CN108559064B - Conjugated main chain doped zwitterionic polyfluorene vinylene and preparation and application thereof - Google Patents
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Abstract
The invention discloses a conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene and preparation and application thereof. A dibromo fluorene derivative (A monomer), a diene fluorene derivative (B monomer) and a small amount of narrow-band-gap dibromo aromatic heterocyclic structure (C monomer) are doped, an organic metal catalyzed Heck reaction is carried out by adopting an A + B + C three-component polymerization method, and the obtained neutral polymer is subjected to quaternary ammonification and/or carboxylic ester hydrolysis and other reactions to obtain the conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene. The synthesis method is simple, can realize proportional fluorescence emission, and improves the detection sensitivity; and can realize red light/near infrared emission and improve the fluorescent biological imaging effect. The zwitterionic structure is beneficial to endocytosis of cells, and can effectively improve the problem that materials are adsorbed by cell membranes, thereby possibly achieving better biological imaging effect.
Description
Technical Field
The invention belongs to the technical field of chemical, biological sensing and fluorescence imaging materials, and particularly relates to a preparation method of a water-soluble zwitterionic water-soluble polymer which takes alternate fluorenyl and vinyl as conjugated main chains and is doped with a small amount of aromatic heterocyclic rings, and application of the polymer in the aspects of chemical/biological sensing and fluorescence biological imaging.
Background
In recent decades, the application of water-soluble conjugated polymers in the information technology field of chemical and biological sensing has attracted more and more extensive and eager attention. The compounds combine the excellent photoelectric property of the traditional conjugated polymer and the water-solubility characteristic of polyelectrolyte. On the one hand, as conjugated polymers, they generally have a strong light-absorbing property in the ultraviolet visible region and have the property of "molecular conducting wires". On the other hand, the water solubility is realized mainly by hooking hydrophilic ionic functional groups on the side chains of a conjugated system, and the ionic functional groups can generate electrostatic interaction with other charged substances, so that the high-sensitivity detection of various organic, inorganic and biological molecules in the surrounding environment can be realized through the electron or energy transfer between the polymer and a quencher with opposite charges.
Further development is carried out on the basis, and in recent years, the research and application of the water-soluble conjugated polymer as a novel fluorescent probe material in the field of fluorescence biological imaging arouse great interest. A review article published in 2012 by chem.rev., entitled "water-soluble conjugated polymers for fluorescence imaging, diagnosis and therapy", and a number of research papers on the application of water-soluble conjugated polymer fluorescence imaging emerged in various international official academic journals. The water-soluble conjugated polymer with typical amphipathy can be self-assembled in an aqueous solution to form nano particles, and can also be effectively combined with biomolecules or drug molecules to form nano particles by utilizing supermolecular acting forces such as static electricity, hydrogen bonds, hydrophobicity and the like; these nanoparticles can be endocytosed by cells for fluorescence imaging by incubation with cells and further for in vivo imaging.
At present, most of the water-soluble conjugated polymers used for fluorescence imaging research use side-chain-attached cationic functional groups, and relatively few studies have been made on side-chain-attached cationic functional groups. Firstly, the traditional cationic water-soluble conjugated polymer nanoparticles are easy to generate nonspecific protein adsorption when circulating in vivo, so that the accumulation and retention effects on tumor tissues are influenced; in addition, when fluorescence imaging is performed in cells, the fluorescence imaging has the problems that the fluorescence imaging is difficult to be endocytosed by the cells, and the fluorescence imaging is easy to be adsorbed by cell membranes after endocytosis, and the like, because most phospholipids in the cell membranes have negative charges. The zwitterionic water-soluble conjugated polymer can effectively resist nonspecific protein adsorption and improve the problem that the material is adsorbed by cell membranes due to the fact that the side chain is simultaneously connected with the anion and the cation, and therefore better tumor targeting effect and biological imaging effect can be achieved. Secondly, the structure of the zwitterionic polymer contains a large number of acidic groups which are easy to dissociate and basic groups which are easy to protonate, and the ionization degree of the groups is influenced by external conditions such as the pH value of the solution, so that the conformation of macromolecular chains is correspondingly changed, the fluorescence spectrum is changed, and the sensing of factors such as the pH value of the environment or fluorescence biological imaging can be realized.
