Polymer, sensor, and detection apparatus

Abstract

The present application provides a polymer, a sensor, and a detection apparatus. The polymer comprises a backbone and a plurality of branches. The plurality of branches may each comprise a transition metal atom and can be connected to the backbone via a polar group. The polymer has a high affinity and good biocompatibility with the human body. The polymer has a relatively high content of transition metal atoms, which is beneficial for improving the reaction rate of the redox reaction. In addition, the lengths of the plurality of branches of the polymer can be designed according to the specific application, and the electron migration rate and oxygen competition coefficient during the redox reaction of the polymer can be improved to a certain extent. The sensor and the detection apparatus that use the polymer can more accurately and reliably measure physiological data such as blood glucose.

Description

Polymers, sensors and detection devices

[0001] This application claims priority to Chinese Patent Application No. 202510237580.4, filed on February 28, 2025, entitled "Polymer, Sensor and Detection Device", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of materials, and more specifically, to a polymer, a sensor, and a detection device. Background Technology

[0003] Biocompatibility and detection accuracy are key factors in evaluating the quality of biosensors. For biosensors that need to be worn for extended periods (such as those used for continuous glucose monitoring), insufficient biocompatibility can trigger the host's immune system to recognize foreign objects and initiate an inflammatory response, leading to foreign body reactions. These reactions can hinder the exchange of substances between the biosensor and surrounding tissues, reduce signal transmission efficiency, and even shorten the sensor's lifespan.

[0004] Electrochemically based biosensors typically use redox mediators (or electronic intermediates) to transfer electrons between human tissue and the sensor's electrodes. Improving the biocompatibility of these redox mediators is a worthwhile consideration. Summary of the Invention

[0005] This application provides a polymer, a sensor, and a detection device. The polymer includes a main chain and multiple branches. The multiple branches can be connected to the main chain through polar groups, such as amide groups. The polymer has high affinity and good biocompatibility with the human body. Sensors and continuous glucose monitoring systems using this polymer as a redox medium have high detection accuracy and long service life.

[0006] In a first aspect, a polymer is provided, comprising: a main chain, a first branch chain, and a second branch chain, the first branch chain comprising a first functional group and a second functional group, the second functional group being connected between the main chain and the first functional group, and the end of the first branch chain away from the main chain being coordinated with a transition metal atom Ma; the second branch chain comprising a third functional group and a fourth functional group, the fourth functional group being connected between the main chain and the third functional group; wherein the first functional group and the third functional group are both aromatic nitrogen-containing groups, and the second functional group and the fourth functional group are both polar groups.

[0007] Here, coordination of one end of the first branch with the transition metal atom Ma can include the connection of a group at one end of the first branch with a complex of the transition metal atom Ma.

[0008] It is understandable that there can be multiple first chains and multiple second chains.

[0009] In conjunction with the first aspect, in certain implementations of the first aspect, the first functional group and the third functional group include at least one of the following: a pyridine group, an imidazole group, a pyrrole group, an indole group, a purine group, a pyrimidine group, a quinoline group, an isoquinoline group, a pyridazine group, or a pyrazine group; and / or, the second functional group and the fourth functional group include at least one of the following: an amide group, an imino group, an ester group, an ether group, or a carbonyl group.

[0010] In conjunction with the first aspect, in some implementations of the first aspect, the first functional group is a first pyridine group, the third functional group is a second pyridine group; and / or, the second functional group is a first amide group, the fourth functional group is a second amide group.

[0011] In conjunction with the first aspect, in certain implementations of the first aspect, the first branch and / or the second branch include at least one of the following functional groups:

[0012] Unlike nonpolar groups such as hydrocarbon groups, amide groups are polar groups, resulting in better biocompatibility and affinity with the human body. Amide groups are common functional groups in biomolecules; polymers containing amide groups have structures similar to biomolecules, enabling them to interact with biological tissues and cells, reducing toxicity and rejection reactions. The nitrogen and oxygen atoms in the amide group can form hydrogen bonds with water molecules, giving it excellent hydrophilicity. This allows polymers containing amide groups to have good solubility in water, making them easier to disperse and transport within the human body, thereby enhancing contact and interaction with human tissues or cells.

[0013] Transition metal atoms generally possess multiple valence states; high-valence transition metal atoms exhibit oxidizing properties, while low-valence transition metal atoms exhibit reducing properties. During redox reactions, the interconversion between these two valence states allows for the transfer of electrons between different reactants and at different sites on the reactants.

[0014] The first and second branches can be connected to the main chain through different functional groups, and the first and second branches can originate from different monomers. In other words, multiple different types of monomers can be used to synthesize the polymer provided in the embodiments of this application. This polymer has a wider variety of raw materials and a broader range of corresponding synthetic routes, which helps to reduce the synthesis difficulty of the polymer and improve the production efficiency of the polymer.

[0015] From another perspective, the above-mentioned polymer can be synthesized from a variety of different types of monomers. The physicochemical properties of different monomers may differ. The physicochemical properties of the polymer are related to the functional groups contained in the polymer. In other words, the physicochemical properties of the polymer provided in the embodiments of this application can be designed by changing the types of reactants in the polymerization reaction. In different application scenarios, the polymer can be synthesized from different monomers, which is beneficial to improving the applicability of the polymer in different application scenarios.

[0016] In conjunction with the first aspect, in some implementations of the first aspect, the second branch is coordinated with the transition metal atom Mb at an end away from the main chain.

[0017] Here, the coordination of one end of the second branch with the transition metal atom Mb can include the connection of a group at one end of the first branch with the transition metal atom Mb.

[0018] When the second branch includes a transition metal atom Mb, it can also participate in the redox reaction. This means that both transition metal atoms Ma and Mb can participate in the redox reaction, which can improve the chemical reaction efficiency of the polymer to some extent. During the chemical reaction, multiple branches within the polymer can transfer electrons. The probability of electron transfer pathways on a particular branch being blocked during the reaction is lower, meaning the polymer has a higher electron transfer efficiency during the reaction.

[0019] In conjunction with the first aspect, in some implementations of the first aspect, the ratio p of the molar amount of the transition metal atom contained in the polymer to the molar amount of the pyridine group contained in the polymer satisfies: p ≥ 0.3.

[0020] For example, p can take values ​​such as 0.5, 0.6, 0.9, 1.0, etc.

[0021] Within a certain range, the higher the content of transition metal atoms, the higher the electron transfer efficiency of the polymer during the chemical reaction process, and the higher the efficiency of the chemical reaction. Within this range, increasing the value of p is beneficial to improving the chemical reaction efficiency of the polymer. When the content of transition metal atoms exceeds the aforementioned range, the competition between transition metal atoms intensifies, which to some extent hinders electron transfer during the reaction process.

[0022] In conjunction with the first aspect, in some implementations of the first aspect, the length of the second branch is different from the length of the first branch.

[0023] In conjunction with the first aspect, in some implementations of the first aspect, the first branch and the second branch are distributed at intervals.

[0024] During redox reactions, electrons are transferred between different branches through collisions. In this case, the length of the branch affects the efficiency of electron transfer. In some cases, the longer the branch segment, the greater the range of motion of the branch, and the higher the corresponding electron transfer efficiency. In other cases, longer branches may become entangled during collisions, which can actually reduce the electron transfer efficiency.

[0025] In this technical solution, first and second branches of different chain lengths are distributed alternately, and the spacing between two first branches (or two second branches) is increased, reducing the probability of entanglement between the first branches. This can improve electron transfer efficiency and improve the efficiency of polymer chemical reaction to a certain extent.

[0026] In conjunction with the first aspect, in some implementations of the first aspect, the first branch further includes a third amide group, the second branch includes a fourth amide group, one end of the third amide group is connected to the pyridine nitrogen of the first branch, and the other end is connected to the complex of the transition metal atom Ma; one end of the fourth amide group is connected to the pyridine nitrogen of the second branch, and the other end is connected to the complex of the transition metal atom Mb.

[0027] In conjunction with the first aspect, in some implementations of the first aspect, the first branch further includes a first hydrocarbon group connected between the third amide group and the pyridine nitrogen of the first branch, and the second branch further includes a second hydrocarbon group connected between the fourth amide group and the pyridine nitrogen of the second branch, wherein the chain length of the second hydrocarbon group is different from the chain length of the first hydrocarbon group.

[0028] In conjunction with the first aspect, in some implementations of the first aspect, the number J of carbon atoms contained in the first hydrocarbon group satisfies: 2≤J≤20, where J is an integer.

