Sodium alginate strong fiber material with light regulation performance and preparation method thereof

Abstract

The present application relates to the technical field of biological fiber materials and stimuli-responsive materials, and mainly relates to a sodium alginate strong fiber material with light regulation performance and a preparation method thereof.The sodium alginate strong fiber material with light regulation performance is prepared by first injecting a water solution of sodium alginate and a double-chain spiropyran surfactant into a water solution of calcium chloride to obtain a fiber material, and then soaking, stretching and drying the obtained fiber material to obtain a sodium alginate fiber material with double-chain spiropyran surfactant and calcium ions as crosslinking points.The sodium alginate strong fiber material with light regulation performance prepared by the present application is a high-strength and high-toughness material with strength and toughness comparable to spider dragline silk, and can realize efficient regulation of strength and toughness under light conditions.The sodium alginate strong fiber material with light regulation performance prepared by the present application can be applied to the fields of biology, medicine and medical materials as an intelligent strong material.

Description

Technical Field

[0001] This invention relates to the field of bio-fiber materials and stimulus-responsive materials, and mainly to a sodium alginate high-strength fiber material with photomodulation properties and its preparation method. Background Technology

[0002] Stimulus-response properties are crucial for smart materials, enabling controlled changes in their physical and chemical properties. Force, temperature, light, electric fields, magnetic fields, humidity, and chemical substances can all serve as effective sources of external stimuli. Among these, light possesses unique advantages, primarily due to its spatiotemporal controllability, lack of waste, and minimal physical damage.

[0003] Achieving photomodulation of material properties requires the application of photosensitive molecules. These molecules are implanted into materials, and under illumination, they undergo changes in structure, charge, and polarity, driving alterations in the material's properties. This approach has led to the rapid development of various photomodulated materials, including information memory materials, isothermal phase change materials, energy storage materials, self-healing materials, and smart adhesives. Spiropyrans are commonly used photosensitive molecules in organic and biomaterials. Compared to other photosensitive molecules, spiropyrans undergo both conformational and charge changes under illumination, driving alterations in the material's physicochemical properties from both structural and charge perspectives. The photoisomerization of spiropyrans is reversible; the non-planar spirocyclic structure can rapidly transform into a planar conjugated structure under ultraviolet light irradiation. Simultaneously, the molecule changes from a charge-free state to a zwitterionic state, while visible light can drive the open-ring spiropyran molecule back to its spirocyclic structure.

[0004] The preparation of high-strength fiber materials with photocontrollable properties is one of the challenges in materials science. In materials design, achieving high mechanical strength often means sacrificing rapid and efficient control over these properties. However, applying spiropyran molecules to the design and synthesis of materials can effectively solve this problem by simultaneously improving mechanical properties and achieving rapid and efficient control over them. Sodium alginate is one of the most abundant polysaccharide molecules in nature, with a linear structure containing a large number of negative charges. By using positively charged metal ions such as calcium and aluminum ions as cross-linking points, the mechanical properties of sodium alginate materials can be effectively improved. Based on this, various types of high-strength biomaterials have been developed. However, sodium alginate materials prepared solely using metal ions as cross-linking points are difficult to respond effectively to external stimuli, especially for materials with strengths exceeding gigapascals (GPa), where rapid and efficient photocontrol of their mechanical properties at room temperature is even more challenging. Therefore, by utilizing the photosensitive properties of spiropyran molecules, sodium alginate high-strength fiber materials with photomodulation properties can be prepared, which is of great significance for expanding the application of sodium alginate and spiropyran materials in basic scientific research and technological fields. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a sodium alginate high-strength fiber material with light-modulating properties and a method for preparing the same.

[0006] The technical solution of the present invention is as follows:

[0007] This invention provides a sodium alginate high-strength fiber material with light-modulating properties, the raw materials for which include sodium alginate and a double-chain spiropyran surfactant.

[0008] In this invention, the sodium alginate is a mixture of polysaccharide polymers with the molecular formula (C6H7O6Na)n.

[0009] In this invention, the double-chain spiropyran surfactant is any one of N-2,5-dioxaheptayl-N,N-dimethyl-8-(1'-(3',3'-dimethyl-6-nitrospiropyranyl))octylammonium bromide and N-3,6,9,12-tetraoxatridecyl-N,N-dimethyl-8-(1'-(3',3'-dimethyl-6-nitrospiropyranyl))octylammonium bromide.