In addition, the water-soluble polyfluorene vinylenes studied in the past are all polymers formed by two monomers, the light-emitting area is single, most of the light-emitting area is concentrated in a blue light area, and the light-emitting area is less in a red light/near infrared light area (600- & gt 1000 nm). In a red light/near infrared light region, the biological tissue absorbs and scatters less light, the penetration capability of the light to the biological tissue is stronger, and the autofluorescence of the organism is weaker, so that the depth detection during the living body imaging is facilitated. Therefore, the invention introduces aromatic heterocycle with narrow band gap as one of monomers into the macromolecular main chain to obtain a series of conjugated main chain doped zwitterionic water-soluble polyfluorene vinylenes. Research results show that the molecular conformation and aggregation state of the polymer can be adjusted by changing external conditions such as solvent, concentration, pH value and the like, fluorescence resonance energy transfer is caused, and a plurality of light emitting regions are shown, for example, 4, 7-bis (thiophene-2-yl) -2,1, 3-benzothiadiazole group doped water-soluble polyfluorene vinylene can emit light in blue light and red light regions. By comparing the fluorescence emission changes (namely proportional fluorescence emission) of different light emitting areas, the interference of other factors can be reduced, the detection sensitivity is improved, and the method can be used for designing diversified detection schemes and meeting the diversified requirements of detection objects, so that the material has potential wide application prospects in the aspects of chemical/biological sensing and fluorescence biological imaging.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene and a preparation method thereof, and provides application of the conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene in the aspects of chemistry, biosensing and fluorescence bioimaging. The characteristics of the materials can be used for designing diversified detection schemes, can improve the detection sensitivity and meet the diversified requirements of detection objects, so that the materials have potential wide application prospects in the aspects of chemical/biological sensing and fluorescence imaging.
The technical scheme is as follows: the zwitterionic water-soluble polyfluorene vinylene doped with the conjugated main chain is prepared by a Heck polymerization reaction catalyzed by organic metal to obtain a neutral polymer, and then the neutral polymer is subjected to quaternary ammonification, carboxylic ester hydrolysis and other reactions to obtain the zwitterionic water-soluble polyfluorene vinylene doped with the conjugated main chain, wherein the molecular structure of the compound is as follows:
wherein the content of the first and second substances,
ar is one of 4, 7-bis (thiophene-2-yl) -2,1, 3-benzothiadiazole group or 2, 5-bis (2-ethylhexyl) -3, 6-bis (thiophene-2-yl) -pyrrolopyrrole diketone group;
the polymerization degree n is a natural number which is more than 1, x and y are decimal numbers which are more than 0 and less than 1, x + y is 1, and y is less than or equal to 0.3;
r and R' are different and are respectively selected from any one of the following groups: r1R2R3R4N+，R5COO-，R1R2R3R6N+Or R, R' are simultaneously R1R2R3R6N+(ii) a Where R is1，R2，R3，R4，R5Are respectively one of the following groups: alkyl, alkoxy; r6Structural formula is R7SO3 -Where R is7Is one of the following groups: alkyl, alkoxy.
Wherein:
a. when Ar is a 4, 7-bis (thien-2-yl) -2,1, 3-benzothiadiazole group, two typical structures are as follows:
a1. both R and R' are locatedIn the 9-position of the fluorenyl group, the structure of R is R1R2R3R4N+，R1Is alkoxy, R2、R3And R4Are all alkyl; the structure of R' is R5COO-，R5Is an alkyl group having the formula:
a2.R and R 'are both in the 9-position of the fluorenyl radical, R, R' are both R1R2R3R6N+Structure of (1), R1Is alkoxy, R2And R3Are each alkyl, R6Structural formula is R7SO3 -Where R is7Is an alkyl group having the formula:
b. when Ar is a2, 5-bis (2-ethylhexyl) -3, 6-bis (thien-2-yl) -pyrrolopyrroledione group, two typical structures are as follows:
b1.R and R' are both in the 9-position of the fluorenyl radical, the structure of R being R1R2R3R4N+，R1Is alkoxy, R2、R3And R4Are all alkyl; the structure of R' is R5COO-，R5Is an alkyl group having the formula:
b2.R and R 'are both in the 9-position of the fluorenyl radical, R and R' are both R1R2R3R6N+Structure of (1), R1Is alkoxy, R2And R3Are each alkyl, R6Structural formula is R7SO3 -Where R is7Is an alkyl group having the formula:
the preparation method of the conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene comprises the following steps:
1) synthesizing neutral conjugated polymer by adopting organic metal catalyzed Heck polymerization reaction and a three-component polymerization method of A + B + C, wherein A is a dibromofluorene derivative monomer, B is a dienylfluorene derivative monomer, C is a dibromoaromatic heterocyclic monomer for doping,
2) the neutral polymer prepared in the step 1) is subjected to quaternary ammonification and/or carboxylic ester hydrolysis reaction to obtain the conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene.