[0029] In conjunction with the first aspect, in some implementations of the first aspect, the second hydrocarbon group contains Q carbon atoms, the difference between J and Q is greater than or equal to 1, and Q is an integer.

[0030] The greater the difference between the number of carbon atoms in the first hydrocarbon group and the number of carbon atoms in the second branch, the greater the difference in chain length between the first and second branches. Correspondingly, the greater the difference in chain length between the monomers corresponding to the first and second branches, and the greater the difference in their space occupancy. In polymer synthesis, this difference facilitates the spaced arrangement of the first and second branches, thereby reducing the probability of branch entanglement and improving the efficiency of electron transfer during redox reactions.

[0031] In conjunction with the first aspect, in some implementations of the first aspect, the polymer further includes a third branch chain, the end of which is far from the main chain and coordinated with a transition metal atom Mc, the chain length of which is different from the chain length of the first branch chain and different from the chain length of the second branch chain, and the first branch chain, the second branch chain and the third branch chain are distributed alternately.

[0032] Understandably, there can be multiple third chains.

[0033] In conjunction with the first aspect, in some implementations of the first aspect, the first branch further includes a fifth functional group connected between the first functional group and the transition metal atom Ma, the fifth functional group including one or more of the following: -COC-, -CSC-, -CNC-.

[0034] Similarly, the second branch may also include one or more of the following: -COC-, -CSC-, -CNC-.

[0035] The first (or second) branch can also include more groups, which can be generated during the preparation of the monomer corresponding to the first branch. In other words, the first branch can be prepared by the reaction of various small molecule compounds. This can enrich the preparation methods of polymers, reduce the difficulty of polymer preparation, and improve the production efficiency of polymers to a certain extent.

[0036] In conjunction with the first aspect, in some implementations of the first aspect, the transition metal atom Ma is one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0037] Similarly, the transition metal atom Mb or Mc can be one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0038] In a second aspect, a polymer is provided, comprising: a main chain, a first branch and a second branch, wherein the first branch includes a first functional group, and the end of the first branch away from the main chain is coordinated with a transition metal atom Ma; the second branch includes a third functional group, and the end of the second branch away from the main chain is coordinated with a transition metal atom Mb; wherein the chain length of the first branch is different from the chain length of the second branch, and both the first functional group and the third functional group are aromatic nitrogen-containing groups.

[0039] Understandably, there are multiple first and second chains.

[0040] Transition metal atoms generally possess multiple valence states; high-valence transition metal atoms exhibit oxidizing properties, while low-valence transition metal atoms exhibit reducing properties. During redox reactions, the interconversion between these two valence states allows for the transfer of electrons between different reactants and at different sites on the reactants.

[0041] In conjunction with the second aspect, in some implementations of the second aspect, the first functional group and the third functional group include at least one of the following: a pyridine group, an imidazole group, a pyrrole group, an indole group, a purine group, a pyrimidine group, a quinoline group, an isoquinoline group, a pyridazine group, or a pyrazine group.

[0042] Here, coordination of one end of the first branch with the transition metal atom Ma can include the connection of a group at one end of the first branch with a complex of the transition metal atom Ma. Similarly, coordination of one end of the second branch with the transition metal atom Mb can include the connection of a group at one end of the first branch with a complex of the transition metal atom Mb.

[0043] When the second branch includes a transition metal atom Mb, it can also participate in the redox reaction. This means that both transition metal atoms Ma and Mb can participate in the redox reaction, which can improve the chemical reaction efficiency of the polymer to some extent. During the chemical reaction, multiple branches within the polymer can transfer electrons. The probability of electron transfer pathways on a particular branch being blocked during the reaction is lower, meaning the polymer has a higher electron transfer efficiency during the reaction.

[0044] During redox reactions, electrons are transferred between different branches through collisions. In this process, the length of the branch affects the efficiency of electron transfer. In some cases, the longer the branch segment, the greater the range of motion of the branch, and the higher the corresponding electron transfer efficiency. In other cases, longer branches may become entangled during collisions, which can actually reduce electron transfer efficiency.

[0045] In conjunction with the second aspect, in some implementations of the second aspect, the first branch further includes a second functional group connected between the main chain and the first functional group; the second branch further includes a fourth functional group connected between the main chain and the third functional group.

[0046] In conjunction with the second aspect, in some implementations of the second aspect, both the second functional group and the fourth functional group are polar groups.

[0047] In conjunction with the second aspect, in some implementations of the second aspect, the first functional group is a first pyridine group, the third functional group is a second pyridine group; and / or, the second functional group is a first amide group, the fourth functional group is a second amide group.

[0048] In conjunction with the second aspect, in some implementations of the second aspect, the first branch and the second branch are distributed at intervals.

[0049] In this technical solution, first and second branches of different chain lengths are distributed alternately, and the spacing between two first branches (or two second branches) is increased, reducing the probability of entanglement between the first branches. This can improve electron transfer efficiency and improve the efficiency of polymer chemical reaction to a certain extent.

[0050] In conjunction with the second aspect, in certain implementations of the second aspect, the first branch and / or the second branch includes at least one of the following functional groups:

[0051] Unlike nonpolar groups such as hydrocarbon groups, amide groups are polar groups, resulting in better biocompatibility and affinity with the human body. Amide groups are common functional groups in biomolecules; polymers containing amide groups have structures similar to biomolecules, enabling them to interact with biological tissues and cells, reducing toxicity and rejection reactions. The nitrogen and oxygen atoms in the amide group can form hydrogen bonds with water molecules, giving it excellent hydrophilicity. This allows polymers containing amide groups to have good solubility in water, making them easier to disperse and transport within the human body, thereby enhancing contact and interaction with human tissues or cells.

[0052] In conjunction with the second aspect, in some implementations of the second aspect, the ratio p of the molar amount of the transition metal atom contained in the polymer to the molar amount of the pyridine group contained in the polymer satisfies: p ≥ 0.3.

[0053] For example, p can take values ​​such as 0.5, 0.6, 0.9, 1.0, etc.

[0054] Within a certain range, the higher the content of transition metal atoms, the higher the electron transfer efficiency of the polymer during the chemical reaction process, and the higher the efficiency of the chemical reaction. Within this range, increasing the value of p is beneficial to improving the chemical reaction efficiency of the polymer. When the content of transition metal atoms exceeds the aforementioned range, the competition between transition metal atoms intensifies, which to some extent hinders electron transfer during the reaction process.

[0055] In conjunction with the second aspect, in some implementations of the second aspect, the first branch and the second branch are distributed at intervals.

[0056] During redox reactions, electrons are transferred between different branches through collisions. In this process, the length of the branch affects the efficiency of electron transfer. In some cases, the longer the branch segment, the greater the range of motion of the branch, and the higher the corresponding electron transfer efficiency. In other cases, longer branches may become entangled during collisions, which can actually reduce electron transfer efficiency.

[0057] In this technical solution, first and second branches of different chain lengths are distributed alternately, and the spacing between two first branches (or two second branches) is increased, reducing the probability of entanglement between the first branches. This can improve electron transfer efficiency and improve the efficiency of polymer chemical reaction to a certain extent.

[0058] In conjunction with the second aspect, in some implementations of the second aspect, the first branch further includes a third amide group, the second branch includes a fourth amide group, one end of the third amide group is connected to the pyridine nitrogen of the first branch, and the other end is connected to the complex of the transition metal atom Ma; one end of the fourth amide group is connected to the pyridine nitrogen of the second branch, and the other end is connected to the complex of the transition metal atom Mb.

[0059] In conjunction with the second aspect, in some implementations of the second aspect, the first branch further includes a first hydrocarbon group connected between the third amide group and the pyridine nitrogen of the first branch, and the second branch further includes a second hydrocarbon group connected between the fourth amide group and the pyridine nitrogen of the second branch, wherein the chain length of the second hydrocarbon group is different from the chain length of the first hydrocarbon group.

[0060] In conjunction with the second aspect, in some implementations of the second aspect, the number of carbon atoms J contained in the first hydrocarbon group satisfies: 2≤J≤20, where J is an integer.

[0061] In conjunction with the second aspect, in some implementations of the second aspect, the second hydrocarbon group contains Q carbon atoms, the difference between J and Q is greater than or equal to 1, and Q is an integer.

