Conductive polymer precursor solution with packaging and reversible removal functions as well as preparation method and application of conductive polymer precursor solution

Abstract

The invention belongs to the crossing field of material science and biotechnology, and discloses a conductive polymer precursor solution with packaging and reversible removal functions, and a preparation method and application thereof. The method comprises the following steps: preparing a high-conductivity nanofiller suspension; uniformly mixing a dynamic cross-linking agent, a conductive monomer, the high-conductivity nanofiller suspension and an optional initiator, and performing in-situ polymerization reaction to obtain a conductive polymer precursor solution with a dynamic cross-linked network; the conductive polymer precursor solution has a microbial cell packaging function and a reversible removal function by introducing the dynamic chemical bond and the high-conductivity nano filler, and the conductivity, stability and functionality of the conductive polymer film for packaging the microbial cells are remarkably improved at the same time.

Description

Technical Field

[0001] The present invention belongs to the cross - field of materials science and biotechnology. More specifically, it relates to a conductive polymer precursor solution with encapsulation and reversible removal functions, a preparation method thereof, and an application thereof. Background Art

[0002] With the exacerbation of global environmental problems and the growth of energy demand, the use of the functional characteristics of microbial cells (such as pollutant degradation, energy conversion, signal response, etc.) has become a research hotspot. However, directly using microbial cells has problems such as poor stability and easy inactivation. Therefore, encapsulating them in functional materials is a key strategy to improve their stability and service life.

[0003] Due to their excellent electrical conductivity, good biocompatibility, and adjustable physical and chemical properties, conductive polymers have become ideal candidate materials for encapsulating microbial cells. Conductive polymers encapsulating microbial cells can be widely applied in fields such as biosensors, bioremediation materials, and intelligent materials. However, the existing technologies have significant deficiencies in the following aspects:

[0004] (1) Irreversibility: Traditional encapsulation methods usually adopt permanent bonding methods. Once the microbial cells are encapsulated, it is difficult to take them out, which limits the reuse and function update of the materials.

[0005] (2) Insufficient electrical conductivity: The electrical conductivity of traditional conductive polymers (such as polypyrrole and polyaniline) is limited, making it difficult to meet the requirements of high - sensitivity sensors or intelligent materials.

[0006] (3) Low encapsulation efficiency: Existing encapsulation methods usually require complex technological processes and have a greater impact on the activity of microbial cells.

[0007] (4) Weak interfacial binding force: The interfacial binding force between microbial cells and conductive polymers is weak, resulting in poor stability of the encapsulated materials.

[0008] In addition, with the promotion of the concept of sustainable development, the development of recyclable functional materials has become a research hotspot. There is currently no research report on combining the reversible removal and re - encapsulation technology of microbial cells with conductive polymers.

[0009] In summary, the existing technologies still have core technical problems in the electrical conductivity of conductive polymers, the encapsulation efficiency of microbial cells, the interfacial binding force, and the reversibility of materials. Summary of the Invention

[0010] The object of the present invention is to address the deficiencies of the prior art and propose a conductive polymer precursor solution with encapsulation and reversible removal functions, as well as a preparation method and application thereof. By introducing dynamic chemical bonds and highly conductive nanomaterials, the conductive polymer precursor solution of the present invention has the functions of microbial cell encapsulation and reversible removal, and simultaneously significantly improves the conductivity, stability, and functionality of the conductive polymer film encapsulating microbial cells.

[0011] To achieve the above object, in a first aspect of the present invention, a preparation method of a conductive polymer precursor solution with encapsulation and reversible removal functions is provided, and the method includes the following steps:

[0012] S1: Prepare a highly conductive nanomaterial suspension;

[0013] S2: Uniformly mix a dynamic crosslinking agent, a conductive monomer, the highly conductive nanomaterial suspension, and an optional initiator, and carry out an in-situ polymerization reaction to obtain a conductive polymer precursor solution with a dynamic crosslinked network.

[0014] According to the present invention, preferably, the highly conductive nanomaterial is graphene quantum dots (GQDs) and / or carbon nanotubes (CNTs).