Wherein the content of the first and second substances,
the sum of the amounts of the substances of the monomer A and the monomer C is equal to the amount of the substance of the monomer B, and the amount of the substance of the monomer C is less than or equal to 30 percent of the amount of the substance of the monomer B.
The conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene is applied to chemical, biological sensing or fluorescence biological imaging.
Has the advantages that: in the invention, aromatic heterocyclic ring is taken as one of monomers and introduced into a polyfluorene vinylene main chain to obtain amphoteric ion type water-soluble polyfluorene vinylene doped with a conjugated main chain, and certain external conditions such as solvent, pH value and the like are changed to adjust the molecular conformation and aggregation state of the polymer, so that fluorescence resonance energy transfer is generated, proportional fluorescence emission of a plurality of light-emitting regions is shown, and red light/near infrared emission can be realized. The zwitterionic structure is beneficial to endocytosis of cells, and can effectively improve the problem that materials are adsorbed by cell membranes, thereby possibly achieving better biological imaging effect. The characteristics of the materials can be used for designing diversified detection schemes, can improve the detection sensitivity and meet the diversified requirements of detection objects, so that the materials have potential wide application prospects in the aspects of chemical/biological sensing and fluorescence imaging.
Drawings
FIG. 1 is a drawing of the present inventionThe ultraviolet-visible absorption spectrum of the prepared zwitterionic water-soluble polyfluorene vinylene in water has the concentration of 2 × 10-5mol/L。
FIG. 2 shows fluorescence emission spectrum of zwitterionic water-soluble polyfluorene vinylene prepared by the present invention in water, with concentration of 2 × 10-5mol/L。
FIG. 3 is a bright field, a dark field and an overlay chart of imaging of the zwitterionic water-soluble polyfluorene vinylene HeLa cell prepared by the invention.
Detailed Description
In order to better understand the contents of the present invention, the following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
the monomers (1) and (2) were prepared by setting the mass ratio of (1), (2) and (3) to 1: 1.25: 0.25 feed, then in Pd (OAc)2/P(o-tolyl)3Coupling the three under catalysis through Heck reaction, and obtaining neutral 4, 7-bi (thiophene-2 group) -2,1, 3-benzothiadiazole group doped water-soluble polyfluorene vinylene P1 after reaction for 12 hours; carrying out quaternization reaction by using methyl iodide for 3 days to obtain cationic 4, 7-bis (thiophene-2 yl) -2,1, 3-benzothiadiazole group doped water-soluble polyfluorene vinylene P1'; and finally, carrying out carboxylic ester hydrolysis reaction by using trifluoroacetic acid, and reacting for 24 hours to obtain the zwitterionic 4, 7-bis (thiophene-2 yl) -2,1, 3-benzothiadiazole group-doped water-soluble polyfluorene vinylene P1'.
Example 2:
in the same manner as in example 1, monomer (2) was prepared, monomer (4) was synthesized by the following method, and the mass ratio of (4), (2) and (3) was 1: 1.25: 0.25 feed, then in Pd (OAc)2/P(o-tolyl)3CatalysisThen, the three are coupled through Heck reaction, after 12 hours of reaction, neutral 4, 7-bis (thiophene-2-yl) -2,1, 3-benzothiadiazole group doped water-soluble polyfluorene vinylene P2 is obtained, and further, iodomethane is used for carrying out quaternization reaction for 3 days to obtain cationic 4, 7-bis (thiophene-2-yl) -2,1, 3-benzothiadiazole group doped water-soluble polyfluorene vinylene P2'; and finally adding 1, 4-butane sultone for reaction for 3 days to obtain the zwitterionic 4, 7-bis (thiophene-2-yl) -2,1, 3-benzothiadiazole group-doped water-soluble polyfluorene vinylene P2'.