[0062] The greater the difference between the number of carbon atoms in the first hydrocarbon group and the number of carbon atoms in the second branch, the greater the difference in chain length between the first and second branches. Correspondingly, the greater the difference in chain length between the monomers corresponding to the first and second branches, and the greater the difference in their space occupancy. In polymer synthesis, this difference facilitates the spaced arrangement of the first and second branches, thereby reducing the probability of branch entanglement and improving the efficiency of electron transfer during redox reactions.

[0063] In conjunction with the second aspect, in some implementations of the second aspect, the polymer further includes a third branch chain, the end of which is coordinated with a transition metal atom Mc at a distance from the main chain, the chain length of the third branch chain being different from the chain length of the first branch chain, the chain length of the third branch chain being different from the chain length of the second branch chain, and the first branch chain, the second branch chain, and the third branch chain being distributed alternately.

[0064] In conjunction with the second aspect, in some implementations of the second aspect, the first branch further includes a fifth functional group connected between the first functional group and the transition metal atom Ma, the fifth functional group including one or more of the following: -COC-, -CSC-, -CNC-.

[0065] Similarly, the second branch may also include one or more of the following: -COC-, -CSC-, -CNC-.

[0066] The first (or second) branch can also include more groups, which can be generated during the preparation of the monomer corresponding to the first branch. In other words, the first branch can be prepared by the reaction of various small molecule compounds. This can enrich the preparation methods of monomers, reduce the difficulty of polymer preparation, and improve the production efficiency of polymers to a certain extent.

[0067] The above-mentioned polymers can be synthesized from various types of monomers. The physicochemical properties of different monomers may differ. The physicochemical properties of the polymer are related to the functional groups contained in the polymer. In other words, the physicochemical properties of the polymers provided in the embodiments of this application can be designed by changing the types of reactants in the polymerization reaction. In different application scenarios, the polymers can be synthesized from different monomers, which is beneficial to improving the applicability of the polymers in different application scenarios.

[0068] In conjunction with the second aspect, in some implementations of the second aspect, the transition metal atom Ma is one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0069] Similarly, the transition metal atom Mb or Mc can be one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0070] The branches of polymers can include more different groups, which can be generated during the preparation of monomers corresponding to the branches. This can enrich the preparation methods of polymers, reduce the difficulty of polymer preparation, and improve the production efficiency of polymers.

[0071] Thirdly, a sensor is provided, comprising a sensing layer, a diffusion control layer, and a biocompatible layer stacked together, the sensing layer comprising a polymer as described in the first aspect and any possible implementation thereof.

[0072] Fourthly, a detection device is provided, including a transmitter, a receiver, and a sensor in the second aspect and any possible implementation thereof.

[0073] Fifthly, a detection device is provided, including a processor and a sensor as described in the second aspect and any possible implementation thereof. Exemplarily, the detection device may be a wearable device.

[0074] In a sixth aspect, a method for synthesizing a polymer is provided, the method comprising: synthesizing a first monomer and a second monomer respectively; dissolving the first monomer and the second monomer in N,N-dimethylamide; adding an initiator to the reaction system and heating the reaction to obtain the polymer; wherein the first monomer comprises a first acrylamide pyridine group and a transition metal atom Ma, and the second monomer comprises a second acrylamide pyridine group.

[0075] In conjunction with the sixth aspect, in some implementations of the fifth aspect, the second monomer further includes a transition metal atom Mb, and the chain lengths of the first monomer and the second monomer are different.

[0076] In this technical solution, the polymer can be synthesized from a variety of monomers. Preparing the monomers before polymer synthesis facilitates effective control of the entire reaction process. During the experiment, reaction conditions can be optimized for both monomer synthesis and polymer synthesis reactions, improving the selectivity and yield of both reactions. After monomer synthesis, the reaction products can be separated and purified, which can reduce impurities introduced into the polymer synthesis system and lower the probability of byproduct formation. Attached Figure Description

[0077] Figures 1 to 6 are schematic diagrams of the detection results of the glucose sensor provided in the embodiments of this application under different oxygen concentrations.

[0078] Figure 7 is a schematic diagram of the detection principle of the glucose sensor provided in the embodiment of this application.

[0079] Figures 8 and 9 are schematic diagrams of the electron transfer process of the polymer provided in the embodiments of this application.

[0080] Figure 10 is a schematic diagram of the structure of a sensor provided in an embodiment of this application. Detailed Implementation

[0081] The embodiments of this application will now be described in conjunction with the accompanying drawings.

[0082] It should be noted that in this application, "-" indicates a numerical range, including two endpoint values. For example, "40%-60%" includes the two endpoint values ​​of 40% and 60%, as well as all values ​​between these two endpoint values.

[0083] This application provides a polymer that exhibits good biocompatibility, high electron transfer efficiency, and high chemical reaction efficiency, enabling its wide application in sensors (such as biosensors and chemical sensors), battery materials (such as positive and negative electrode materials), electronic devices (such as photoelectric conversion devices and electroluminescent devices), catalysts, and drug carriers. Furthermore, this biocompatible polymer also improves the biocompatibility and detection accuracy of biosensors using this polymer.

[0084] In some examples, the polymer may include a main chain, multiple first branches and multiple second branches, wherein the first branches may include a first functional group and a second functional group, and the second branches may include a third functional group and a fourth functional group; wherein the first and third functional groups are groups containing aromatic nitrogen, the second and fourth functional groups are polar groups, the second functional group is connected between the main chain and the first functional group, and the fourth functional group is connected between the main chain and the third functional group.

[0085] For example, the first or third functional group may include one or more of the following: pyridine group, imidazole group, pyrrole group, indole group, purine group, pyrimidine group, quinoline group, isoquinoline group, pyridazine group, or pyrazine group, etc.

[0086] For example, the second or fourth functional group may include one or more of the following: amide group, imino group, ester group, ether group, carbonyl group, etc.

[0087] As an example, the first branch may include a first pyridine group and a first amide group, and the second branch may include a second pyridine group and a second amide group; wherein the first amide group is connected between the main chain and the first pyridine group, and the second amide group is connected between the main chain and the second pyridine group.

[0088] As an example, the first branch may include a first imidazole group and a first ester group, and the second branch may include a second imidazole group and a second ester group; wherein the first ester group is connected between the main chain and the first imidazole group, and the second ester group is connected between the main chain and the second imidazole group.

[0089] In the following examples, the first functional group is a first pyridine group, the second functional group is a first amide group, the third functional group is a second pyridine group, and the fourth functional group is a second amide group. It is understood that these examples should not be construed as limiting the present application.

[0090] Unlike nonpolar groups such as hydrocarbon groups, polar groups, such as amide groups, have better biocompatibility and a better affinity with the human body. Amide groups are common functional groups in biomolecules. Polymers containing amide groups have structures similar to biomolecules, enabling them to interact with biological tissues and cells, reducing toxicity and rejection reactions.

[0091] The nitrogen and oxygen atoms in the amide group can form hydrogen bonds with water molecules, thus giving the amide group good hydrophilicity. This makes polymers containing amide groups have good solubility in water, making them easier to disperse and transport in the human body, thereby enhancing their contact and interaction with human tissues or cells.

[0092] For example, the end of the first branch furthest from the main chain is coordinated with the transition metal atom Ma.

[0093] As an example, the transition metal atom Ma can be one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron, etc.

[0094] Here, coordination of one end of the first branch with the transition metal atom Ma can include the connection of a group at one end of the first branch with a complex of the transition metal atom Ma.

[0095] A complex of a transition metal atom Ma can be a complex of one or more transition metal atoms Ma, or in other words, the complex can contain one or more transition metal atoms. A complex of a transition metal atom Ma can contain one type of transition metal atom, or it can contain multiple types of transition metal atoms.

[0096] The following examples illustrate the use of transition metal osmium and osmium complexes containing one osmium atom. It is understood that these examples should not be construed as limiting the scope of this application.

[0097] For example, complexes of transition metal atom Ma may include one or more of the following: hydrated complexes (using water molecules as ligands), halide complexes (using halide ions as ligands), ammonia complexes (using ammonia molecules as ligands), cyanide complexes (using CN... - As ligands), metal carbonyl compounds (using carbon monoxide as ligands), and chelate complexes.

[0098] Taking osmium atoms as an example, complexes of osmium atoms may include: osmium-pyridine complexes and / or osmium-imidazolium complexes.

[0099] Transition metal atoms Ma can have different valence states. For example, osmium atoms (Os) can have +2 and +3 valences, ruthenium atoms (Ru) can have +3 and +4 valences, vanadium atoms (V) can have +4 and +5 valences, cobalt atoms (Co) can have +2 and +3 valences, and iron atoms (Fe) can have +2 and +3 valences.