[0015] According to the present invention, preferably, the dynamic crosslinking agent is at least one of polyvinyl formal (PFM), a dynamic carbamate bond compound, a borate bond compound, and a disulfide bond compound.

[0016] According to the present invention, preferably, the conductive monomer is polyaniline (PANI) and / or polypyrrole (PPy).

[0017] According to the present invention, preferably, the initiator is at least one of persulfate, metal chloride, and a hydroxy photoinitiator; in the present invention, as a preferred embodiment, the initiator is at least one of ammonium persulfate, ferric chloride, and Irgacure 2959.

[0018] According to the present invention, preferably, the dosage ratio of the highly conductive nanomaterial suspension, the dynamic crosslinking agent, the conductive monomer, and the initiator is (10 - 20):(0.1 - 0.5):(0.4 - 2.0):(0.01 - 0.05) mL / g / g / g; the mass concentration of the highly conductive nanomaterial suspension is 0.05 - 0.15 mg / mL.

[0019] According to the present invention, preferably, the step of preparing the highly conductive nanomaterial suspension includes: mixing the highly conductive nanomaterial, a solvent, and an optional surfactant to obtain a mixture; subjecting the mixture to ultrasonic treatment so that the highly conductive nanomaterial is uniformly dispersed in the mixture to obtain the highly conductive nanomaterial suspension.

[0020] According to the present invention, preferably, the solvent is deionized water and / or ethanol.

[0021] In the present invention, adding an appropriate amount of surfactant can improve the dispersibility of highly conductive nanofillers. As a preferred embodiment, the present invention selects sodium dodecyl sulfate (SDS) with a mass concentration of 0.05-0.1% as the surfactant.

[0022] In the present invention, the device used for ultrasonic treatment is an ultrasonic disperser, with a power of 200-400 W, a frequency of 20-40 kHz, and a duration of 30-60 minutes, to ensure that the highly conductive nanofillers are uniformly dispersed in the mixed solution, obtaining a suspension of highly conductive nanofillers.

[0023] According to the present invention, preferably, the reaction temperature of the in-situ polymerization reaction is 50-80 °C, and the reaction time is 30-120 min.

[0024] In the present invention, the in-situ polymerization reaction can be achieved by light irradiation or other heating methods well-known in the art. Preferably, the intensity of the light irradiation is 50-200 mW / cm 2 。

[0025] The second aspect of the present invention provides a conductive polymer precursor solution prepared by the preparation method of the conductive polymer precursor solution with encapsulation and reversible removal functions as described above.

[0026] The third aspect of the present invention provides the application of the conductive polymer precursor solution as a functional material for encapsulating microbial cells.

[0027] According to the present invention, preferably, the encapsulation method includes: first, introducing the conductive polymer precursor solution into a microfluidic device; then, introducing a microbial cell suspension into the microfluidic device to be uniformly mixed with the conductive polymer precursor solution, and completing the encapsulation in a flowing state to obtain an encapsulated product; and performing curing and drying treatments on the encapsulated product to obtain a conductive polymer film encapsulating microbial cells.

[0028] In the present invention, if the conductive polymer precursor solution of the present invention is used as a functional material for encapsulating microbial cells, then the in-situ polymerization reaction can be carried out in a microfluidic device to obtain a conductive polymer precursor solution. Any microfluidic device well-known in the art can be used in the present invention to achieve encapsulation.

[0029] According to the present invention, preferably, the conditions of the encapsulation method include: an encapsulation temperature of 40-60°C, an encapsulation time of 30-120 min, a flow rate of the microbial cell suspension of 0.5-1 mL / min, and a total flow rate of the microbial cell suspension of 10-40 mL; optionally also including the pH value of the encapsulation system, and / or an anaerobic environment.

[0030] In the present invention, the anaerobic / aerobic characteristics of microorganisms need to be considered during encapsulation. If anaerobic microbial cells are encapsulated, care should be taken to maintain an anaerobic environment in the microfluidic device and during operation. In addition, for specific microbial cells, the pH value of the encapsulation system during encapsulation needs to be considered. For example, for lactobacilli, the pH value of the encapsulation system is 5.5-6.5.

