for the research and the invention of bionic artificial muscles.
Skeletal muscle contraction is the basic process of life exercise and is mainly divided into three processes of myofilament excitation contraction, myofilament sliding and muscle relaxation. In these three processes, calcium ions play a critical regulatory role. The quantity, concentration, etc. of calcium ions directly affect the speed and strength of skeletal muscle contraction, and also have significant effects on body shaping, living standard, etc. The muscle cells in skeletal muscle are fibrous, are not branched, have obvious transverse lines and have a lot of nuclei and are all positioned below cell membranes. There are a number of filamentary myofibrils in the muscle cell that are aligned in parallel along the long axis of the cell. The muscle cells consist of thick and thin muscle filaments. The thick myofilaments mainly consist of myosin, which are arranged in parallel and staggered to form the trunk of the thick myofilaments. The thin filaments consist of actin, tropomyosin and troponin. Among them, troponin has three subunits Tn-C, tn-T and Tn-1. The major calcium ions in human muscle cells are stored in mitochondria and the sarcoplasmic reticulum. When life activities are stimulated, calcium ions are released from the sarcoplasmic reticulum to be immersed in cytoplasm, the concentration of calcium ions in cytoplasm is increased, the calcium ions are combined with Tn-C, the conformation of Tn-C is changed, and myosin is combined with actin to induce muscle contraction. When excitation is terminated, calcium ions are absorbed again by the sarcoplasmic reticulum through active transport under the energy provided by ATP hydrolysis, the concentration of calcium ions in the plasma cells decreases, and the muscles relax.
The most conventional power systems are internal combustion engines, steam engines, and now electric motors, etc. However, there are many limitations to these systems in order to simulate and achieve movement of biological tissue. Most artificial muscle materials are polymer materials at present, and the reasonable construction of the polymer materials enables the materials to have various stimulus response behaviors. When the material is affected by acousto-optic, photo-thermal and magnetic factors, microscopic structural changes of the material can cause macroscopic dimensional changes. Because of these characteristics, researchers have developed many thermally, optically, magnetically, and pH responsive artificial muscles to convert chemical energy into mechanical energy, simulating the stretching motion of the muscles. However, artificial muscle materials with calcium ion response have been rarely reported.
Chitosan, sodium alginate and carboxymethyl cellulose are common polymers for constructing biological materials, and have the characteristics of no toxicity, environment friendliness, reproducibility and the like. The chitosan is polycation electrolyte, the sodium alginate and the carboxymethyl cellulose are polyanion electrolyte, and polyelectrolyte complexes can be formed between the polyelectrolytes with opposite charges. Because of the unique molecular structure of sodium alginate and carboxymethyl cellulose, and the strong coordination ability of calcium ions. However, reversibly stabilized elongation shrinkage cannot be achieved without covalently crosslinked polyelectrolyte complexes.
Therefore, the invention provides an artificial muscle fiber which has calcium ion response and can achieve reversible and stable extension and contraction and a preparation method thereof, and has very important significance in solving the problems existing in the prior art.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide an artificial muscle fiber with calcium ion response and a preparation method thereof. The invention provides a polydopamine crosslinked polyelectrolyte composite fiber which has the functions of stabilizing the structure and enhancing the mechanical strength. When the fiber absorbs calcium ions, the calcium ions form coordination bonds with sodium alginate or carboxymethyl cellulose, the molecular chains are compact, the size shrinkage is caused, and the mechanical strength is enhanced; when the fiber releases calcium ions, the coordination structure is dissociated, molecular chains are dispersed, the size is relaxed, and the mechanical strength is reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an artificial muscle fiber with calcium ion response has a skin-core structure, and comprises an inner layer, an intermediate layer and an outer layer from inside to outside in sequence;
the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
The inner layer and the middle layer are both polyelectrolytes, and when the inner layer is a polycation electrolyte A, the middle layer is a polyanion electrolyte B; when the inner layer is the polyanion electrolyte B, the middle layer is the polycation electrolyte A;
the outer layer is a polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer;
the artificial muscle fiber with calcium ion response can simulate the processes of 'calcium absorption' and 'calcium losing' of human muscle fiber to carry out reversible extension and contraction, the fiber with certain relaxation state can 'absorb calcium ions' to shrink in a solution containing calcium ions, and can 'lose calcium ions' to elongate in a solution with the capability of chelating calcium ions, can recover to the original relaxation state, and can repeatedly carry out 'calcium absorption' and 'calcium losing' circulation along with the change of the mechanical properties of the fiber in the processes of 'calcium absorption' and 'calcium losing'.
As a preferable technical scheme:
the artificial muscle fiber with calcium ion response has the advantages that the polycation electrolyte A is chitosan, and the polyanion electrolyte B is more than one of sodium alginate and carboxymethyl cellulose; the polycation electrolyte and the polyanion electrolyte are polysaccharide biomacromolecules; the polyanion electrolyte has a large number of carboxylate groups, so that the polyanion electrolyte can not only form a polyelectrolyte complex with the polycation electrolyte due to electrostatic interaction, but also absorb calcium ions to form a coordination crosslinking structure, thereby causing mechanical strength change and dimensional shrinkage.
An artificial muscle fiber with calcium ion response as described above, wherein the mass ratio of all polydopamine, polyelectrolyte of the middle layer and polyelectrolyte of the inner layer is 1-2:1-2:8-9, the inner layer polyelectrolyte is formed by spinning solution and is the main body of the whole fiber, and the amount of polyelectrolyte of the middle layer is much less than that of polyelectrolyte of the inner layer due to diffusion complexation in the spinning process.
The artificial muscle fiber with calcium ion response has the diameter of 80-100 microns and the water content of 60-80 wt%.
As the artificial muscle fiber with calcium ion response, the solution containing calcium ion is CaCl with the concentration of 1-10 mg/mL 2 Solutions or CaSO 4 The solution with the capability of chelating calcium ions is phosphate buffer salt solution (PBS buffer solution), ethylenediamine tetraacetic acid solution (EDTA solution) or citric acid solution with the concentration of 0.01-0.2M.