[0100] Taking osmium atoms as an example, divalent osmium ions possess reducing properties and can participate as reducing agents in redox reactions. After losing electrons, divalent osmium ions can be converted into trivalent osmium ions. Trivalent osmium ions possess oxidizing properties and can participate as oxidizing agents in redox reactions. After gaining electrons, trivalent osmium ions can be converted back into divalent osmium ions. During redox reactions, the interconversion between these two valence states of osmium ions enables the transfer of electrons between different reactants and between different sites on the reactants.

[0101] The first branch in the polymer is coordinated with the transition metal atom Ma, which enables the polymer to participate in redox reactions.

[0102] When the first branch contains a first amide group and a first pyridine group, the imino group of the first amide group may be attached to the first pyridine group, and the first amide group may be attached to the ortho, meta, or para position of the pyridine nitrogen in the first pyridine group. Similarly, the imino group of the second amide group on the second branch may be attached to the second pyridine group, and the second amide group may be attached to the ortho, meta, or para position of the pyridine nitrogen in the second pyridine group.

[0103] In other words, the first or second branch may include at least one of the following functional groups:

[0104] In some other examples, the amide group may be replaced by a thioamide group (-NH-CS-) or (-NH-CO-NH-). In this case, the first or second branch may include at least one of the following functional groups:

[0105] In the above examples, the imino group (-NH-) of the amide group in the first (or second) branch can be connected to a pyridine group, and the carbonyl group (-CO-) of the amide group can be connected to the main chain; or, the imino group of the thioamide group in the first (or second) branch can be connected to a pyridine group, and the carbonyl group (-CO-) of the thioamide group... The group can be attached to the main chain; or, the first branch (or the second branch) can be attached to the main chain. One end of the group is connected to a pyridine group, and the other end is connected to the main chain.

[0106] In some other examples, the imino group of the amide group in the first (or second) branch can be attached to the main chain, and the carbonyl group of the amide group can be attached to the pyridine group; or, the imino group of the thioamide group in the first (or second) branch can be attached to the main chain, and the carbonyl group of the thioamide group... The group can be linked to a pyridine group.

[0107] amide groups, thioamide groups and The group can be attached to the ortho, meta, or para position of the pyridine nitrogen on the pyridine group of the first branch; similarly, amide groups, thioamide groups, and The group can also be attached to the ortho, meta, or para position of the pyridine nitrogen on the pyridine group of the second branch. This application does not impose any limitation in this regard.

[0108] In the above example, the first and second branches can be connected to the main chain through different functional groups, and the first and second branches can originate from different monomers. In other words, multiple different types of monomers can be used to synthesize the polymer provided in this application embodiment. This polymer has a wider variety of raw materials and a broader range of corresponding synthetic routes, which helps to simplify the synthesis of the polymer and also helps to improve the production efficiency of the polymer.

[0109] From another perspective, the above-mentioned polymer can be synthesized from a variety of different types of monomers. The physicochemical properties of different monomers may differ. The physicochemical properties of the polymer are related to the functional groups contained in the polymer. In other words, the physicochemical properties of the polymer provided in the embodiments of this application can be designed by changing the types of reactants in the polymerization reaction. In different application scenarios, the polymer can be synthesized from different monomers, which is beneficial to improving the applicability of the polymer in different application scenarios.

[0110] In some examples, the end of the second branch furthest from the main chain can coordinate with the transition metal atom Mb.

[0111] Similar to the transition metal atom Ma, the transition metal atom Mb can be one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0112] As a result, the transition metal atom Ma and the transition metal atom Mb can be the same.

[0113] Here, the coordination of one end of the first branch with the transition metal atom Ma can include the connection of a group at one end of the first branch with a complex of the transition metal atom Mb.

[0114] For example, complexes of the transition metal atom Mb may include one or more of the following: hydrated complexes (using water molecules as ligands), halogenated complexes (using halide ions as ligands), ammonia complexes (using ammonia molecules as ligands), cyanide complexes (using CN... - As ligands), metal carbonyl compounds (using carbon monoxide as ligands), and chelate complexes.

[0115] When the second branch includes a transition metal atom Mb, it can also participate in the redox reaction. This means that both transition metal atoms Ma and Mb can participate in the redox reaction, which can improve the chemical reaction efficiency of the polymer to some extent. During the chemical reaction, multiple branches within the polymer can transfer electrons. The probability of electron transfer pathways on a particular branch being blocked during the reaction is lower, meaning the polymer has a higher electron transfer efficiency during the reaction.

[0116] In some examples, the ratio p of the molar amount of transition metal atoms contained in the polymer to the molar amount of pyridine groups contained in the polymer satisfies: p ≥ 0.3.

[0117] For example, p can take values ​​such as 0.5, 0.6, 0.9, 1.0, etc.

[0118] In practice, each of the multiple transition metal atoms in the polymer is coordinated with a branch chain, in which case the value of p can be 1.

[0119] As a result, the polymer consists of a main chain, multiple first branches and multiple second branches, and the multiple transition metal atoms contained in the polymer are coordinated only with the first branches. In this case, the value of p can be determined based on the number of transition metal atoms contained in the complex of the transition metal atoms on the first branch, the molar amount of the first branch and the molar amount of the second branch.

[0120] When the complex containing one transition metal atom in the first branch contains one transition metal atom, p is the ratio of the molar amount of the first branch (n1) to the sum of the molar amounts of the first and second branches (n2) in the polymer. When the complex containing N transition metal atoms in the first branch (N is an integer greater than or equal to 2), p is the ratio of the product of the molar amount of the first branch (n1) and N to the sum of the molar amounts of the first and second branches (n2). It is understandable that, in the latter case, the value of p can be greater than 1.

[0121] The value of p can roughly represent the relative content of transition metal atoms in the polymer: the larger the value of p, the higher the relative content of transition metal atoms in the polymer. Increasing the value of p is beneficial to improving the chemical reaction efficiency of the polymer to a certain extent.

[0122] Within a certain range, the higher the content of transition metal atoms, the higher the electron transfer efficiency of the polymer during the chemical reaction process, and the higher the efficiency of the chemical reaction. Within this range, increasing the value of p is beneficial to improving the chemical reaction efficiency of the polymer. When the content of transition metal atoms exceeds the aforementioned range, the competition between transition metal atoms intensifies, which to some extent hinders electron transfer during the reaction process.

[0123] In order to ensure that the content of transition metal atoms in the polymer is conducive to increasing the rate of chemical reaction, the value of p can also satisfy: 0.3≤p≤C, where C is greater than 0.3. For example, C can be 0.5, 0.7, 0.9, 1.0, etc.

[0124] In some examples, the length of the second branch may be different from that of the first branch, and the first and second branches may be distributed alternately.

[0125] In other words, branches of different chain lengths on a polymer can be arranged alternately, or branches of the same chain length are not adjacent.

[0126] Here's a brief explanation of chain length. The chain length of organic compounds typically refers to the length of the carbon skeleton within the molecule, commonly used to describe hydrocarbons and their derivatives. The carbon atoms forming the skeleton can be linked together by covalent bonds to form a chain, which can be straight, branched, or cyclic.

[0127] The length of the first branch or the length of the second branch can refer to the number of carbon atoms contained in the backbone of the first branch and the number of carbon atoms contained in the backbone of the second branch, respectively.

[0128] During redox reactions, electrons are transferred between different branches through collisions. In this process, the length of the branch affects the efficiency of electron transfer. In some cases, the longer the branch segment, the greater the range of motion of the branch, and the higher the corresponding electron transfer efficiency. In other cases, longer branches may become entangled during collisions, which can actually reduce electron transfer efficiency.

[0129] In this technical solution, first and second branches of different chain lengths are distributed alternately, and the spacing between two first branches (or two second branches) is increased, reducing the probability of entanglement between the first branches. This can improve electron transfer efficiency and improve the efficiency of polymer chemical reaction to a certain extent.

[0130] In one possible implementation, the first branch further includes a third amide group, one end of which is connected to the pyridine nitrogen of the first branch and the other end of which can be coordinated with the transition metal atom Ma.

[0131] Here, the pyridine nitrogen in the first branch can refer to the nitrogen atom on the pyridine ring of the first branch.

[0132] In some examples, the third amide group can be connected to the pyridine nitrogen of the first branch via a first bridging group.