[0031] According to the present invention, preferably, the microbial cells are photosynthetic bacteria and / or enzyme-producing bacteria.

[0032] According to the present invention, preferably, the concentration of the microbial cell suspension is 1×10 7 -1×10 9 cells / mL.

[0033] According to the present invention, preferably, the volume ratio of the conductive polymer precursor solution to the microbial cell suspension is 1:(1-2).

[0034] According to the present invention, preferably, the curing temperature is 55-65° C. and the curing time is 1-2.5 h.

[0035] According to the present invention, preferably, the drying temperature is 60-80° C. and the drying time is 4-12 h.

[0036] According to the present invention, preferably, the application also includes: the film is de-crosslinked by a dynamic cross-linking network to de-seal and remove the microbial cells encapsulated in the film, and the non-cross-linked system obtained by de-cross-linking is re-cross-linked to obtain a recombinant conductive polymer precursor solution and new microbial cells are re-encapsulated according to the encapsulation method.

[0037] According to the present invention, preferably, the conditions for achieving decrosslinking of the dynamic crosslinked network include: setting the decrosslinking temperature and decrosslinking time, optionally also including setting the decrosslinking pH value and / or setting light; preferably, the decrosslinking temperature is 80-100°C, and the decrosslinking time is 10-30min.

[0038] In the present invention, in most cases, de-crosslinking is achieved by temperature. For pH-responsive crosslinking agents, such as borate bond compounds, pH value needs to be assisted to complete the de-crosslinking, and a certain temperature may also be required at this time.

[0039] According to the present invention, preferably, the conditions for realizing network re-crosslinking include: setting the re-crosslinking temperature and the re-crosslinking time, and optionally further including setting the pH value of re-crosslinking and / or setting light irradiation; preferably, the re-crosslinking temperature is 20-50 °C and the re-crosslinking time is 30-60 min.

[0040] According to the present invention, preferably, the de-crosslinking and network re-crosslinking of the dynamic crosslinked network are carried out multiple times, preferably 1-3 times.

[0041] In the present invention, the released microbial cells are inactivated or functionally deteriorated microbial cells, and the present invention removes the inactivated or functionally deteriorated microbial cells by centrifugation or filtration. Among them, the sequential steps for realizing reversible removal and re-encapsulation in the present invention are: de-crosslinking of the dynamic crosslinked network - releasing inactivated or functionally deteriorated microbial cells - centrifuging or filtering to remove inactivated or functionally deteriorated microbial cells - network re-crosslinking - re-encapsulating new microbial cells.

[0042] In the present invention, for example, for Lactobacillus cells, the encapsulated conductive polymer film is immersed in a liquid with a pH of 4.0-4.5 for 10 min to break the dynamic bonds, realizing the de-crosslinking of the dynamic crosslinked network, reversibly releasing the Lactobacillus encapsulated in the film, and filtering and separating; the pH of the de-crosslinked non-crosslinked system is restored to 5.5-6.5 to realize network re-crosslinking, obtaining a recombinant conductive polymer precursor solution, and re-encapsulating new microbial cells according to the encapsulation method.

[0043] The technical principle of the present invention:

[0044] (1) Design and construction of the dynamic crosslinked network: The design of the dynamic crosslinked network is the core for realizing reversibility. The present invention constructs a reversible crosslinked network by introducing a dynamic crosslinking agent (polyvinyl formal (PFM)) to achieve reversible binding between microbial cells and conductive polymers. Specifically: The present invention first prepares a highly conductive nanofiller suspension, then adds a dynamic crosslinking agent to induce a crosslinking reaction, and by controlling the reaction conditions, promotes the covalent bond and non-covalent interaction between the dynamic crosslinking agent and the conductive monomer, forming a dynamic crosslinked network of the conductive polymer.