As the artificial muscle fiber with calcium ion response has the shrinkage rate of 30-40% after the balance of the artificial muscle fiber with calcium ion response 'absorbs calcium ion' (the shrinkage rate test standard refers to national standard GB/T6505-2017), and the shrinkage of the muscle after troponin absorption in human muscle tissue is 20-40%;
The artificial muscle fiber with calcium ion response has a tensile strength of 10-20 MPa when not absorbing calcium ions and a tensile strength of 100-120 MPa after absorbing calcium ions. If the polydopamine is not crosslinked, the mechanical strength before absorbing calcium ions is 10-100 kPa, and the mechanical strength after absorbing calcium ions is 20-30 MPa. Fibers that have not been cross-linked with polydopamine cannot maintain dimensional stability and calcium cycling stability for long periods of time.
In the artificial muscle fiber with calcium ion response, the tensile strength of the artificial muscle fiber with calcium ion response is changed between 10-20 MPa and 100-120 MPa and the shrinkage rate is stabilized between 30-40% in the cycle process of absorbing calcium ions and losing calcium ions for 20 times.
The invention also provides a method for preparing the artificial muscle fiber with calcium ion response, which comprises the steps of sequentially immersing polyelectrolyte composite fiber into dopamine solution and deionized water to prepare the artificial muscle fiber with calcium ion response;
the polyelectrolyte composite fiber is immersed into the dopamine solution for swelling, and then sodium periodate is added into the dopamine solution; the biological polysaccharide macromolecules are high polymers with a multi-element sugar ring structure, are suitable for constructing rigid polymer materials due to the rigidity of the structures of the biological polysaccharide macromolecules, and are environment-friendly. Dopamine is the most abundant catecholamine neurotransmitter in the brain, and can be polymerized into polydopamine under the oxidation condition, and has good stability and viscosity;
The polyelectrolyte composite fiber is soaked in deionized water until saturated water absorption, and meanwhile, superfluous inorganic salts and the like on the surface can be removed;
the preparation method of the polyelectrolyte composite fiber comprises the following steps: taking polyelectrolyte solution X as spinning solution (the spinning solution is subjected to centrifugal defoaming before spinning), and simultaneously taking polyelectrolyte solution Y as coagulating bath for wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
the solute of the polyelectrolyte solution X is the polycation electrolyte A, and the solute of the polyelectrolyte solution Y is the polyanion electrolyte; alternatively, the solute of polyelectrolyte solution X is the polyanion electrolyte B and the solute of polyelectrolyte solution Y is the polycation electrolyte A.
As a preferable technical scheme:
the method has the advantages that the concentration of the dopamine solution is 1-2 mg/mL, and the temperature is 20-25 ℃;
the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 1-2 g:1-2L, the polyelectrolyte composite fiber is immersed in the dopamine solution for 15-20 min, then sodium periodate is added into the dopamine solution, the immersion is continued for 1-6 h, and the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.1-0.5 mg/mL; when the polyelectrolyte composite fiber is soaked in a dopamine solution or a strong oxidant sodium periodate is added into the dopamine solution, hydrochloric acid is needed to adjust the pH value of the solution to pH=4, so that the high pH value and the low pH value are prevented from damaging electrostatic composite; during impregnation, dopamine fully diffuses into a fiber internal network, after a strong oxidant is added, crosslinking is carried out, fibers with different covalent crosslinking degrees can be obtained in different crosslinking times, the fiber after crosslinking treatment has a covalent crosslinking structure, and meanwhile, the fiber has a polydopamine layer on the outer surface, and the fiber has a crosslinking structure, so that the stability of the fiber structure is improved.
The method as described above, the mass fraction of polyelectrolyte in polyelectrolyte solution X or polyelectrolyte solution Y is 0.5-1.5 wt.%; the concentration of the spinning solution is in the range, so that the problems that the spinning solution is too high in concentration and too high in viscosity and is not suitable for extrusion can be avoided, and the problems that the concentration is too low and the fluid is unstable during extrusion can be avoided; the concentration of the coagulating bath is in the range, so that the problem that the spinning solution cannot flow stably in the coagulating bath when the concentration of the coagulating bath is too high can be avoided, and the problems that the concentration is too low and the compounding process is slow can be avoided;
the polyelectrolyte solution X and the polyelectrolyte solution Y are prepared by dissolving polyelectrolyte in water with a certain pH value, and the polyelectrolyte is in a completely dissolved state, wherein the acid for regulating the pH value is hydrochloric acid and/or acetic acid, and the alkali is sodium hydroxide; the pH of the polyelectrolyte solution X is 3.5-4, and the pH of the polyelectrolyte solution Y is 6.0-7.0;
the residence time of the spinning solution in the coagulating bath after extrusion is 15 min-24 h, the residence time is too low, the fiber compounding process is incomplete, the fiber performance is poor, the compounding process is basically completed after the residence time reaches 24h, and no more benefits are generated after the residence time is prolonged; in addition, the spinning solution extrusion speed needs to be set according to the type of the spinning hole, for example, the type of the spinning hole is: the length is 20mm, the outer diameter is 0.31mm, the inner diameter is 0.13mm, the extrusion speed of the spinning solution is 0.8mL/min, the extrusion speed is too slow, one-dimensional jet flow cannot be stabilized, the extrusion speed is too fast, and the solidification process cannot occur.
In the method, the polyelectrolyte complex fiber is dried to the water content of <5wt.% before being immersed in the dopamine solution, so as to avoid the difficulty of immersing the dopamine into the polyelectrolyte complex fiber caused by the excessive water content in the polyelectrolyte complex fiber.
The temperature of the drying treatment is 40-60 ℃ and the time is 12-24 h.
