CN111849006B - Bionic functionalized PEDOT (PEDOT-PSS) film and preparation method thereof - Google Patents

Bionic functionalized PEDOT (PEDOT-PSS) film and preparation method thereof Download PDF

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CN111849006B
CN111849006B CN202010544342.5A CN202010544342A CN111849006B CN 111849006 B CN111849006 B CN 111849006B CN 202010544342 A CN202010544342 A CN 202010544342A CN 111849006 B CN111849006 B CN 111849006B
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朱波
赵国欣
张述华
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Abstract

The invention discloses a biomimetic functionalized PEDOT PSS film and a preparation method thereof, the film has a double-layer structure, the bottom layer is the PEDOT PSS film, the upper layer is a biomimetic functionalized conductive polymer, the film is prepared by homopolymerization of a monomer containing a hydrophilic group or copolymerization of the monomer containing the hydrophilic group and a monomer containing a biological coupling group, and the polymerization method comprises solution oxidation deposition, oxidation vapor deposition and electrochemical deposition polymerization. The film can be integrated on the surface of a microelectrode or a channel of a transistor, remarkably inhibits nonspecific adhesion interference under complex biological environment conditions, can realize specific action with cells, viruses and biomolecules, realizes specific combination with target biomolecules under the background of nonspecific adhesion resistance, and effectively improves the selectivity and accuracy of sensing or recording of a device. The material has strong non-specific adhesion resistance, excellent biomolecule coupling capacity and simple process, and is suitable for industrial production.