[0010] In this invention, the preparation method of the sodium alginate high-strength fiber material with light-modulating properties includes:

[0011] At room temperature, an aqueous solution of sodium alginate was mixed with an aqueous solution of a double-chain spiropyran surfactant. The resulting mixture was injected into an aqueous solution of calcium chloride in an S-shaped motion to generate a fiber material. The generated fiber material was immersed in pure water for 1 minute and then removed. The wet fiber material removed from the pure water was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and at a relative humidity of less than 50% to obtain a sodium alginate strong fiber material with light-regulating properties.

[0012] In this invention, in the preparation method of the sodium alginate strong fiber material with light-modulating properties, the concentration of the sodium alginate aqueous solution is 20-30 mmol / L, based on the sodium alginate repeating monosaccharide unit being C6H7O6Na; the concentration of the sodium alginate aqueous solution is 10-15 mmol / L; and the mass concentration of calcium chloride in the calcium chloride aqueous solution is 0.5%.

[0013] In the present invention, in the preparation method of the sodium alginate strong fiber material with light-modulating properties, in the obtained mixture, the sodium alginate is calculated as C6H7O6Na as the repeating monosaccharide unit of sodium alginate, and the molar ratio of sodium alginate to double-chain spiropyran surfactant is 30:1.

[0014] In the present invention, in the preparation method of the sodium alginate strong fiber material with light-modulating properties, the rate at which the obtained mixture is injected into the aqueous solution of calcium chloride in an S-shaped movement is 0.1 to 0.5 mL / s, and the drying time of the stretched wet fiber material at room temperature and relative humidity below 50% is 30 minutes.

[0015] In this invention, after obtaining the sodium alginate strong fiber material with light-modulating properties, the process further includes regulating the mechanical properties of the sodium alginate strong fiber material with light-modulating properties by irradiation with visible light and ultraviolet light at room temperature.

[0016] In this invention, the process of regulating the mechanical properties of the sodium alginate strong fiber material with photo-regulating properties under room temperature conditions by irradiation with visible light and ultraviolet light includes: visible light irradiation, which reduces the strength and toughness of the sodium alginate strong fiber material with photo-regulating properties to less than 30% of the initial value; and ultraviolet light irradiation, which restores the strength and toughness of the sodium alginate strong fiber material with photo-regulating properties.

[0017] In this invention, during the process of regulating the mechanical properties of the sodium alginate high-strength fiber material with photomodulation properties at room temperature through visible light and ultraviolet light irradiation: the visible light irradiation conditions are a wavelength of 520 nm and an intensity of 90 mW / cm².2 The duration is 3 minutes; the ultraviolet light irradiation conditions are a wavelength of 365 nm and an intensity of 30 mW / cm². 2 Time: 3 minutes.

[0018] This invention provides a sodium alginate high-strength fiber material with light-modulating properties and its preparation method. The sodium alginate high-strength fiber material with light-modulating properties and its preparation method have the following characteristics:

[0019] 1. The sodium alginate strong fiber material with light-regulating properties obtained by the present invention is a sodium alginate fiber material with double-chain spiropyran surfactant and calcium ions as crosslinking points.

[0020] 2. The sodium alginate high-strength fiber material with light-modulating properties obtained by this invention possesses both high strength and high toughness. The average tensile strength and toughness of the sodium alginate high-strength fiber material with light-modulating properties can reach 1.3 GPa and 175.4 MJ / m, respectively. 3 These two mechanical properties are comparable to the strength and toughness of spider silk.

[0021] 3. The sodium alginate strong fiber material with light-modulating properties obtained by the present invention can rapidly change its mechanical strength and toughness through light stimulation. Attached Figure Description

[0022] Figure 1 The stress-strain curve of the sodium alginate high-strength fiber material with light-modulating properties described in Example 1 under tensile conditions.

[0023] Figure 2 Scanning electron microscope (SEM) image of the sodium alginate high-strength fiber material with light-modulating properties described in Example 1, taken at room temperature.

[0024] Figure 3 The graph shows the change in mechanical strength of the sodium alginate strong fiber material with light-modulating properties described in Example 1 after irradiation with visible and ultraviolet light.

[0025] Figure 4 The image shows the change in toughness of the sodium alginate strong fiber material with light-modulating properties described in Example 1 after exposure to visible and ultraviolet light. Detailed Implementation

[0026] This invention provides a sodium alginate high-strength fiber material with light-modulating properties and its preparation method. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the same result. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments. Those skilled in the art can obviously make modifications or appropriate alterations and combinations to the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0027] The present invention will be further illustrated below with reference to the embodiments:

[0028] Example 1:

[0029] At room temperature, 5 mL of a 30 mmol / L sodium alginate aqueous solution (based on the sodium alginate repeating monosaccharide unit being C6H7O6Na) and 0.5 mL of a 10 mmol / L N-2,5-dioxahepty-N,N-dimethyl-8-(1'-(3',3'-dimethyl-6-nitrospiropyranyl))octylammonium bromide aqueous solution were mixed. The resulting mixture was injected into 500 mL of a 0.5% calcium chloride aqueous solution using a syringe in an S-shaped motion (at a rate of 0.3 mL / s). The resulting fiber material was immersed in pure water for 1 minute and then removed. The wet fiber material removed from the pure water was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and a relative humidity of less than 50% for 30 minutes to obtain a sodium alginate strong fiber material with light-regulating properties.