The principle of the invention is as follows:
the concentrations of the polycation electrolyte a (hereinafter abbreviated as a) and the polyanion electrolyte B (hereinafter abbreviated as B) of the present invention are 0.5 to 1.5wt.%, and a and B can form a polyelectrolyte complex in an aqueous solution by electrostatic interaction. The invention utilizes a wet spinning method to process the composite formed by the A and the B into fibers. Finally, a polydopamine cross-linked network is introduced, wherein the polydopamine network has two layers of functions, firstly, a covalent cross-linked network is formed in the fiber, and an energy dissipation mechanism is formed due to the existence of the covalent network, so that the mechanical property of the fiber is improved; secondly, a thin nano-garment is formed outside the fiber, and the structure can enable the fiber to maintain certain dimensional stability.
In the artificial muscle fiber of the present invention, a large amount of moisture exists. When water molecules enter the fiber, the movement space of the molecular chain is increased due to the lubrication effect, the whole chain moves more freely, and the macroscopic appearance of the material becomes softer. After absorbing calcium ions, because a large number of carboxylic acid groups exist in the sodium alginate, a coordination cross-linking structure can be formed with the calcium ions, and the inside of the fiber forms the coordination cross-linking structure, so that molecular chains of the sodium alginate are tightly connected together, the mechanical strength of the fiber is improved, and the macroscopic appearance of the material is material shrinkage. When calcium ions are lost, the coordination crosslinking structure is dissociated, a loose molecular chain structure is formed in the fiber again, the mechanical strength of the fiber is reduced, and the macroscopic material is elongated. The polyelectrolyte compound fiber which is not crosslinked by dopamine can be completely dissolved in water environment after losing calcium ions, the repeated calcium absorption and calcium loss processes can not be achieved, and the tensile strength is very weak. After dopamine is crosslinked, the stability of the polyelectrolyte compound fiber can be maintained, and the tensile strength can be improved.
The existing chitosan sodium alginate crosslinking technology mainly has three crosslinking modes, wherein the first mode is direct crosslinking at high temperature, the amino groups and the carboxyl groups of polyelectrolyte react to form amide bonds, but most of the amino groups and the carboxyl groups are ionization groups, electrostatic acting force is generated, few groups capable of generating amide reaction are generated, the crosslinking degree is low, and poor stability can be caused when the chitosan sodium alginate crosslinking technology is applied to the invention; the second is to add glutaraldehyde, glutaraldehyde and chitosan to react, and crosslink the chitosan, because the chitosan and sodium alginate fibers have core-shell structures, the fibers cannot be stabilized; the third is that ethylenediamine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide are added to react with sodium alginate to crosslink sodium alginate, and the defects are similar to the second. In addition, the above reactions involve high temperatures and use of biotoxic reagents, which are cumbersome to operate, and the high temperatures destroy the biomacromolecule structure and undergo dehydration condensation, which is not suitable for constructing the artificial muscle fiber of the present invention. The coordination crosslinking structure formed by the second and third crosslinking modes is formed by crosslinking one of chitosan or sodium alginate with small molecules, and the prepared chitosan/sodium alginate fiber has a skin-core structure, so that the method does not have a molecular chain interlocking structure in a molecular network structure. The cross-linking network structure is inserted into the whole fiber network by utilizing the polydopamine for cross-linking, polydopamine cross-linking nano particles are arranged at the outermost layer and the inside of the fiber, and the interlocking structure of polydopamine, chitosan and sodium alginate is arranged in the molecular network structure, so that the fiber size can be well stabilized, and the mechanical property is enhanced.
The beneficial effects are that:
(1) According to the preparation method of the artificial muscle fiber with calcium ion response, the artificial muscle fiber with excellent performance is constructed in a green simple mode, the contraction rate after absorbing calcium ions is 30-40% (the contraction rate of muscle after absorbing calcium ions by troponin in human muscle tissue is 20-40%), and the fiber can recover the original relaxation state after losing calcium ions.
(2) The artificial muscle fiber with calcium ion response can effectively control the relaxation and contraction behaviors by controlling the concentration of calcium ions in an environment solution, can simulate various movements, the relaxation and contraction movements of muscles, and the driver actively lifts the heavy objects to bloom flowers.
(3) The artificial muscle fiber with calcium ion response can reversibly reach the circulation of 'calcium absorption' and 'calcium loss', the tensile strength of the fiber is changed between 10-20 MPa and 100-120 MPa in the process of 20 repeated circulation, and the shrinkage rate of the fiber is stabilized at 30-40%.
Drawings
FIG. 1 is a schematic illustration of simulated muscle relaxation and contraction by calcium ion cycling;
FIG. 2 is a schematic diagram of a calcium ion artificial muscle driver;
FIG. 3 is a schematic representation of a simulation of flower bloom by calcium cycling;
FIG. 4 is a graph showing the tensile strength and shrinkage for each of 20 "calcium ion absorbed", "calcium ion lost" cycles of example 1 of the present invention;
FIG. 5 is a graph of tensile strength and shrinkage for each of the 20 "calcium ion absorbed", "calcium ion lost" cycles of comparative example 1;
FIG. 6 is a graph of tensile strength and shrinkage for each of the 20 "calcium ion absorbed", "calcium ion lost" cycles of comparative example 2;
FIG. 7 is a graph of tensile strength and shrinkage for each of the 20 "calcium ion absorbed", "calcium ion lost" cycles of comparative example 3;
fig. 8 is a graph of tensile strength and shrinkage for each of the 20 cycles of comparative example 4, calcium ion absorption and calcium ion loss.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
In the invention, when the pH values of the polyelectrolyte solution X and the polyelectrolyte solution Y are regulated, the acid used is hydrochloric acid and/or acetic acid, and the alkali is sodium hydroxide.
The invention adopts the following material sources:
(1) Chitosan: from Sigma-Aldrich under the designation C3646;
(2) Sodium alginate: from the national drug group company, the brand is 30164424;
(3) Carboxymethyl cellulose: from Sigma-Aldrich under the designation C5678;
(4) Phosphate buffered saline: prepared by laboratory, first using 0.2M NaH 2 PO 4 Solution 19mL and 0.2M Na 2 HPO 4 81mL of solution is uniformly mixed to prepare 0.2M phosphate buffer solution; then, 50mL of a 0.2M PBS solution was measured and the volume was set to 200mL, thereby obtaining a 0.05M phosphate buffer salt solution.