[0045] (2) Introduction of highly conductive nanofillers: The conductive polymer of the present invention introduces highly conductive nanofillers (graphene quantum dots (GQDs)). By surface modification of the nanofillers, the dispersibility and interfacial binding of the conductive polymer are optimized, significantly improving the conductive performance of the conductive polymer.

[0046] (3) Encapsulation process optimization of microbial cells: By using microfluidic technology to achieve precise control, the conductive polymer precursor solution of the present invention can be obtained through in-situ polymerization reaction in a microfluidic device; then, a microbial cell suspension is introduced into the microfluidic device and further added to the dynamic cross-linking network of the conductive polymer obtained by in-situ polymerization reaction to achieve uniform encapsulation of the cells. The encapsulation efficiency is optimized and cell viability is maintained by controlling the flow rate and flow volume. At the same time, by using microfluidic technology, the interfacial binding force between the microbial cells and the conductive polymer is significantly enhanced. After curing, a stable conductive polymer film encapsulating the microbial cells is formed.

[0047] (4) Reversible removal and re-encapsulation technology: It includes the controllable fracture of the dynamic cross-linking network and the re-encapsulation of microbial cells. The controllable fracture of the dynamic cross-linking network of the conductive polymer of the present invention includes the fracture of covalent bonds and the recombination of non-covalent interactions. Among them:

[0048] First, through a first specific condition (such as a temperature condition, a light condition, or a pH value condition), the covalent bonds of the cross-linking agent are fractured to achieve network de-crosslinking;

[0049] After that, in a second specific condition (such as a temperature condition, a light condition, or a pH value condition), non-covalent interactions such as hydrogen bonds are re-established to promote network re-crosslinking, and controllable fracture and recombination are achieved through dynamic covalent bonds and non-covalent interactions;

[0050] In addition, the inactivated or functionally deteriorated microbial cells released by de-encapsulation are removed by centrifugation or filtration;

[0051] And, new microbial cells are introduced again to complete re-encapsulation.

[0052] The present invention significantly improves the reusability and functional updating potential of the conductive polymer material.

[0053] The beneficial effects of the technical solution of the present invention are as follows:

[0054] By introducing dynamic chemical bonds and highly conductive nano-fillers, the present invention achieves efficient encapsulation and reversible removal of microbial cells, as well as functional updates of functional materials composed of microbial cells, conductive polymers, and reversible encapsulation technology (specifically, multi-functional strain compatibility: supporting the encapsulation of various microorganisms such as photosynthetic bacteria and enzyme-producing bacteria; controllable release function: precisely releasing inactivated microorganisms under specific de-crosslinking conditions (such as soaking in 80°C hot water); interface strengthening function: the dynamic cross-linking network enhances the interfacial binding force through the recombination of non-covalent bonds (such as hydrogen bonds); environmental responsiveness: the film encapsulating photosynthetic bacteria can convert light energy into chemical energy and utilize the sensitivity of bacteria to pollutants for in-situ detection). At the same time, the conductivity, stability, and functionality of the conductive polymer film encapsulating microbial cells are significantly improved, providing a new solution for the fields of intelligent materials and biomanufacturing.

[0055] The present invention combines microbial cells, conductive polymers, and reversible encapsulation technology to prepare a functional material with high sensitivity, reusability, and high stability. The conductive polymer precursor solution of the present invention is not only applicable to the encapsulation of various functional strains, but also particularly suitable for the development of reusable biosensors, bioremediation materials, intelligent materials, and sustainable functional materials, and has important application values in the fields of environmental protection, biotechnology, and energy. At the same time, the green preparation process of the present invention (such as the recycling of materials, the selection of environmentally friendly solvents, and the re-crosslinking without additional purification steps) and the sustainable (i.e., reversible encapsulation) design also provide strong support for environmental protection and resource conservation, and have good industrial scaling potential and broad application prospects.

[0056] Other features and advantages of the present invention will be described in detail in the following specific implementation section. Brief Description of the Drawings

[0057] By describing the exemplary embodiments of the present invention in more detail in conjunction with the drawings, the above and other objects, features, and advantages of the present invention will become more obvious. Among them, in the exemplary embodiments of the present invention, the same reference numerals generally represent the same components.