[0030] The prepared sodium alginate high-strength fiber material with photomodulation properties, under room temperature conditions, exhibits a stress-strain diagram in a tensile test, as shown below. Figure 1 As shown, according to Figure 1 The results showed that the average tensile strength and toughness of the sodium alginate high-strength fiber material with light-modulating properties reached 1.3 GPa and 175.4 MJ / m, respectively. 3 The average tensile strength and toughness of the sodium alginate strong fiber material with light-modulating properties are comparable to those of spider traction silk, indicating that the sodium alginate strong fiber material with light-modulating properties possesses both high strength and high toughness.

[0031] The prepared sodium alginate high-strength fiber material with photomodulation properties is shown in the scanning electron microscope image at room temperature, as follows: Figure 2 As shown, according to Figure 2 It was found that the sodium alginate high-strength fiber material with light-modulating properties has a smooth surface structure and a solid internal structure, and is uniform in thickness.

[0032] The prepared sodium alginate high-strength fiber material with photomodulation properties exhibits the following changes in mechanical strength after irradiation with visible and ultraviolet light at room temperature: Figure 3 As shown, according to Figure 3 It was found that the sodium alginate strong fiber material with light-modulating properties can regulate its mechanical strength to 0.36 GPa after visible light irradiation, and the sodium alginate strong fiber material with light-modulating properties can regulate its mechanical strength to recover after ultraviolet light irradiation.

[0033] The prepared sodium alginate strong fiber material with photomodulation properties exhibits the following toughness changes after visible and ultraviolet light irradiation at room temperature: Figure 4 As shown, according to Figure 4 The results showed that the sodium alginate high-strength fiber material with light-modulating properties could modulate its toughness to 6.8 MJ / m after visible light irradiation. 3 The sodium alginate strong fiber material with light-modulating properties can restore its toughness after ultraviolet light irradiation.

[0034] Example 2:

[0035] At room temperature, 5 mL of a 30 mmol / L sodium alginate aqueous solution (based on the sodium alginate repeating monosaccharide unit being C6H7O6Na) and 0.5 mL of a 10 mmol / L N-3,6,9,12-tetraoxatridecyl-N,N-dimethyl-8-(1'-(3',3'-dimethyl-6-nitrospiropyranyl))octylammonium bromide aqueous solution were mixed. The resulting mixture was injected into 500 mL of a 0.5% calcium chloride aqueous solution using a syringe in an S-shaped motion (at a rate of 0.3 mL / s). The resulting fiber material was immersed in pure water for 1 minute and then removed. The wet fiber material removed from the pure water was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and at a relative humidity of less than 50% for 30 minutes to obtain a sodium alginate strong fiber material with light-regulating properties.

[0036] Comparative Example 1:

[0037] At room temperature, 5 mL of a 30 mmol / L sodium alginate aqueous solution (based on the sodium alginate repeating monosaccharide unit being C6H7O6Na) and 0.75 mL of a 10 mmol / L N-2,5-dioxaheptyro-N,N-dimethyl-8-(1'-(3',3'-dimethyl-6-nitrospiropyranyl))octylammonium bromide aqueous solution were mixed. The resulting mixture was injected into 500 mL of a 0.5% calcium chloride aqueous solution using a syringe in an S-shaped motion (at a rate of 0.3 mL / s). The resulting fiber material was immersed in pure water for 1 minute and then removed. The wet fiber material removed from the pure water was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and relative humidity below 50% for 30 minutes to obtain a sodium alginate fiber material containing a double-chain spiropyran surfactant.

[0038] The sodium alginate fiber material containing a double-chain spiropyran surfactant prepared in Comparative Example 1, after testing, showed an average mechanical strength below 0.85 GPa and an average toughness of 80 MJ / m. 3 In the following, the mechanical strength and toughness of the sodium alginate fiber material containing double-chain spiropyran surfactant prepared in Comparative Example 1 are significantly weaker than the sodium alginate high-strength fiber material with photomodulation properties described in this invention.