The invention adopts the following test method:
(1) Tensile strength: testing the tensile strength of the artificial muscle fiber by using a GB/T14344-2008 method;
(2) Shrinkage ratio: the contractility of the artificial muscle fiber was tested by using the GB/T6505-2017 method.
Example 1
A preparation method of artificial muscle fiber with calcium ion response comprises the following specific steps:
(1) Raw material preparation:
polyelectrolyte solution X: dissolving chitosan in water, and adjusting the pH value of the chitosan to 3.5 to obtain polyelectrolyte solution X with the mass fraction of 1.5 wt%;
Polyelectrolyte solution Y: sodium alginate is dissolved in water, and the pH value of the sodium alginate is regulated to be 6, so that polyelectrolyte solution Y with the mass fraction of 0.5wt.% is obtained;
solution containing calcium ions: caCl is added with 2 Dissolving in water to obtain CaCl with concentration of 10mg/mL 2 A solution;
solutions with the ability to sequester calcium ions: phosphate buffer salt solution with concentration of 0.2M;
(2) Preparing polyelectrolyte composite fibers;
taking polyelectrolyte solution X as spinning solution, taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
wherein, the residence time of the spinning solution in the coagulating bath after extrusion is 15min;
(3) Drying the polyelectrolyte composite fiber prepared in the step (2) at 50 ℃ for 24 hours until the water content is 2%;
(4) Immersing the polyelectrolyte composite fiber prepared in the step (3) into a dopamine solution with the concentration of 1mg/mL and the temperature of 25 ℃, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, immersing for 18min to swell the polyelectrolyte composite fiber, adding sodium periodate into the dopamine solution, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, and then continuing immersing for 3h;
wherein the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 2 g/2L; the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.1mg/mL;
(5) And (3) taking out the polyelectrolyte composite fiber in the step (4), immersing the polyelectrolyte composite fiber in deionized water, and immersing the polyelectrolyte composite fiber in the deionized water until the polyelectrolyte composite fiber is saturated and absorbed by water to obtain the artificial muscle fiber with the calcium ion response, wherein the diameter of the artificial muscle fiber is 100 mu m, and the water content of the artificial muscle fiber is 80 wt.%.
The prepared artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer is chitosan, the middle layer is sodium alginate, the outer layer is polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force; the mass ratio of all polydopamine, sodium alginate in the middle layer and chitosan in the inner layer is 1:1:9;
the artificial muscle fiber with calcium ion response has a tensile strength of 10MPa, is contracted in a solution containing calcium ions, has a contraction rate of 40%, has a tensile strength of 100MPa after the calcium ions are absorbed, and is elongated in a solution with the capability of chelating the calcium ions, and can be restored to an original relaxed state as shown in FIG. 1;
as shown in FIG. 4, the tensile strength of the artificial muscle fiber having a calcium ion response was varied between 10 to 12MPa and 100 to 102MPa and the shrinkage was stabilized between 38 to 40% during the cycles of "absorbing calcium ions" and "losing calcium ions" of 20 times.
Comparative example 1
A method for producing artificial muscle fiber, the specific steps are basically the same as in example 1, except that step (4) and step (5) are omitted, and the dried polyelectrolyte composite fiber is directly saturated with water as the artificial muscle fiber;
the tensile strength of the prepared artificial muscle fiber is 10kPa, the contraction is carried out on the artificial muscle fiber in a solution containing calcium ions, the contraction rate is 60 percent, the tensile strength after the artificial muscle fiber absorbs the calcium ions is 20MPa, and the artificial muscle fiber can only recover to 60 percent of the original relaxation state after the artificial muscle fiber loses the calcium ions in the solution with the capability of chelating the calcium ions;
as shown in fig. 5, in the course of 20 cycles of "absorbing calcium ions" and "losing calcium ions", the tensile strength of the artificial muscle fiber varies between 0 to 20MPa and 0 to 10kPa (the tensile strength of 0 means that the artificial muscle fiber has been completely hydrolyzed after the cycle and cannot be tested), and the shrinkage varies between 0 to 60%; and after 4 cycles of "absorbing calcium ions" and "losing calcium ions", the artificial muscle fiber cannot contract and elongate any more.
Comparing comparative example 1 with example 1, it was found that the tensile strength and shrinkage of comparative example 1 were reduced all the time during the 20 cycles of "absorbing calcium ions", "losing calcium ions", and that the degree of change in strength after the 3 rd cycle of "absorbing calcium ions", "losing calcium ions" was small in comparative example 1, because there was no covalent cross-linking structure, and a large amount of water molecules damaged the internal structure of the fiber, and the fiber was gradually decomposed during the cycle.
Comparative example 2
A method for producing artificial muscle fibers, comprising the steps of substantially the same as in example 1, wherein the step (4) comprises:
placing the polyelectrolyte composite fiber prepared in the step (3) at a high temperature to directly crosslink;
wherein the crosslinking temperature is 80 ℃ and the crosslinking time is 24 hours;
the tensile strength of the prepared artificial muscle fiber is 1MPa, the contraction is carried out on the artificial muscle fiber in a solution containing calcium ions, the contraction rate is 50%, the tensile strength after the artificial muscle fiber absorbs the calcium ions is 30MPa, and the artificial muscle fiber can only recover to 70% of the original relaxation state after the artificial muscle fiber loses the calcium ions in the solution with the capability of chelating the calcium ions;
as shown in fig. 6, the tensile strength of the artificial muscle fiber is varied between 0 to 30MPa and 0 to 1MPa and the shrinkage is varied between 0 to 50% in the course of 20 cycles of "absorbing calcium ions", "losing calcium ions"; and after 9 cycles of "absorbing calcium ions" and "losing calcium ions", the artificial muscle fiber cannot contract and elongate any more.