[0133] For example, the first bridging group may include one or more of the following: hydrocarbon group, -CO-, -CS-, -CN-, etc. The carbon atom of the first bridging group may be connected to the pyridine nitrogen of the first branch, and the oxygen atom (or sulfur atom, nitrogen atom) of the first bridging group may be connected to the third amide group.

[0134] In other words, in addition to the third amide group, the first branch may also include one or more of the following: hydrocarbon group, -COC-, -CSC-, -CNC-, etc.

[0135] When the first bridging group includes a hydrocarbon group, the number of carbon atoms in the first bridging group can be greater than or equal to 2.

[0136] When the first bridging group does not include a hydrocarbon group, or when the first bridging group includes any one of -CO-, -CS-, -CN-, etc., the number of carbon atoms in the first bridging group can be greater than or equal to 1.

[0137] When the first bridging group includes both a hydrocarbon group and one or more of -CO-, -CS-, -CN-, etc., the number of carbon atoms in the first bridging group can be greater than or equal to 2.

[0138] As one implementation, the first bridging group includes only hydrocarbon groups, so the chemical formula of the first branch can be any of the following:

[0139] In the above formula, This can serve as an example of a first bridging group.

[0140] As another implementation, the first bridging group includes only one of -CO-, -CS-, -CN-, etc., so that the chemical formula of the first branch can be any of the following:

[0141] In the above formula, This can serve as another example of a first bridging group.

[0142] In one possible implementation, the second branch also includes a fourth amide group, one end of which is connected to the pyridine nitrogen of the second branch, and the other end of which can be coordinated with the transition metal atom Mb.

[0143] Here, the pyridine nitrogen in the second branch can refer to the nitrogen atom on the pyridine ring of the second branch.

[0144] Similar to the first branch, in some examples, the fourth amide group can be connected to the pyridine nitrogen of the second branch via a second bridging group.

[0145] For example, the second bridging group may include one or more of the following: hydrocarbon group, -CO-, -CS-, -CN-, etc. The carbon atom of the second bridging group may be connected to the pyridine nitrogen of the second branch, and the oxygen atom (or sulfur atom, nitrogen atom) of the second bridging group may be connected to the fourth amide group.

[0146] In other words, in addition to the fourth amide group, the second branch may also include one or more of the following: hydrocarbon group, -COC-, -CSC-, -CNC-, etc.

[0147] When the second bridging group includes a hydrocarbon group, the number of carbon atoms in the second bridging group can be greater than or equal to 2.

[0148] When the second bridging group does not include a hydrocarbon group, or when the second bridging group includes any one of -CO-, -CS-, -CN-, etc., the number of carbon atoms in the second bridging group can be greater than or equal to 1.

[0149] When the second bridging group includes both a hydrocarbon group and one or more of -CO-, -CS-, -CN-, etc., the number of carbon atoms in the second bridging group can be greater than or equal to 2.

[0150] As one implementation, the second bridging group includes only hydrocarbon groups, so the chemical formula of the second branch can be any of the following:

[0151] In the above formula, This can serve as an example of a second bridging group.

[0152] As another implementation, the second bridging group includes only one of -CO-, -CS-, -CN-, etc., so the chemical formula of the second branch can be any of the following:

[0153] In the above formula, This can serve as another example of a second bridging group.

[0154] The first (or second) branch can also include more groups, which can be generated during the preparation of the monomer corresponding to the first branch. In other words, the first branch can be prepared by the reaction of various small molecule compounds. This can enrich the preparation methods of polymers, reduce the difficulty of polymer preparation, and improve the production efficiency of polymers to a certain extent.

[0155] In some examples, the first bridging group is a first hydrocarbon group, which is attached between the third amide group and the pyridine nitrogen of the first branch. The chain length of the first hydrocarbon group can be J, or in other words, the first hydrocarbon group contains J carbon atoms, where J is an integer.

[0156] For example, J can satisfy: 2≤J≤20, where J is an integer. For instance, J can be 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, etc.

[0157] Similarly, the second bridging group mentioned above is a second hydrocarbon group, which can be attached between the fourth amide group and the pyridine nitrogen of the second branch. The chain length of the second hydrocarbon group can be Q, or in other words, the second hydrocarbon group contains Q carbon atoms, where Q is an integer.

[0158] For example, Q can satisfy: 2≤Q≤20, where Q is an integer. For instance, Q can be 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, etc.

[0159] In some examples, the chain length of the second hydrocarbon group is different from that of the first hydrocarbon group. That is, J is not equal to Q.

[0160] For example, the difference between J and Q can be greater than or equal to 1, i.e., JQ≥1.

[0161] For example, J = 4, Q = 3; J = 6, Q = 4; J = 12, Q = 6; J = 16, Q = 10; J = 20, Q = 12.

[0162] The greater the difference between the number of carbon atoms in the first hydrocarbon group and the number of carbon atoms in the second branch, the greater the difference in chain length between the first and second branches. Correspondingly, the greater the difference in chain length between the monomers corresponding to the first and second branches, and the greater the difference in their space occupancy. In polymer synthesis, this difference facilitates the spaced arrangement of the first and second branches, thereby reducing the probability of branch entanglement and improving the efficiency of electron transfer during redox reactions.

[0163] In some examples, the polymer may also include multiple third branches, one end of which is coordinated with a transition metal atom Mc at a distance from the main chain. The length of the third branch may be different from that of the first branch, and the length of the third branch may be different from that of the second branch. The first, second, and third branches are distributed alternately.

[0164] For example, the transition metal atom Mc can be one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0165] For example, the third branch may have a similar structure to the aforementioned first or second branch.

[0166] As an example, the third branch may include a third pyridine group, a fifth amide group, a third hydrocarbon group, and a sixth amide group. The fifth amide group is connected between the main chain and the third pyridine group. One end of the third hydrocarbon group is connected to the pyridine nitrogen of the third pyridine group, and the other end is connected to one end of the sixth amide group. The end of the sixth amide group away from the third hydrocarbon group is coordinated with the aforementioned transition metal atom Mc.

[0167] The third hydrocarbon group mentioned above can contain Nc carbon atoms, where Nc satisfies the following condition: 2 ≤ Nc ≤ 20, and Nc is an integer. For example, Nc can be 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, etc.

[0168] In some scenarios, the chain lengths of the first, second, and third hydrocarbon groups can represent the chain lengths of the first, second, and third branches, respectively. The relationship between these three branch lengths can be reflected by the chain lengths of the three hydrocarbon groups. In other words, the statement that the chain length of the first branch is greater than the chain length of the second branch can be expressed as the statement that the chain length of the first hydrocarbon group is greater than the chain length of the second hydrocarbon group, and the statement that the chain length of the second branch is greater than the chain length of the third branch can be expressed as the statement that the chain length of the second hydrocarbon group is greater than the chain length of the third hydrocarbon group. That is, the chain lengths J of the first hydrocarbon group, Q of the second hydrocarbon group, and Nc of the third hydrocarbon group can satisfy the following relationship: Nc < Q < J.

[0169] For example, J = 16, Q = 10, Nc = 6; or, J = 20, Q = 12, Nc = 4; or, J = 20, Q = 10, Nc = 6.

[0170] In some examples, the polymer may also include more branches of different chain lengths. For example, the polymer may also include a fourth branch, which may be shorter than the aforementioned third branch.

[0171] For a description of the structure of the fourth branch, please refer to the introductions of the first, second, and third branches mentioned earlier.

[0172] Polymers can also include more branches of different chain lengths, and different branches can be arranged alternately. In this case, branches of the same chain length are more widely spaced on the main chain, the probability of branches entangled with each other is lower, the efficiency of electron transfer in the redox reaction is higher, and the reaction efficiency is higher.

[0173] In some examples, the first, second, and third branches of the polymer may also include one or more of the following functional groups: -COC-, -CSC-, and -CNC-. These functional groups can be attached between the pyridine group and the transition metal atom complex on the branch. In other words, the aforementioned first and second bridging groups may include hydrocarbon groups, as well as at least one of -CO-, -CS-, and -CN-.

[0174] Thus, by way of example, the first branch, the second branch, or the third branch described above can be any of the following:

[0175] In the above formula, M represents a transition metal atom, such as one or more of osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

[0176] The branches of polymers can include more different groups, which can be generated during the preparation of monomers corresponding to the branches. This can enrich the preparation methods of monomers, reduce the difficulty of polymer preparation, and improve the production efficiency of polymers.