Claims (6)
1. A conjugated main chain doped amphoteric ion type water-soluble polyfluorene vinylene is characterized by having the following molecular formula:
wherein the content of the first and second substances,
ar is one of 4, 7-bis (thiophene-2-yl) -2,1, 3-benzothiadiazole group or 2, 5-bis (2-ethylhexyl) -3, 6-bis (thiophene-2-yl) -pyrrolopyrrole diketone group;
the polymerization degree n is a natural number which is more than 1, x and y are decimal numbers which are more than 0 and less than 1, x + y is 1, and y is less than or equal to 0.3;
r and R' are different and are respectively selected from any one of the following groups: r1R2R3R4N+，R5COO-Or R, R' are simultaneously R1R2R3R6N+(ii) a Where R is1，R2，R3，R4，R5Are respectively one of the following groups: alkyl, alkoxy; r6Structural formula is R7SO3 -Where R is7Is one of the following groups: alkyl, alkoxy.
2. The conjugated backbone doped zwitterionic water soluble polyfluororenylvinylene of claim 1, wherein:
a. when Ar is a 4, 7-bis (thien-2 yl) -2,1, 3-benzothiadiazole group, two structures selected from:
a1.R and R' are both in the 9-position of the fluorenyl radical, R has the structure R1R2R3R4N+，R1Is alkoxy, R2、R3And R4Are all alkyl; the structure of R' is R5COO-，R5Is an alkyl group having the formula:
a2.R and R 'are both in the 9-position of the fluorenyl radical, R, R' are both R1R2R3R6N+Structure of (1), R1Is alkoxy, R2And R3Are each alkyl, R6Structural formula is R7SO3 -Where R is7Is an alkyl group having the formula:
3. the conjugated backbone doped zwitterionic water soluble polyfluororenylvinylene of claim 1, wherein:
b. when Ar is a2, 5-bis (2-ethylhexyl) -3, 6-bis (thien-2-yl) -pyrrolopyrroledione group, two structures selected from:
b1.R and R' are both in the 9-position of the fluorenyl radical, the structure of R being R1R2R3R4N+，R1Is alkoxy, R2、R3And R4Are all alkyl; the structure of R' is R5COO-，R5Is an alkyl group having the formula:
b2.R and R 'are both in the 9-position of the fluorenyl radical, R and R' are both R1R2R3R6N+Structure of (1), R1Is alkoxy, R2And R3Are each alkyl, R6Structural formula is R7SO3 -Where R is7Is an alkyl group having the formula:
4. a method for preparing the zwitterionic water-soluble polyfluororenylvinylene doped with the conjugated main chain according to claim 1, 2 or 3, which is characterized by comprising the following steps:
1) synthesizing neutral conjugated polymer by adopting organic metal catalyzed Heck polymerization reaction and a three-component polymerization method of A + B + C, wherein A is a dibromofluorene derivative monomer, B is a dienylfluorene derivative monomer, C is a dibromoaromatic heterocyclic monomer for doping,
2) and (2) carrying out quaternary ammonification and carboxylic ester hydrolysis reaction or quaternization and sulfonic ester hydrolysis reaction on the neutral polymer prepared in the step 1) to obtain the conjugated main chain doped zwitterionic water-soluble polyfluorene vinylene.
5. The method for preparing a conjugated main chain doped zwitterionic water-soluble polyfluororenylene as claimed in claim 4, wherein the sum of the amounts of the substances of monomer A and monomer C is equal to the amount of the substance of monomer B, and the amount of the substance of C is less than or equal to 30% of the amount of the substance of B.
6. Use of the conjugated backbone doped zwitterionic water soluble polyfluorene vinylene of claim 1 in chemical sensing, biosensing or fluorescence bioimaging.
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| CN114106297B (en) * | 2021-12-16 | 2024-01-05 | 香港中文大学（深圳） | Fluorescent polymer containing zwitterionic groups and preparation method and application thereof |
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