Comparing comparative example 2 with example 1, it was found that the tensile strength and shrinkage of comparative example 2 were always reduced during the cycles of "absorbing calcium ions" and "losing calcium ions" of 20 times, and that the degree of change in strength of comparative example 2 after the cycles of "absorbing calcium ions" and "losing calcium ions" of 8 th time was already small because amine groups and carboxyl groups of the polyelectrolyte reacted to form amide bonds, but most amine groups and carboxyl groups were ionized groups, electrostatic force had been generated, few groups that could undergo amide reaction were low in degree of crosslinking, resulting in poor stability, and stable elongation and shrinkage could not be performed.
Comparative example 3
A method for producing artificial muscle fibers, the specific steps of which are basically the same as those of example 1, except that the step (4) is to soak the polyelectrolyte complex fibers in 0.1M glutaraldehyde solution and crosslink them by heating.
Wherein the crosslinking temperature is 40 ℃ and the crosslinking time is 24 hours;
the tensile strength of the prepared artificial muscle fiber is 5MPa, the contraction is carried out on the artificial muscle fiber in a solution containing calcium ions, the contraction rate is 50%, the tensile strength after the artificial muscle fiber absorbs the calcium ions is 50MPa, and the artificial muscle fiber can only recover to 75% of the original relaxation state after the artificial muscle fiber loses the calcium ions in the solution with the capability of chelating the calcium ions;
as shown in fig. 7, the tensile strength of the artificial muscle fiber is varied between 0 to 50MPa and 0 to 5MPa and the shrinkage is varied between 0 to 50% in the course of 20 cycles of "absorbing calcium ions", "losing calcium ions"; and after 13 cycles of "absorbing calcium ions" and "losing calcium ions", the artificial muscle fiber cannot contract and elongate any more.
Comparing comparative example 3 with example 1, it was found that the tensile strength and shrinkage of comparative example 2 were always reduced during the cycles of "absorbing calcium ions" and "losing calcium ions" of 20 times, and that the degree of change in strength of comparative example 3 after the cycles of "absorbing calcium ions" and "losing calcium ions" of 10 times was already small because glutaraldehyde reacted with chitosan to crosslink chitosan, and the artificial muscle fiber could not perform stable elongation and shrinkage because chitosan and sodium alginate fiber had a core-shell structure and could not stabilize the fiber.
Comparative example 4
A method for producing artificial muscle fibers, the specific steps of which are substantially the same as in example 1, except that step (4) is to soak the fibers into a mixed solution of ethylenediamine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide in a molar ratio of 10:1, and heat-crosslink the fibers.
Wherein the crosslinking temperature is 40 ℃ and the crosslinking time is 24 hours;
the tensile strength of the prepared artificial muscle fiber is 10MPa, the contraction is carried out on the artificial muscle fiber in a solution containing calcium ions, the contraction rate is 40%, the tensile strength after the artificial muscle fiber absorbs the calcium ions is 60MPa, and the artificial muscle fiber can only recover to 80% of the original relaxation state after the artificial muscle fiber loses the calcium ions in the solution with the capability of chelating the calcium ions;
as shown in fig. 8, the tensile strength of the artificial muscle fiber is changed between 15 to 60MPa and 2 to 10MPa and the shrinkage rate is changed between 10 to 40% in the course of 20 cycles of "absorbing calcium ions" and "losing calcium ions"; and after 20 cycles, the original loose state can be recovered to 20%.
Comparing comparative example 4 with example 1, it was found that the tensile strength and shrinkage of comparative example 2 were always reduced during the cycle of going through 20 times of "absorbing calcium ions", "losing calcium ions", and that the degree of change in strength of comparative example 4 after going through 15 th time of "absorbing calcium ions", "losing calcium ions" was already small because ethylenediamine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide reacted with sodium alginate, crosslinked sodium alginate, and the artificial muscle fiber could not be stably elongated and shrunk because the chitosan and sodium alginate fiber had a core-shell structure.
Example 2
A preparation method of artificial muscle fiber with calcium ion response comprises the following specific steps:
(1) Raw material preparation:
polyelectrolyte solution X: dissolving chitosan in water, and adjusting the pH value of the chitosan to 3.8 to obtain polyelectrolyte solution X with the mass fraction of 0.5 wt%;
polyelectrolyte solution Y: dissolving carboxymethyl cellulose in water, and adjusting the pH value of the carboxymethyl cellulose to 6.5 to obtain polyelectrolyte solution Y with the mass fraction of 0.6 wt%;
solution containing calcium ions: caCl is added with 2 Dissolving in water to obtain CaCl with concentration of 1mg/mL 2 A solution;
solutions with the ability to sequester calcium ions: dissolving ethylenediamine tetraacetic acid in water to obtain a ethylenediamine tetraacetic acid solution with the concentration of 0.01M;
(2) Preparing polyelectrolyte composite fibers;
taking polyelectrolyte solution X as spinning solution, taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
wherein the residence time of the spinning solution in the coagulating bath after extrusion is 1h;
(3) Drying the polyelectrolyte composite fiber prepared in the step (2) at 60 ℃ for 12 hours until the water content is 4wt.%;
(4) Immersing the polyelectrolyte composite fiber prepared in the step (3) into a dopamine solution with the concentration of 1.2mg/mL and the temperature of 20 ℃, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, immersing for 20min to swell the polyelectrolyte composite fiber, adding sodium periodate into the dopamine solution, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, and then continuing immersing for 1h;
Wherein the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 2g to 1L; the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.5mg/mL;
(5) And (3) taking out the polyelectrolyte composite fiber in the step (4), immersing the polyelectrolyte composite fiber in deionized water, and immersing the polyelectrolyte composite fiber in the deionized water until the polyelectrolyte composite fiber is saturated and absorbed by water to obtain the artificial muscle fiber with the calcium ion response, wherein the diameter of the artificial muscle fiber is 85 mu m, and the water content of the artificial muscle fiber is 75 wt.%.