[0177] Based on the above description of polymer branching, as an example, the polymer may include at least one of the following:

[0178] In the above formula, Ta and Tb can be used to represent groups in which the polymer's branches are connected to transition metal atoms, such as the amide groups mentioned earlier; M, Ma, and Mb can be used to represent transition metal atoms; x, y, and z can be used to represent the number of branches in the polymer. The polymer can include branches connected to complexes of transition metal atoms, or it can include branches not connected to complexes of transition metal atoms. That is, in the above polymer chemical formula, Tc can represent a group containing a complex of transition metal atoms, or it can represent a group not containing a transition metal atom.

[0179] It is understood that the chemical formulas of the polymers described above are merely exemplary, and the polymers provided in the embodiments of this application are not limited thereto.

[0180] The polymer provided in this application embodiment may include a main chain and multiple branches, each of which may include transition metal atoms, and these branches may be connected to the main chain via amide groups. This polymer exhibits high affinity and good biocompatibility with the human body. The high content of transition metal atoms in this polymer is beneficial for increasing the reaction rate of redox reactions. Furthermore, the lengths of the polymer's multiple branches can be designed according to application requirements, which can, to some extent, improve the electron migration rate and oxygen competition coefficient during the redox reaction process.

[0181] The structure of the polymer provided in the embodiments of this application has been described above. The synthesis method of the polymer is described below. It should be understood that the synthesis methods provided in the following examples are only examples of methods for synthesizing the polymer provided in the embodiments of this application and should not be construed as limiting this application.

[0182] The method for synthesizing the polymer provided in this application embodiment can generally include two stages: a first stage of synthesizing monomers (hereinafter referred to as monomer synthesis stage), and a second stage of synthesizing the polymer using multiple monomers (hereinafter referred to as polymer synthesis stage). The two stages will be described separately below.

[0183] Preparing monomers before polymer synthesis allows for effective control of the entire reaction process. During experiments, reaction conditions can be optimized for both monomer and polymer synthesis, improving the selectivity and yield of both reactions. After monomer synthesis, the reaction products can be separated and purified, which can reduce impurities introduced into the polymer synthesis system and decrease the probability of byproduct formation.

[0184] Furthermore, as mentioned above, the polymers provided in this application can have various different types of molecular structures. Based on the two-stage synthesis method, the monomers required for the polymer synthesis reaction can be determined according to the polymer's properties and molecular structure, thereby designing the monomer synthesis reaction. This can improve the overall efficiency of the polymer synthesis reaction to a certain extent.

[0185] 1. Monomer synthesis stage

[0186] S101, 10 mmol of 4-aminopyridine and 11 mmol of triethylamine were dissolved in 500 mL of dichloromethane, followed by the addition of 11 mmol of acryloyl chloride. After reacting for 12 h, the filtrate was obtained by filtration and purified by column chromatography to obtain the product acrylamide pyridine (AA-Py).

[0187] S102, 5 mmol of acrylamide pyridine obtained in step S101 was added to 100 mL of N,N-dimethylformamide, 5.5 mol of bromoalkyl acid was added, and after reacting for 12 h, the solvent was removed by rotary evaporation, and the product carboxyalkylacrylamidopyridine was purified by column chromatography.

[0188] In step S103, 3 mol of carboxyalkylacrylamidopyridine obtained in step S102 was dissolved in 100 mL of N,N-dimethylformamide. 3.3 mol of N,N,N′,N′-tetramethyl-O-(N-succinimidyl)urea tetrafluoroborate was added for activation for 1 h. Subsequently, 6 mol of N,N-diisopropylethylamine was added for activation for 12 h. Then, 3.3 mol of a complex of N,N′-dimethyl-2,2′-biimidazole containing an amino functional group and osmium (the complex in the following formula is an example) was added. After reacting for 24 h, the solvent was removed by rotary evaporation, and the monomer product was purified by column chromatography. In the formula, n can be used to represent the number of -CH2- atoms. In the following reaction equations, [Os] is used to represent the coordination compound of the osmium atom, and this representation is used in the following examples.

[0189] Specifically, when the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are bromobutyric acid and carboxybutylacrylamidopyridine, respectively, the following monomer 1 (AA-4C) is obtained:

[0190] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are bromohexanoic acid and carboxyhexylacrylamidopyridine respectively, monomer 2 (AA-6C) is obtained:

[0191] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are bromodecanoic acid and carboxydecylacrylamidopyridine respectively, monomer 3 (AA-10C) is obtained:

[0192] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are bromododecanoic acid and carboxydodecylacrylamidopyridine, respectively, monomer 4 (AA-12C) is obtained:

[0193] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are bromohexadecanoic acid and carboxyhexadecylacrylamidopyridine, respectively, monomer 5 (AA-16C) is obtained:

[0194] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are bromoeicosanoic acid and carboxyeicosanoacrylamidopyridine, respectively, monomer 6 (AA-20C) is obtained:

[0195] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are 3-(2-bromoethoxy)propionic acid and carboxyethoxyethylacrylamidopyridine, respectively, monomer 7 (AA-1EO) is obtained:

[0196] When the bromoalkyl acid in step S102 and the carboxyalkylacrylamidopyridine in step S103 are 3-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)propionic acid and carboxytriethoxyethylacrylamidopyridine, respectively, monomer 8 (AA-3EO) is obtained:

[0197] Other monomers can also be prepared using the methods described above, such as monomers containing -CSC- groups, monomers containing -CNC- groups, etc., which will not be elaborated here.

[0198] For monomers containing thioamide groups, they can be prepared by reacting thiocyanates with primary amines; for monomers containing... The monomer of the group can be prepared by reacting a compound containing an isocyanate group with an amino group. Further details are omitted here.

[0199] 2. Polymer Synthesis Stage

[0200] Polymers containing different types of branches can be synthesized according to the reactant ratios in Table 1 below. The monomers of the synthesized polymers have different chain lengths. During the reaction process of synthesizing the polymer, the branches already attached to the main chain have a steric hindrance effect, which can affect the connection position of other groups subsequently attached to the main chain, so that branches of different chain lengths on the main chain can be distributed at intervals, increasing the distance between branches of the same chain length and reducing the proportion of entanglement between branches.

[0201] Table 1

[0202] The specific experimental plan is as follows:

[0203] Example 1

[0204] 7g of acrylamide pyridine, 1g of monomers AA-6C, 1g of monomers AA-10C, and 1g of monomers AA-16C were dissolved in 100mL of N,N-dimethylformamide. 0.01g of azobisisobutyronitrile initiator was added. After three vacuum-nitrogen cycles, the tube was sealed and reacted at 70℃ for 24h. The product was precipitated in ethyl acetate. The crude product was collected, dissolved in about 100mL of methanol, and precipitated again in ethyl acetate to obtain polymer P1 as shown below. In the following formula, x, y, m, and n can be used to represent the number of corresponding branches in polymer P1.

[0205] Example 2

[0206] 6g of acrylamide pyridine, 1g of monomers AA-4C, 1g of monomers AA-6C, 1g of monomers AA-12C, and 1g of monomers AA-20 were dissolved in 100mL of N,N-dimethylformamide. 0.01g of azobisisobutyronitrile initiator was added. After three vacuum-nitrogen circulation cycles, the tube was sealed and reacted at 70℃ for 24h. The product was precipitated in ethyl acetate. The crude product was collected, dissolved in about 100mL of methanol, and precipitated again in ethyl acetate to obtain polymer P2. In the following formula, x, y, z, m, and n can be used to represent the number of corresponding branches in polymer P2.

[0207] Example 3

[0208] 5g of acrylamide pyridine, 1g of monomers AA-4C, 1g of monomers AA-6C, 1g of monomers AA-10C, 1g of monomers AA-12C, and 1g of monomers AA-20C were dissolved in 100mL of N,N-dimethylformamide. 0.01g of azobisisobutyronitrile initiator was added. After three vacuum-nitrogen circulation cycles, the tube was sealed and reacted at 70℃ for 24h. The product was precipitated in ethyl acetate. The crude product was collected, dissolved in about 100mL of methanol, and precipitated again in ethyl acetate to obtain polymer P3. In the following formula, x, y, z, r, m, and n can be used to represent the number of corresponding branches in polymer P3.