[0039] Comparative Example 2:

[0040] At room temperature, 5 mL of sodium alginate aqueous solution with a concentration of 30 mmol / L (calculated as sodium alginate repeating monosaccharide unit C6H7O6Na) was injected into 500 mL of calcium chloride aqueous solution with a mass concentration of 0.5% using a syringe in an S-shaped movement (rate of 0.3 mL / s). The resulting fiber material was immersed in pure water for 1 minute and then removed. The wet fiber material removed from the pure water was stretched to a strain of 110%. Finally, the stretched wet fiber material was dried at room temperature and relative humidity below 50% for 30 minutes to obtain sodium alginate fiber material.

[0041] The sodium alginate fiber material prepared in Comparative Example 2, after testing, showed that at room temperature, it had an average tensile strength of less than 400 MPa and a toughness of less than 20 MJ / m. 3 Its strength and toughness are far lower than those of the sodium alginate high-strength fiber material with light-modulating properties described in Example 1.

[0042] The sodium alginate fiber material prepared in Comparative Example 2 was tested and found to lack light modulation properties.

[0043] The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art can make several improvements without departing from the principle of the present invention, and these improvements should also be considered within the scope of protection of the present invention.

Claims

1. A sodium alginate high-strength fiber material with light-modulating properties, characterized in that, The raw materials for its preparation include sodium alginate and a double-chain spiropyran surfactant. The sodium alginate is a mixture of polysaccharide polymers with the molecular formula (C6H7O6Na)n, and the double-chain spiropyran surfactant is... N -2,5-dioxaheptyl- N,N -Dimethyl-8-(1'-(3',3'-dimethyl-6-nitrospiropyranyl))octylammonium bromide and N -3,6,9,12-tetraoxatridecyl- N,N The method for preparing the sodium alginate strong fiber material with photomodulation properties comprises: mixing an aqueous solution of sodium alginate with an aqueous solution of a double-chain spiropyran surfactant at room temperature; injecting the resulting mixture into an aqueous solution of calcium chloride in an S-shaped motion to generate fiber material; immersing the generated fiber material in pure water for 1 minute and then removing it; stretching the wet fiber material removed from the pure water to a strain of 110%; and finally drying the stretched wet fiber material at room temperature and a relative humidity of less than 50% to obtain the sodium alginate strong fiber material with photomodulation properties. In the preparation method of the sodium alginate strong fiber material with photomodulation properties, the concentration of the sodium alginate aqueous solution is 20-30 mmol / L, calculated as sodium alginate repeating monosaccharide unit C6H7O6Na; the concentration of the double-chain spiropyran surfactant aqueous solution is 10-15 mmol / L; and the mass concentration of calcium chloride in the calcium chloride aqueous solution is 0.5%. In the preparation method of the sodium alginate strong fiber material with photomodulation properties, in the resulting mixture, the molar ratio of sodium alginate to double-chain spiropyran surfactant is 30:1, calculated as sodium alginate repeating monosaccharide unit C6H7O6Na.

2. The method for preparing sodium alginate high-strength fiber material with light-modulating properties according to claim 1, characterized in that, include: At room temperature, an aqueous solution of sodium alginate is mixed with an aqueous solution of a double-chain spiropyran surfactant. The resulting mixture is injected into an aqueous solution of calcium chloride in an S-shaped motion to generate a fiber material. The generated fiber material is immersed in pure water for 1 minute and then removed. The wet fiber material removed from the pure water is stretched to a strain of 110%. Finally, the stretched wet fiber material is dried at room temperature and a relative humidity of less than 50% to obtain a sodium alginate strong fiber material with photomodulation properties. In the preparation method of the sodium alginate strong fiber material with photomodulation properties, the alginate... The sodium aqueous solution is calculated based on sodium alginate repeating monosaccharide units of C6H7O6Na, and the concentration of the sodium alginate aqueous solution is 20-30 mmol / L. The concentration of the double-chain spiropyran surfactant aqueous solution is 10-15 mmol / L. The mass concentration of calcium chloride in the calcium chloride aqueous solution is 0.5%. In the preparation method of the sodium alginate strong fiber material with light-modulating properties, in the obtained mixture, the sodium alginate is calculated based on sodium alginate repeating monosaccharide units of C6H7O6Na, and the molar ratio of sodium alginate to double-chain spiropyran surfactant is 30:

1.

3. The method for preparing sodium alginate high-strength fiber material with light-modulating properties according to claim 2, characterized in that, The rate at which the obtained mixture is injected into the aqueous solution of calcium chloride in an S-shaped motion is 0.1~0.5 mL / s, and the drying time of the stretched wet fiber material at room temperature and relative humidity below 50% is 30 minutes.

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