The prepared artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer is chitosan, the middle layer is carboxymethyl cellulose, the outer layer is a polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; the mass ratio of all polydopamine, middle layer (carboxymethyl cellulose) and inner layer (chitosan) is 1:1.5:8; the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
the artificial muscle fiber with calcium ion response has a tensile strength of 12MPa, is contracted in a solution containing calcium ions, has a contraction rate of 37%, has a tensile strength of 102MPa after the calcium ions are absorbed, and is elongated in a solution with the capability of chelating the calcium ions, and can be restored to an original relaxed state as shown in FIG. 1;
In the process of 20 times of circulation of absorbing calcium ions and losing calcium ions, the tensile strength of the artificial muscle fiber with calcium ion response is changed between 12-14 MPa and 102-105 MPa, and the shrinkage is stabilized at 37-40%.
Example 3
A preparation method of artificial muscle fiber with calcium ion response comprises the following specific steps:
(1) Raw material preparation:
polyelectrolyte solution X: dissolving chitosan in water, and adjusting the pH value of the chitosan to be 4 to obtain polyelectrolyte solution X with the mass fraction of 0.6 wt%;
polyelectrolyte solution Y: dissolving a mixture of sodium alginate and carboxymethyl cellulose in a mass ratio of 1:1 in water, and regulating the pH value of the mixture to 7 to obtain polyelectrolyte solution Y with a mass fraction of 0.8 wt.%;
solution containing calcium ions: caCl is added with 2 Dissolving in water to obtain CaCl with concentration of 5mg/mL 2 A solution;
solutions with the ability to sequester calcium ions: dissolving citric acid in water to obtain a citric acid solution with the concentration of 0.15M;
(2) Preparing polyelectrolyte composite fibers;
taking polyelectrolyte solution X as spinning solution, taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
Wherein the residence time of the spinning solution in the coagulating bath after extrusion is 6 hours;
(3) Drying the polyelectrolyte composite fiber prepared in the step (2) at 40 ℃ for 18 hours until the water content is 3wt.%;
(4) Immersing the polyelectrolyte composite fiber prepared in the step (3) into a dopamine solution with the concentration of 1.5mg/mL and the temperature of 22 ℃, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, immersing for 15min to swell the polyelectrolyte composite fiber, adding sodium periodate into the dopamine solution, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, and then continuing immersing for 6h;
wherein the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 1g to 2L; the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.3mg/mL;
(5) And (3) taking out the polyelectrolyte composite fiber in the step (4), immersing the polyelectrolyte composite fiber in deionized water, and immersing the polyelectrolyte composite fiber in the deionized water until the polyelectrolyte composite fiber is saturated and absorbed by water to obtain the artificial muscle fiber with the calcium ion response, wherein the diameter of the artificial muscle fiber is 85 mu m, and the water content of the artificial muscle fiber is 75 wt.%.
The prepared artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer is chitosan, the middle layer is a mixture of sodium alginate and carboxymethyl cellulose in a mass ratio of 1:1, the outer layer is a polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; all polydopamine, middle layer (mixture of sodium alginate and carboxymethyl cellulose with mass ratio of 1:1) and inner layer (chitosan) with mass ratio of 1.5:2:8; the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
The artificial muscle fiber with calcium ion response has a tensile strength of 18MPa, is contracted in a solution containing calcium ions, has a contraction rate of 33%, has a tensile strength of 108MPa after the calcium ions are absorbed, and is elongated in a solution with the capability of chelating the calcium ions, and can be restored to an original relaxed state as shown in FIG. 1;
in the process of 20 times of circulation of absorbing calcium ions and losing calcium ions, the tensile strength of the artificial muscle fiber with calcium ion response is changed between 15-16 MPa and 106-109 MPa, and the shrinkage rate is stabilized at 35-38%.
Example 4
A preparation method of artificial muscle fiber with calcium ion response comprises the following specific steps:
(1) Raw material preparation:
polyelectrolyte solution X: sodium alginate is dissolved in water, and the pH value of the sodium alginate is regulated to be 3.5, so that polyelectrolyte solution X with the mass fraction of 0.8wt.% is obtained;
polyelectrolyte solution Y: dissolving chitosan in water, and adjusting the pH value of the chitosan to 6.2 to obtain polyelectrolyte solution Y with the mass fraction of 1 wt%;
solution containing calcium ions: caCl is added with 2 Dissolving in water to obtain CaCl with concentration of 8mg/mL 2 A solution;
Solutions with the ability to sequester calcium ions: dissolving ethylenediamine tetraacetic acid in water to obtain a ethylenediamine tetraacetic acid solution with the concentration of 0.1M;
(2) Preparing polyelectrolyte composite fibers;
taking polyelectrolyte solution X as spinning solution, taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
wherein the residence time of the spinning solution in the coagulating bath after extrusion is 12 hours;
(3) Drying the polyelectrolyte composite fiber prepared in the step (2) at 45 ℃ for 15 hours until the water content is 3wt.%;
(4) Immersing the polyelectrolyte composite fiber prepared in the step (3) into a dopamine solution with the concentration of 1.5mg/mL and the temperature of 20 ℃, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, immersing for 18min to swell the polyelectrolyte composite fiber, adding sodium periodate into the dopamine solution, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, and then continuing immersing for 2h;
wherein the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 2g to 1.5L; the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.4mg/mL;
(5) And (3) taking out the polyelectrolyte composite fiber in the step (4), immersing the polyelectrolyte composite fiber in deionized water, and immersing the polyelectrolyte composite fiber in the deionized water until the polyelectrolyte composite fiber is saturated and absorbed by water to obtain the artificial muscle fiber with the calcium ion response, wherein the diameter of the artificial muscle fiber is 90 mu m, and the water content of the artificial muscle fiber is 78 wt.%.
The prepared artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer is sodium alginate, the middle layer is chitosan, the outer layer is polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; the mass ratio of all the polydopamine, the middle layer (chitosan) and the inner layer (sodium alginate) is 2:1.5:8; the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
the artificial muscle fiber with calcium ion response has a tensile strength of 15MPa, is contracted in a solution containing calcium ions, has a contraction rate of 36%, has a tensile strength of 105MPa after the calcium ions are absorbed, and is elongated in a solution with the capability of chelating the calcium ions, and can be restored to an original relaxed state as shown in FIG. 1;
in the process of 20 times of circulation of absorbing calcium ions and losing calcium ions, the tensile strength of the artificial muscle fiber with calcium ion response is changed between 13-16 MPa and 105-108 MPa, and the shrinkage rate is stabilized between 34-37%.