[0058] Figure 1 Shows the process flow chart of the preparation of a conductive polymer film encapsulating microbial cells provided by the present invention.

[0059] Figure 2 Shows the SEM image of the conductive polymer film encapsulating photosynthetic bacteria obtained in Example 2 of the present invention.

[0060] Figure 3 Shows the three-cycle test result diagram of the conductive polymer film encapsulating photosynthetic bacteria obtained in Example 2 of the present invention. Detailed Description of the Invention

[0061] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present invention more thorough and complete, and to fully convey the scope of the present invention to those skilled in the art.

[0062] Example 1

[0063] This example provides a method for preparing a conductive polymer precursor solution with encapsulation and reversible removal functions, and the method includes the following steps:

[0064] S1: Weigh an appropriate amount of graphene quantum dots (GQDs), add deionized water, and configure a mixed solution with a concentration of 0.1 mg / mL. Use an ultrasonic disperser to perform ultrasonic treatment on the mixed solution, with a power of 200 - 400 W, a frequency of 20 - 40 kHz, and a duration of 30 - 60 minutes to ensure the uniform dispersion of GQDs, and obtain a highly conductive nanofiller suspension;

[0065] S2: Uniformly mix 0.2 g of polyvinyl formal (PFM), 0.5 g of polyaniline (PANI), 20 mL of the highly conductive nanofiller suspension, and 0.015 g of ammonium persulfate (APS), and perform an in-situ polymerization reaction (reaction temperature is 60 °C, reaction time is 60 min) to obtain a conductive polymer precursor solution with a dynamic crosslinked network.

[0066] Example 2

[0067] This example encapsulates photosynthetic bacteria using the conductive polymer precursor solution with a dynamic crosslinked network prepared in Example 1. Specifically, it includes:

[0068] (1) Cultivate photosynthetic bacteria to the logarithmic growth phase, and centrifuge and concentrate them to a concentration of 1×10 8 cells / mL to obtain a microbial cell suspension;

[0069] (2) Pass the conductive polymer precursor solution into a microfluidic device;

[0070] (3) Pass the microbial cell suspension in step (1) into the microfluidic device to be uniformly mixed with the conductive polymer precursor solution, and complete encapsulation under a flowing state to obtain an encapsulated product;

[0071] Wherein: the encapsulation temperature is 50 °C, the encapsulation time is 3 h, the flow rate of the microbial cell suspension is 0.75 mL / min, and the total flow rate of the microbial cell suspension is 20 mL; the volume ratio of the conductive polymer precursor solution to the microbial cell suspension is 1:1;

[0072] (4) curing the encapsulated product at 60° C. for 2 hours. After curing, the cured material was placed in a vacuum drying oven and dried at 80° C. for 6 hours to obtain a conductive polymer film encapsulating photosynthetic bacteria;

[0073] This embodiment also includes:

[0074] (5) soaking the encapsulated conductive polymer film in hot water at 80° C. for 10-30 minutes to decrosslink the dynamic crosslinked network, so that the photosynthetic bacteria encapsulated in the film can be reversibly decapsulated, filtered, separated and removed;

[0075] (6) Cooling the non-crosslinked system obtained by de-crosslinking to 25°C to achieve network re-crosslinking to obtain a recombinant conductive polymer precursor solution, repeating the above steps (1)-(4), and re-sealing a new photosynthetic bacterial suspension (concentration of 1×10 8 cells / mL).