[0209] Example 4

[0210] 8g of acrylamide pyridine, 1g of monomer AA-1EO, and 1g of monomer AA-3EO were dissolved in 100mL of N,N-dimethylformamide. 0.01g of azobisisobutyronitrile initiator was added. After three vacuum-nitrogen circulation cycles, the tube was sealed and reacted at 70℃ for 24h. The product was precipitated in ethyl acetate. The crude product was collected, dissolved in about 100mL of methanol, and precipitated again in ethyl acetate to obtain polymer P4. In the following formula, x, y, and z can be used to represent the number of corresponding branches in polymer P4.

[0211] Example 5

[0212] 6g of acrylamide pyridine, 1g of monomers AA-6C, 1g of monomers AA-12C, 1g of monomers AA-1EO, and 1g of monomers AA-3EO were dissolved in 100mL of N,N-dimethylformamide. 0.01g of azobisisobutyronitrile initiator was added. After three vacuum-nitrogen circulation cycles, the tube was sealed and reacted at 70℃ for 24h. The product was precipitated in ethyl acetate. The crude product was collected, dissolved in about 100mL of methanol, and precipitated again in ethyl acetate to obtain polymer P5. In the following formula, x, y, z, m, and n can be used to represent the number of corresponding branches in polymer P5.

[0213] Example 6

[0214] 5g of acrylamide pyridine and 5g of mono-AA-10C were dissolved in 100mL of N,N-dimethylformamide, and 0.01g of azobisisobutyronitrile initiator was added. After three vacuum-nitrogen circulation cycles, the tube was sealed and reacted at 70℃ for 24h. The product was precipitated in ethyl acetate, the crude product was collected, dissolved in about 100mL of methanol, and precipitated again in ethyl acetate to obtain polymer P6 as shown below. In the following formula, x and y can be used to represent the number of corresponding branches in polymer P6.

[0215] It should be noted that the chemical formula of the polymer described above is only used to represent the polymer and should not be construed as a limitation on the spatial structure of the polymer. Specifically, the branches of different chain lengths of the polymer can be arranged in various different ways, and this application does not impose any restrictions on this.

[0216] The following results were obtained from the analysis of the above redox polymers P1 to P6 using Fourier transform infrared spectroscopy:

[0217] At wavelengths of 1280-1340cm -1 A characteristic peak FP1 was detected nearby. This peak reflects the stretching vibration of the CN bond in the polymer. FP1 can reflect either the amide group attached to the pyridine ring or the amide group coordinated to the transition metal atom. One possibility is that the vibrational characteristics of the CN bond attached to the pyridine ring may be affected by the pyridine ring, causing a shift in the characteristic peak of the CN bond's stretching vibration. In other words, the aforementioned characteristic peak FP1 may slightly deviate from the wavelength of 1280-1340 cm⁻¹. -1 The range.

[0218] At wavelengths of 1590-1620cm -1A characteristic peak FP2 was detected nearby, which can reflect the stretching vibration of the C=N bond in the polymer.

[0219] Analysis of the polymer fragments was performed using gas chromatography-mass spectrometry (GCMS). For example, polymer P1 was subjected to nitrogen atmosphere pyrolysis at 300°C, followed by direct gas chromatography separation via GCMS injection. This yielded the main monomer fragment peaks in the system. Mass spectrometry comparison revealed that the monomer structures composing polymer P1 were AA-Py, AA-6C, AA-10C, and AA-16C, as mentioned earlier.

[0220] Similarly, the monomer structures that make up polymers such as polymer P2 and polymer P3 can also be determined using the above analytical methods.

[0221] Furthermore, after deep alkaline hydrolysis of the aforementioned polymers, the structure of different carbon chains can be reflected in the GCMS spectrum. By combining the products obtained from thermal pyrolysis and alkaline hydrolysis, the integrated area calculation of the structure of the hydrogen and carbon NMR spectra can identify the carbon chain lengths in polymers such as P1.

[0222] To verify the redox properties of the polymer provided in this application, a biosensor can be fabricated using the polymer, and the sensing current of the biosensor under different oxygen concentrations can be tested. The following example illustrates the fabrication of a glucose sensor using the polymer; the specific experimental procedure is as follows:

[0223] Aqueous solutions of polymer (e.g., 20 mg / mL), glucose oxidase (e.g., 20 mg / mL), and polyethylene glycol diglycidyl ether (e.g., 10 mg / mL) of a certain concentration were prepared separately. These three solutions were mixed thoroughly and then drop-coated onto the electrode surface. After the water evaporated, the electrode was vacuum-dried at room temperature for 24 hours to obtain a glucose sensing electrode. A glucose restriction membrane solution was then coated onto the surface of the glucose sensing electrode to form a semi-permeable polymer glucose restriction layer membrane.

[0224] Referring to Figures 1 to 6, the sensing currents of glucose sensors made of the above 6 polymers under different oxygen concentrations are respectively shown. The difference between the sensing current of the sensor corresponding to polymer P1 under saturated oxygen and zero oxygen conditions (hereinafter referred to as the oxygen competition coefficient) ΔE1 is approximately 2%, the oxygen competition coefficient ΔE2 of the sensor corresponding to polymer P2 is approximately 8%, the oxygen competition coefficient ΔE3 of the sensor corresponding to polymer P3 is approximately 6%, the oxygen competition coefficient ΔE4 of the sensor corresponding to polymer P4 is approximately 4%, the oxygen competition coefficient ΔE5 of the sensor corresponding to polymer P5 is approximately 6%, and the oxygen competition coefficient ΔE6 of the sensor corresponding to polymer P6 is approximately 28%.

[0225] In other words, compared to glucose sensors made of polymer P6, the electrochemical reaction efficiency of glucose sensors made of polymers P1 to P5 does not change significantly under different oxygen concentrations; or, in other words, changes in the oxygen concentration in the reaction system have little effect on the efficiency of the electrochemical reaction of these glucose sensors. Since the efficiency of redox reactions is largely influenced by the electron transfer efficiency of the reactants, the above experimental results also demonstrate that changes in the oxygen concentration in the reaction system have little effect on the electron transfer efficiency of polymers P1 to P5 during the reaction process. Sensors using these polymers P1 to P5 can obtain relatively stable and reliable physiological data detection results under different measurement environments.

[0226] Figure 7 shows a schematic diagram of the chemical reaction process of the glucose sensor.

[0227] Glucose in the sample can be oxidized to gluconic acid by glucose oxidase and other enzymes. During this reaction, glucose releases electrons, and oxidized glucose oxidase binds electrons. Oxidized glucose oxidase transforms into reduced glucose oxidase after binding electrons. The electrons gained by reduced glucose oxidase can combine with oxidizing substances in the reaction system, and the reduced glucose oxidase that has lost electrons can revert back to oxidized glucose oxidase.

[0228] The electrons of the reduced glucose oxidase can bind to the polymer provided in this application, allowing the oxidized polymer to transform into a reduced polymer after electron binding; the electrons of the reduced glucose oxidase can also bind to dissolved oxygen (oxygen) in the reaction system, allowing the oxygen to transform into hydrogen peroxide after gaining electrons. In other words, for the excess electrons contained in the reduced glucose oxidase, the oxidized polymer and dissolved oxygen in the reaction system are in competition.

[0229] Oxidized polymers can transfer electrons to the working electrode after gaining electrons, forming a sensing current used to determine the glucose content in the sample. If more electrons are transferred to the working electrode, the intensity of the sensing current is higher, and the detection of glucose content in the sample is more accurate. Conversely, if more electrons are bound by oxygen in the reaction system, the intensity of the sensing current on the working electrode is lower, and the detection of glucose content in the sample is less accurate.

[0230] Figures 8 and 9 illustrate the microscopic electron transfer process of the polymers provided in the embodiments of this application during the redox reaction. Figure 8 can be used to represent the electron transfer process of polymers P1 to P5 (hereinafter, polymer P1 will be the main focus of the description), and Figure 9 can be used to represent the electron transfer process of polymer P6.

[0231] Referring to Figure 8, the main chain of polymer P1 can be connected to various branches of different lengths. These branches are arranged loosely and interspersed, resulting in a low proportion of entanglement between branches. During the reaction, the branches oscillate, and electron transfer occurs between the active sites of adjacent branches during collisions. This allows electrons from the active sites furthest from the working electrode to gradually transfer to the working electrode, forming a sensing current. Due to the low proportion of branch entanglement, polymer P1 exhibits high electron transfer efficiency during the reaction, is less affected by the oxygen concentration in the reaction system, and generates a stronger sensing current at the working electrode, leading to more accurate sensor measurements.