Example 5
A preparation method of artificial muscle fiber with calcium ion response comprises the following specific steps:
(1) Raw material preparation:
polyelectrolyte solution X: dissolving carboxymethyl cellulose in water, and adjusting the pH value of the carboxymethyl cellulose to 3.8 to obtain polyelectrolyte solution X with the mass fraction of 1 wt%;
polyelectrolyte solution Y: dissolving chitosan in water, and adjusting the pH value of the chitosan to 6.5 to obtain polyelectrolyte solution Y with the mass fraction of 1.2 wt%;
solution containing calcium ions: caCl is added with 2 Dissolving in water to obtain CaCl with concentration of 6mg/mL 2 A solution;
solutions with the ability to sequester calcium ions: phosphate buffer salt solution with concentration of 0.05M;
(2) Preparing polyelectrolyte composite fibers;
taking polyelectrolyte solution X as spinning solution, taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
wherein the residence time of the spinning solution in the coagulating bath after extrusion is 18 hours;
(3) Drying the polyelectrolyte composite fiber prepared in the step (2) at 45 ℃ for 20 hours until the water content is 2wt.%;
(4) Immersing the polyelectrolyte composite fiber prepared in the step (3) into a dopamine solution with the concentration of 1.8mg/mL and the temperature of 22 ℃, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, immersing for 18min to swell the polyelectrolyte composite fiber, adding sodium periodate into the dopamine solution, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, and then continuing immersing for 4h;
Wherein the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 1.5 g/2L; the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.2mg/mL;
(5) And (3) taking out the polyelectrolyte composite fiber in the step (4), immersing the polyelectrolyte composite fiber in deionized water, and immersing the polyelectrolyte composite fiber in the deionized water until the polyelectrolyte composite fiber is saturated and absorbed by water to obtain the artificial muscle fiber with the calcium ion response, wherein the diameter of the artificial muscle fiber is 80 mu m, and the water content of the artificial muscle fiber is 65 wt.%.
The prepared artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer is carboxymethyl cellulose, the middle layer is chitosan, the outer layer is polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; the mass ratio of all polydopamine, middle layer (chitosan) and inner layer (carboxymethyl cellulose) is 2:2:9; the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
the artificial muscle fiber with calcium ion response has a tensile strength of 20MPa, is contracted in a solution containing calcium ions, has a contraction rate of 31%, has a tensile strength of 115MPa after the calcium ions are absorbed, and is elongated in a solution with the capability of chelating the calcium ions, and can be restored to an original relaxed state as shown in FIG. 1;
In the process of 20 times of circulation of absorbing calcium ions and losing calcium ions, the tensile strength of the artificial muscle fiber with calcium ion response is changed between 18-20 MPa and 114-118 MPa, and the shrinkage rate is stabilized between 32-34%.
Example 6
A preparation method of artificial muscle fiber with calcium ion response comprises the following specific steps:
(1) Raw material preparation:
polyelectrolyte solution X: dissolving a mixture of sodium alginate and carboxymethyl cellulose in a mass ratio of 1:1 in water, and regulating the pH value of the mixture to be 4 to obtain polyelectrolyte solution X with a mass fraction of 1.2 wt%;
polyelectrolyte solution Y: dissolving chitosan in water, and adjusting the pH value of the chitosan to 6.8 to obtain polyelectrolyte solution Y with the mass fraction of 1.5 wt%;
solution containing calcium ions: caSO is carried out 4 Dissolving in water to obtain CaSO with concentration of 3mg/mL 4 A solution;
solutions with the ability to sequester calcium ions: dissolving citric acid in water to obtain a citric acid solution with the concentration of 0.18M;
(2) Preparing polyelectrolyte composite fibers;
taking polyelectrolyte solution X as spinning solution, taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
Wherein the residence time of the spinning solution in the coagulating bath after extrusion is 24 hours;
(3) Drying the polyelectrolyte composite fiber prepared in the step (2) at 55 ℃ for 22 hours until the water content is 2wt.%;
(4) Immersing the polyelectrolyte composite fiber prepared in the step (3) into a dopamine solution with the concentration of 2mg/mL and the temperature of 25 ℃, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, immersing for 20min to swell the polyelectrolyte composite fiber, adding sodium periodate into the dopamine solution, adjusting the pH value of the solution to pH=4 by using hydrochloric acid, and then continuing immersing for 5h;
wherein the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 1.5g to 1.5L; the concentration of the sodium periodate in the dopamine solution after the sodium periodate is added is 0.35mg/mL;
(5) And (3) taking out the polyelectrolyte composite fiber in the step (4), immersing the polyelectrolyte composite fiber in deionized water, and immersing the polyelectrolyte composite fiber in the deionized water until the polyelectrolyte composite fiber is saturated and absorbed by water to obtain the artificial muscle fiber with the calcium ion response, wherein the diameter of the artificial muscle fiber is 80 mu m, and the water content of the artificial muscle fiber is 60 wt.%.
The prepared artificial muscle fiber with calcium ion response has a skin-core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside; the inner layer is a mixture of sodium alginate and carboxymethyl cellulose in a mass ratio of 1:1, the middle layer is chitosan, the outer layer is a polydopamine layer, and polydopamine is dispersed in the inner layer and the middle layer; all polydopamine, middle layer (chitosan) and inner layer (mixture of sodium alginate and carboxymethyl cellulose with mass ratio of 1:1) have mass ratio of 2:2:8; the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
The artificial muscle fiber with calcium ion response has 20MPa of tensile strength, the contraction rate is 30% when the artificial muscle fiber absorbs calcium ions in a solution containing calcium ions, the tensile strength is 120MPa after the artificial muscle fiber absorbs calcium ions, and the artificial muscle fiber loses calcium ions in a solution with the capability of chelating calcium ions to elongate and can be restored to the original relaxed state as shown in figure 1;
in the process of 20 times of circulation of absorbing calcium ions and losing calcium ions, the tensile strength of the artificial muscle fiber with calcium ion response is changed between 19-20 MPa and 115-120 MPa, and the shrinkage rate is stabilized at 30-32%.