[0076] Performance test results of the conductive polymer film encapsulating photosynthetic bacteria in this example:

[0077] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.047Ω·cm, which is significantly lower than the resistivity of the polyaniline (PANI) film (0.5-100Ω·cm). It can be seen that the conductive polymer film encapsulating photosynthetic bacteria in this embodiment shows excellent conductivity;

[0078] Packaging efficiency: Figure 2 The results of the conductivity test showed that the survival rate of photosynthetic bacteria reached 95%, and its photosynthetic activity remained unchanged;

[0079] Interface bonding strength: Figure 2 , which is a SEM image of the conductive polymer film encapsulating photosynthetic bacteria in this embodiment, Figure 2 The microscopic morphology of the conductive polymer encapsulating photosynthetic bacteria is shown. Figure 2 It can be seen that the microbial cells are evenly distributed in the conductive polymer of the present invention. In addition, after the conductive polymer film encapsulating photosynthetic bacteria of this embodiment is ultrasonically treated at a power of 150W for 10 minutes, the cell shedding rate is less than 3%, indicating that the microbial cells and the conductive polymer of the present invention have good interface bonding strength.

[0080] Reversibility test: After three cycles of removal and repackaging (i.e., steps (5) and (6) were cycled three times), the conductivity of the film remained at the initial level, e.g. Figure 3 shown.

[0081] The conductive polymer film encapsulating photosynthetic bacteria in this embodiment utilizes the sensitivity of photosynthetic bacteria to environmental changes and combines the electrical conductivity of the conductive polymer, and can be used to prepare sensors for real-time monitoring of environmental parameters; in addition, photosynthetic bacteria can carry out photosynthesis and convert light energy into chemical energy. Therefore, the conductive polymer film encapsulating photosynthetic bacteria in this embodiment can also be used to prepare bio-solar cells; furthermore, photosynthetic bacteria are sensitive to pollutants in the environment (such as heavy metal ions, organic pollutants, etc.). Therefore, the film in this embodiment can also be used to prepare instruments for detecting the concentration of specific pollutants in water or air.

[0082] Example 3

[0083] The difference between this embodiment and Example 1 is only that: the high-conductivity nanofiller suspension is 15 mL, and the concentration of the high-conductivity nanofiller suspension is 0.08 mg / mL.

[0084] Performance test results of the conductive polymer film encapsulating photosynthetic bacteria in this embodiment:

[0085] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.113 Ω·cm, which is significantly lower than the resistivity of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the conductive polymer film encapsulating photosynthetic bacteria in this embodiment shows excellent electrical conductivity;

[0086] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 92.6%, and its photosynthetic activity remains unchanged.

[0087] Example 4

[0088] The difference between this embodiment and Example 1 is only that: the high-conductivity nanofiller suspension is 10 mL, and the concentration of the high-conductivity nanofiller suspension is 0.12 mg / mL.

[0089] Performance test results of the conductive polymer film encapsulating photosynthetic bacteria in this embodiment:

[0090] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.11 Ω·cm, which is significantly lower than the resistivity of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the conductive polymer film encapsulating photosynthetic bacteria in this embodiment shows excellent electrical conductivity;

[0091] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 92.2%, and its photosynthetic activity remains unchanged.

[0092] Example 5

[0093] The difference between this embodiment and Example 1 is only that: the polyvinyl formal (PFM) is 0.1 g.

[0094] Performance test results of the conductive polymer film encapsulating photosynthetic bacteria in this example:

[0095] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.152 Ω·cm, which is significantly lower than that of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the conductive polymer film encapsulating photosynthetic bacteria in this example exhibits excellent conductivity;

[0096] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 90.3%, and its photosynthetic activity remains unchanged.

[0097] Interface bonding force: The cell shedding rate is < 3% after ultrasonic treatment at a power of 150 W for 10 min.

[0098] Reversibility test: The conductivity remains 80.5% of the initial value after 2 cycles.

[0099] Example 6

[0100] The difference between this example and Example 1 is only that: the polyvinyl formal (PFM) is 0.5 g.

[0101] Performance test results of the conductive polymer film encapsulating photosynthetic bacteria in this example:

[0102] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.056 Ω·cm, which is significantly lower than that of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the conductive polymer film encapsulating photosynthetic bacteria in this example exhibits excellent conductivity;

[0103] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 85.5%, and its photosynthetic activity basically remains unchanged.

[0104] Interface bonding force: The cell shedding rate is < 4% after ultrasonic treatment at a power of 150 W for 10 min.