[0232] Referring to Figure 9, the chain lengths of the side chains connected to the main chain of polymer P6 are basically the same, and the proportion of entanglement between the side chains is relatively high. During the reaction, the entangled side chains have a smaller range of motion, reducing the probability of collisions between active sites and decreasing electron transfer efficiency. As the oxygen concentration in the reaction system increases, more electrons combine with oxygen, reducing the proportion of electrons transferred to the working electrode. This results in a lower intensity of the sensing current formed by the working electrode and a larger measurement error in the sensor.

[0233] Compared to polymer P2, the reactants used to synthesize polymer P3 contain more AA-12C monomers and fewer AA-Py monomers. The oxygen competition coefficient of the glucose sensor containing polymer P3 is smaller than that of the glucose sensor containing polymer P2. In other words, the glucose sensor containing polymer P3 is less affected by the oxygen concentration in the reaction system. This may be because more AA-12C monomers introduce a higher proportion of active sites into the polymer, improving the electron transfer efficiency of polymer P3 during the reaction process.

[0234] Compared to polymer P4, the reaction for synthesizing polymer P5 contains more monomers AA-6C and AA-12C, and less monomer AA-Py. The oxygen competition coefficient of the glucose sensor containing polymer P4 is greater than that of the glucose sensor containing polymer P5; in other words, the glucose sensor containing polymer P4 is more affected by the oxygen concentration in the reaction system. Considering that monomers AA-6C and AA-1E0 have similar chain lengths, and monomers AA-12C and AA-3E0 have similar chain lengths, the above experimental results may be due to the increased proportion of entanglement between branches of similar chain lengths in polymer P5, leading to a decrease in the efficiency of electron transfer during the reaction process.

[0235] Based on the polymer provided in the above example, as shown in FIG10, this application embodiment also provides a sensor 100, which may include a sensing layer 110, a diffusion control layer 120, and a biocompatible layer 130. These three functional layers can be stacked along the thickness direction of the sensor 100.

[0236] In some examples, sensor 100 can be used to detect one or more of glucose, ascorbic acid, uric acid, lactic acid, ketone bodies, etc.

[0237] For example, the sensing layer 110 may include one or more of the polymers provided in the embodiments of this application; the sensing layer 110 may also include glucose oxidase or other enzymes that catalyze glucose metabolism. During the use of the sensor 100, the sensing layer 110 may be located on the side away from the user's skin.

[0238] For example, the diffusion control layer 120 can be used to regulate the rate at which glucose molecules enter the sensing layer 110, thereby improving the stability and accuracy of the signal acquired by the sensor 100. For example, the diffusion control layer 120 may include a glucose restriction layer membrane.

[0239] For example, the biocompatible layer 130 can be used to contact the user's skin or subcutaneous tissue. The biocompatible layer 130 can be made of a biocompatible material to reduce immune responses and extend the lifespan of the sensor 100.

[0240] This application also provides a continuous glucose monitoring (CGM) system, which may include a transmitter, a receiver, and a sensor 100.

[0241] The transmitter can be used to acquire data collected by sensor 100 and transmit this data to a receiver and / or other electronic devices. Exemplarily, the transmitter may include a microprocessor and a wireless communication module. Exemplarily, the transmitter may also include a battery that can power the aforementioned microprocessor and wireless communication module.

[0242] The receiver can be used to receive data (such as blood glucose readings) from the transmitter. Alternatively, the receiver can be a standalone device or integrated into an electronic device, such as a mobile phone. Users can view blood glucose test results, trends, and other information through the receiver. As an example, the receiver can also provide alarm reminders, historical data analysis, and other functions; this application does not limit its scope.

[0243] This application also provides a wearable device, which may include the aforementioned sensor 100. The wearable device may be one or more of a watch, bracelet, ring, patch, etc., and this application does not limit it.

[0244] It is understood that the sensor 100 provided in this application embodiment contains the polymers described in the above examples, therefore, it has higher accuracy in detecting values ​​such as blood glucose levels, and the oxygen content in the environment has less impact on the use of the sensor 100. The sensor 100 can be used in a variety of different environments. Similarly, the continuous glucose monitoring system and wearable device provided in this application embodiment have higher accuracy in detection results and a wider range of applications.

[0245] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A polymer, characterized in that, include: Main chain, first side chain, and second side chain. The first branch includes a first functional group and a second functional group, the second functional group is connected between the main chain and the first functional group, and the end of the first branch away from the main chain is coordinated with the transition metal atom Ma; The second branch includes a third functional group and a fourth functional group, wherein the fourth functional group connects the main chain and the third functional group; Wherein, the first functional group and the third functional group are both aromatic nitrogen-containing groups, and the second functional group and the fourth functional group are both polar groups.

2. The polymer according to claim 1, characterized in that, The end of the second branch furthest from the main chain coordinates with the transition metal atom Mb.

3. The polymer according to claim 1 or 2, characterized in that, The length of the second branch is different from the length of the first branch.

4. A polymer, characterized in that, include: Main chain, first side chain, and second side chain. The first branch includes a first functional group, and the end of the first branch away from the main chain is coordinated with a transition metal atom Ma; The second branch includes a third functional group, and the end of the second branch furthest from the main chain is coordinated with the transition metal atom Mb; The chain length of the first branch is different from that of the second branch, and both the first functional group and the third functional group are aromatic nitrogen-containing groups.

5. The polymer according to claim 4, characterized in that, The first branch further includes a second functional group, which connects the main chain and the first functional group; the second branch further includes a fourth functional group, which connects the main chain and the third functional group.

6. The polymer according to claim 5, characterized in that, Both the second functional group and the fourth functional group are polar groups.

7. The polymer according to any one of claims 1 to 6, characterized in that, The first functional group is a first pyridine group, and the third functional group is a second pyridine group; and / or, the second functional group is a first amide group, and the fourth functional group is a second amide group.

8. The polymer according to claim 7, characterized in that, The first branch and / or the second branch include at least one of the following functional groups:

9. The polymer according to claim 7 or 8, characterized in that, The ratio p of the molar amount of transition metal atoms contained in the polymer to the molar amount of pyridine groups contained in the polymer satisfies: p ≥ 0.

3.

10. The polymer according to any one of claims 7 to 9, characterized in that, The first branch and the second branch are distributed at intervals.

11. The polymer according to any one of claims 7 to 10, characterized in that, The first branch further includes a third amide group, and the second branch includes a fourth amide group. One end of the third amide group is connected to the pyridine nitrogen of the first branch, and the other end is connected to the complex of the transition metal atom Ma; One end of the fourth amide group is connected to the pyridine nitrogen of the second branch, and the other end is connected to the complex of the transition metal atom Mb.

12. The polymer according to claim 11, characterized in that, The first branch further includes a first hydrocarbon group, which is attached between the third amide group and the pyridine nitrogen of the first branch. The second branch further includes a second hydrocarbon group, which is attached between the fourth amide group and the pyridine nitrogen of the second branch. The chain length of the second hydrocarbon group is different from that of the first hydrocarbon group.

13. The polymer according to claim 12, characterized in that, The number of carbon atoms J contained in the first hydrocarbon group satisfies: 2≤J≤20, where J is an integer.

14. The polymer according to claim 13, characterized in that, The second hydrocarbon group contains Q carbon atoms, the difference between J and Q is greater than or equal to 1, and Q is an integer.

15. The polymer according to any one of claims 1 to 14, characterized in that, The first branch further includes a fifth functional group, which is connected between the first functional group and the complex of the transition metal atom Ma. The fifth functional group includes one or more of the following: -COC-, -CSC-, and -CNC-.

16. The polymer according to any one of claims 1 to 15, characterized in that, The transition metal atom Ma and the transition metal atom Mb are one or more of the following: osmium, ruthenium, vanadium, cobalt, rhodium, palladium, or iron.

17. The polymer according to any one of claims 1 to 16, characterized in that, The first functional group and the third functional group include at least one of the following: pyridine group, imidazole group, pyrrole group, indole group, purine group, pyrimidine group, quinoline group, isoquinoline group, pyridazine group or pyrazine group; and / or, the second functional group and the fourth functional group include at least one of the following: amide group, imino group, ester group, ether group, carbonyl group.

18. A sensor, characterized in that, It includes a sensing layer, a diffusion control layer and a biocompatible layer stacked together, wherein the sensing layer comprises the polymer according to any one of claims 1 to 17.

19. A detection device, characterized in that, It includes a transmitter, a receiver, and the sensor as described in claim 18.

20. A detection device, characterized in that, Includes a processor and the sensor as described in claim 18.

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