In addition, by effectively controlling the concentration of calcium ions in the environmental solution to be 0-10 mg/mL and controlling the relaxation and contraction behaviors of artificial muscle fibers with calcium ion responses, the artificial muscle can simulate various movements, the relaxation-contraction movements of muscles, and the driver actively lifts heavy objects to lead flowers to bloom; when Ca in solution 2+ The concentration is increased to 10mg/mL, which can actively lift a weight 1000 times the self weight, as shown in FIG. 2; flowers bloom and contracting movements can be simulated in calcium ion solutions of different concentrations of 0-10 mg/mL, as shown in figure 3.
Claims (11)
1. An artificial muscle fiber having a calcium ion response, characterized by: the leather core has a leather core structure, and an inner layer, an intermediate layer and an outer layer are sequentially arranged from inside to outside;
the inner layer is combined with the middle layer through electrostatic force, and the middle layer is combined with the outer layer through adhesion force;
the inner layer and the middle layer are both polyelectrolytes, and when the inner layer is a polycation electrolyte A, the middle layer is a polyanion electrolyte B; when the inner layer is the polyanion electrolyte B, the middle layer is the polycation electrolyte A;
the polycation electrolyte A is chitosan, and the polyanion electrolyte B is more than one of sodium alginate and carboxymethyl cellulose;
the outer layer is a polydopamine layer; the inner layer and the middle layer are dispersed with polydopamine;
the artificial muscle fiber with calcium ion response is contracted in the solution containing calcium ions, and is lengthened in the solution with the capacity of chelating the calcium ions by losing the calcium ions, so that the artificial muscle fiber can be restored to the original relaxed state.
2. The artificial muscle fiber with calcium ion response according to claim 1, wherein the mass ratio of all polydopamine, polyelectrolyte of the middle layer and polyelectrolyte of the inner layer is 1-2:1-2:8-9.
3. The artificial muscle fiber with calcium ion response according to claim 1, wherein the diameter of the artificial muscle fiber with calcium ion response is 80-100 μm, and the water content is 60-80 wt.%.
4. The artificial muscle fiber with calcium ion response of claim 1, wherein the calcium ion-containing solution is CaCl with a concentration of 1-10 mg/mL 2 Solutions or CaSO 4 The solution with the capability of chelating calcium ions is phosphate buffer salt solution, ethylenediamine tetraacetic acid solution or citric acid solution with the concentration of 0.01-0.2M.
5. The artificial muscle fiber with calcium ion response according to claim 4, wherein the contraction rate of the artificial muscle fiber with calcium ion response after the balance of "absorbing calcium ion" is 30-40%;
the tensile strength of the artificial muscle fiber with the calcium ion response is 10-20 MPa when the artificial muscle fiber does not absorb calcium ions, and the tensile strength of the artificial muscle fiber after absorbing calcium ions is 100-120 MPa.
6. The artificial muscle fiber with calcium ion response of claim 5, wherein the tensile strength of the artificial muscle fiber with calcium ion response is varied between 10-20 mpa and 100-120 mpa and the shrinkage is stabilized at 30-40% after 20 cycles of "absorbing calcium ion" and "losing calcium ion".
7. A method for preparing the artificial muscle fiber with calcium ion response according to any one of claims 1 to 6, which is characterized in that: sequentially immersing polyelectrolyte composite fibers into dopamine solution and deionized water to prepare artificial muscle fibers with calcium ion response;
the polyelectrolyte composite fiber is immersed into the dopamine solution for swelling, and then sodium periodate is added into the dopamine solution;
the polyelectrolyte composite fiber is soaked in deionized water until saturated water absorption;
the preparation method of the polyelectrolyte composite fiber comprises the following steps: taking polyelectrolyte solution X as spinning solution, simultaneously taking polyelectrolyte solution Y as coagulating bath, carrying out wet spinning, and compounding by the coagulating bath to obtain polyelectrolyte composite fibers;
the solute of the polyelectrolyte solution X is the polycation electrolyte A, and the solute of the polyelectrolyte solution Y is the polyanion electrolyte B; alternatively, the solute of polyelectrolyte solution X is the polyanion electrolyte B and the solute of polyelectrolyte solution Y is the polycation electrolyte A.
8. The method of claim 7, wherein the concentration of the dopamine solution is 1-2 mg/mL and the temperature is 20-25 ℃;
the mass volume ratio of the polyelectrolyte composite fiber to the dopamine solution is 1-2 g:1-2L, sodium periodate is added into the dopamine solution after the polyelectrolyte composite fiber is immersed in the dopamine solution for 15-20 min, then the immersion is continued for 1-6 h, and the concentration of sodium periodate in the dopamine solution after the sodium periodate is added is 0.1-0.5 mg/mL.
9. The method according to claim 7, wherein the mass fraction of polyelectrolyte in polyelectrolyte solution X or polyelectrolyte solution Y is 0.5-1.5 wt.%; the residence time of the spinning solution in the coagulating bath after extrusion is 15 min-24 h.
10. The method of claim 7, wherein the polyelectrolyte complex fiber is dried to a water content of <5wt.% prior to immersion in the dopamine solution.
11. The method according to claim 10, wherein the drying treatment is performed at a temperature of 40-60 ℃ for a time of 12-24 hours.
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| CN114908568A (en) * | 2022-05-11 | 2022-08-16 | 东华大学 | Ligament fiber constructed by natural polymer and preparation method thereof |
| CN114917327A (en) * | 2022-06-16 | 2022-08-19 | 嘉兴学院 | Hydrogel micro-beads with core-shell structure and preparation method and application thereof |
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| CN108186555A (en) * | 2017-12-20 | 2018-06-22 | 华南理工大学 | Shape memory gel with calcium ion complexing and redox double-response and preparation method thereof |
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