[0105] Reversibility test: The survival rate drops to 79.8% after 2 cycles because the amount of dynamic crosslinking agent is large. Therefore, the conductive polymer has a high crosslinking density, and high crosslinking density will lead to incomplete de-crosslinking.

[0106] Example 7

[0107] The difference between this example and Example 2 is only that: the flow rate of the microbial cell suspension is 0.5 mL / min, and the total flow rate of the microbial cell suspension is 12 mL.

[0108] Performance test results of the conductive polymer film encapsulating photosynthetic bacteria in this example:

[0109] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.059 Ω·cm, significantly lower than that of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the encapsulated conductive polymer film with photosynthetic bacteria in this example shows excellent conductivity;

[0110] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 91.4%, and its photosynthetic activity remains unchanged.

[0111] Interface binding force: The cell shedding rate is <4% after ultrasonic treatment at a power of 150 W for 10 min.

[0112] Reversibility test: The conductivity drops to 82.6% after 2 cycles.

[0113] Example 8

[0114] The difference between this example and Example 2 is only that: the flow rate of the microbial cell suspension is 1 mL / min, and the total flow rate of the microbial cell suspension is 40 mL.

[0115] Performance test results of the encapsulated conductive polymer film with photosynthetic bacteria in this example:

[0116] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.049 Ω·cm, significantly lower than that of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the encapsulated conductive polymer film with photosynthetic bacteria in this example shows excellent conductivity;

[0117] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 90.1%, and its photosynthetic activity remains unchanged.

[0118] Interface binding force: The cell shedding rate is <4% after ultrasonic treatment at a power of 150 W for 10 min.

[0119] Reversibility test: The conductivity drops to 84.2% after 2 cycles.

[0120] Example 9

[0121] The difference between this example and Example 1 is only that: the reaction temperature of the in-situ polymerization reaction is 50 °C, and the reaction time is 90 min.

[0122] Performance test results of the encapsulated conductive polymer film with photosynthetic bacteria in this example:

[0123] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.126 Ω·cm, which is significantly lower than that of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the encapsulated conductive polymer film with photosynthetic bacteria in this example exhibits excellent conductivity;

[0124] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 90.4%, and its photosynthetic activity remains unchanged.

[0125] Interface bonding force: The cell detachment rate is <5% after ultrasonic treatment at a power of 150 W for 10 min.

[0126] Reversibility test: The conductivity drops to 81.5% after 2 cycles.

[0127] Example 10

[0128] The difference between this example and Example 1 is only that: the reaction temperature of the in-situ polymerization reaction is 80 °C and the reaction time is 120 min.

[0129] Performance test results of the encapsulated conductive polymer film with photosynthetic bacteria in this example:

[0130] Conductivity test: The resistivity of the encapsulated conductive polymer film is 0.137 Ω·cm, which is significantly lower than that of the polyaniline (PANI) film (0.5 - 100 Ω·cm). Thus, it can be seen that the encapsulated conductive polymer film with photosynthetic bacteria in this example exhibits excellent conductivity;

[0131] Encapsulation efficiency: The survival rate of photosynthetic bacteria reaches 89.3%, and its photosynthetic activity remains unchanged.

[0132] Interface bonding force: The cell detachment rate is <5% after ultrasonic treatment at a power of 150 W for 10 min.

[0133] Reversibility test: The conductivity drops to 80.1% after 2 cycles.

[0134] The above has described the embodiments of the present invention. The above description is exemplary and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A method for preparing a conductive polymer precursor solution with encapsulation and reversible removal functions, characterized in that, The method includes the following steps: S1: Prepare a highly conductive nanofiller suspension; S2: Uniformly mix a dynamic crosslinking agent, a conductive monomer, the highly conductive nanofiller suspension, and an optional initiator, and conduct an in-situ polymerization reaction to obtain a conductive polymer precursor solution with a dynamic crosslinking network.

2. The method for preparing a conductive polymer precursor solution with encapsulation and reversible removal functions according to claim 1, wherein, The highly conductive nanofiller is graphene quantum dots and / or carbon nanotubes; The dynamic crosslinking agent is at least one of polyvinyl formal, a dynamic carbamate bond compound, a borate ester bond compound, and a disulfide bond compound; The conductive monomer is polyaniline and / or polypyrrole; The initiator is at least one of persulfate, metal chloride, and a hydroxy photoinitiator; The dosage ratio of the highly conductive nanofiller suspension, the dynamic crosslinking agent, the conductive monomer, and the initiator is (10 - 20):(0.1 - 0.5):(0.4 - 2.0):(0.01 - 0.05) mL / g / g / g; the mass concentration of the highly conductive nanofiller suspension is 0.05 - 0.15 mg / mL.

3. The preparation method of the conductive polymer precursor solution with encapsulation and reversible removal functions according to claim 1 or 2, wherein, The steps for preparing the highly conductive nanofiller suspension include: mixing the highly conductive nanofiller, a solvent, and an optional surfactant to obtain a mixture; subjecting the mixture to ultrasonic treatment to obtain the highly conductive nanofiller suspension; Preferably, the solvent is deionized water and / or ethanol.

4. The preparation method of the conductive polymer precursor solution with encapsulation and reversible removal functions according to claim 1, wherein, The reaction temperature of the in-situ polymerization reaction is 50 - 80 °C, and the reaction time is 30 - 120 min.

5. A conductive polymer precursor solution prepared by the method for preparing a conductive polymer precursor solution with encapsulation and reversible removal functions according to any one of claims 1 - 4.

6. Application of the conductive polymer precursor solution according to claim 5 as a functional material for encapsulating microbial cells.

7. The application according to claim 6, wherein The encapsulation method includes: first introducing the conductive polymer precursor solution into a microfluidic device; then introducing a microbial cell suspension into the microfluidic device to be uniformly mixed with the conductive polymer precursor solution, and completing encapsulation in a flowing state to obtain an encapsulated product; performing curing and drying treatments on the encapsulated product to obtain a conductive polymer film encapsulating microbial cells; Preferably, the conditions of the encapsulation method include: the encapsulation temperature is 40 - 60 °C, the encapsulation time is 30 - 90 min, the flow rate of the microbial cell suspension is 0.5 - 1 mL / min, and the total flow rate of the microbial cell suspension is 10 - 40 mL; optionally, it also includes the pH value of the encapsulation system, and / or, an anaerobic environment.

8. According to the application of claim 7, wherein, The microbial cells are photosynthetic bacteria and / or enzyme-producing bacteria; The concentration of the microbial cell suspension is 1×10 7 -1×10 9 cells / mL; The volume ratio of the conductive polymer precursor solution to the microbial cell suspension is 1:(1 - 2); The curing temperature is 55 - 65 °C, and the time is 1 - 2.5 h; The drying temperature is 60 - 80 °C, and the time is 4 - 12 h.

9. The application according to claim 7, wherein, The application further includes: removing the microbial cells encapsulated in the thin film by de-crosslinking the dynamic crosslinking network, and re-crosslinking the non-crosslinked system obtained by de-crosslinking to obtain a recombinant conductive polymer precursor solution and re-encapsulating new microbial cells according to the encapsulation method.

10. The application according to claim 9, wherein The conditions for realizing the de-crosslinking of the dynamic crosslinking network include: setting the de-crosslinking temperature and the de-crosslinking time, and optionally further including setting the pH value of the de-crosslinking and / or setting the light; preferably, the de-crosslinking temperature is 80-100 °C, and the de-crosslinking time is 10-30 min; The conditions for realizing the re-crosslinking of the network include: setting the re-crosslinking temperature and the re-crosslinking time, and optionally further including setting the pH value of the re-crosslinking and / or setting the light; preferably, the re-crosslinking temperature is 20-50 °C, and the re-crosslinking time is 30-60 min; The de-crosslinking of the dynamic crosslinking network and the re-crosslinking of the network are cycled multiple times, preferably 1-3 times.

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