Description

Bionic functionalized PEDOT (PEDOT-PSS) film and preparation method thereof
Technical Field
The invention relates to a bionic functionalized PEDOT PSS film and a preparation method thereof. The material can be integrated on the surface of an electrode or a channel of a transistor, remarkably inhibits nonspecific adhesion interference under complex biological environment conditions, can be further coupled with biomolecules, and realizes specific action with cells, viruses and biomolecules. Is applied to the technical field of bionic conductive high polymer materials.
Background
Microelectrode devices based on PEDOT: PSS, as well as devices such as transistors, have been widely used in the biomedical field. The PEDOT-PSS has excellent conductivity, processability, mechanical properties and aqueous phase electrochemical stability. However, PEDOT, PSS non-specific adhesion proteins and other biomolecules, cells, viruses and the like, cause an increase in the resistance to electrical signal sensing; meanwhile, the nonspecific group can further trigger tissue inflammation reaction to form a colloid scar coating device. Moreover, the nonspecific effect of PEDOT and PSS greatly interferes with the accuracy and precision of sensing and signal recording. PSS, which is beneficial to improving the accuracy and precision of device sensing and signal recording, and establishing specific identification under the background of non-specific adhesion resistance after coupling with biomolecules, thereby obviously improving the selectivity of the device.
So far, the main approach to modify PEDOT: PSS materials has been to introduce bioactive dopants (e.g. heparin, gelatin, etc.). The method is simple and easy, but the conductivity of the material can be obviously reduced, the electrochemical impedance of the material can be improved, the doping modification is unstable, and the biomolecules can be gradually exhausted in the using process of the device; PSS can improve the affinity effect of a device and a detected target, but the non-specific effect of PSS is not completely inhibited or eliminated, so that the requirements of practical use on sensing and signal recording selectivity and device implantation stability are difficult to meet.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the existing materials and technologies and provide a biomimetic functionalized PEDOT, namely a PSS film material and a preparation method thereof. The material can be applied to devices such as microelectrode arrays and transistors based on PEDOT, PSS and the like, and the long-term stability, selectivity and precision of sensing and signal recording of the material are obviously improved. The preparation method of the bionic polymer has strong operability, is simple and feasible, and is suitable for actual production.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the bionically functionalized PEDOT PSS film has a double-layer structure, wherein the PEDOT PSS film is arranged on the bottom layer, and the bionically functionalized conductive high polymer material is arranged on the upper layer. Wherein the upper layer conductive polymer contains hydrophilic group, and can repel cell, virus, fungus, bacteria and biomolecule.
Preferably, the conductive polymer has a pendant bio-couplable group that bio-couples with the biomolecule, allowing the material to perform specific functions with cells, viruses, and biomolecules.
Preferably, the conductive polymer material contains a monomer unit represented by the structural formula (i):
Figure BDA0002540013570000021
in formula (I):
Figure BDA0002540013570000022
the repeating unit constituting the main chain of the conductive polymer is
Figure BDA0002540013570000023
Figure BDA0002540013570000024
And derivatives thereof;
-L 1 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -wherein x, y are integers and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 2 is- (CH) 2 ) x -、-(CH 2 ) x -O-、-CO-O-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、-C(CH 3 ) 2 -CO-O-(CH 2 ) x 、-CH(CH 3 )-O-(CH 2 ) x 、-S-CH 2 -CH 2 -O-(CH 2 ) x 、-S-CH 2 -CH(CH 3 )-CO-O-(CH 2 ) x Wherein x is an integer and is more than or equal to 0 and less than or equal to 20; -R 2 Is a hydrophilic group.
Preferably, the conductive polymer may further include a monomer unit represented by formula (ii) in addition to the monomer unit represented by formula (i):
Figure BDA0002540013570000031
in formula (II):
Figure BDA0002540013570000032
the repeating unit constituting the main chain of the conductive polymer is
Figure BDA0002540013570000033
Figure BDA0002540013570000034
And derivatives thereof;
-L 3 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -NH-CO-O-、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y-, wherein x and y are integers, and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 4 -is-O-, -CO-O-, -O-CH 2 -CO-O-、-S-(CH 2 ) x -CO-O-(CH 2 ) y -、-CO-NH-(CH 2 ) x -、-NH-(CH 2 ) x -、-NH-CO-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、
Figure BDA0002540013570000035
Figure BDA0002540013570000036
Wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 20,0 and less than or equal to 20;
-R 3 are bio-couplable groups.
Preferably, the conductive polymer has a monomer unit represented by formula (i):
Figure BDA0002540013570000037
in formula (I):
Figure BDA0002540013570000041
the repeating unit constituting the main chain of the conductive polymer is
Figure BDA0002540013570000042
Figure BDA0002540013570000043
And derivatives thereof;
-L 1 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -wherein x, y are integers and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 2 is- (CH) 2 ) x -、-(CH 2 ) x -O-、-CO-O-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、-C(CH 3 ) 2 -CO-O-(CH 2 ) x 、-CH(CH 3 )-O-(CH 2 ) x 、-S-CH 2 -CH 2 -O-(CH 2 ) x 、-S-CH 2 -CH(CH 3 )-CO-O-(CH 2 ) x Wherein x is an integer and is more than or equal to 0 and less than or equal to 20;
-R 2 is a hydrophilic group.
And a monomer unit represented by the formula (II):
Figure BDA0002540013570000044
in formula (II):
Figure BDA0002540013570000045
the repeating unit constituting the main chain of the conductive polymer is
Figure BDA0002540013570000046
Figure BDA0002540013570000047
And derivatives thereof;
-L 3 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -NH-CO-O-、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y-, wherein x and y are integers, and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 4 -is-O-, -CO-O-) -O-CH 2 -CO-O-、-S-(CH 2 ) x -CO-O-(CH 2 ) y -、-CO-NH-(CH 2 ) x -、-NH-(CH 2 ) x -、-NH-CO-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、
Figure BDA0002540013570000051
Figure BDA0002540013570000052
Wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 20,0 and less than or equal to 20;
-R 3 are bio-couplable groups.
Preferably, in view of polymerization difficulty and stability, the structural formulas (I), (II)
Figure BDA0002540013570000053
Independently of one another preferably
Figure BDA0002540013570000054
Any one of them.
Preferably, -L in the general structural formula (I) is 1 -is preferably- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -wherein x, y are integers and 0 ≦ x ≦ 5,0 ≦ y ≦ 5; -L 2 Is- (CH) 2 ) x -、-(CH 2 ) x -O-、-CO-O-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、-C(CH 3 ) 2 -CO-O-(CH 2 ) x 、-CH(CH 3 )-O-(CH 2 ) x 、-S-CH 2 -CH 2 -O-(CH 2 ) x 、-S-CH 2 -CH(CH 3 )-CO-O-(CH 2 ) x Wherein x is an integer and is not less than 0 and not more than 5.
Preferably, in the general structural formula (II), -L 3 -is preferably- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -NH-CO-O-、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y-, wherein x and y are integers, and 0. Ltoreq. X.ltoreq. 5,0. Ltoreq. Y.ltoreq.5; -L 4 -is-O-, -CO-O-, -O-CH 2 -CO-O-、-S-(CH 2 ) x -CO-O-(CH 2 ) y -、-CO-NH-(CH 2 ) x -、-NH-(CH 2 ) x -、-NH-CO-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、
Figure BDA0002540013570000055
Figure BDA0002540013570000056
Wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 5,0 and less than or equal to 5.
Preferably, R in the general structural formula (I) is R in consideration of anti-adhesion property and chemical feasibility 2 Preferably a
Figure BDA0002540013570000061
Wherein p is 2 or 3.
Preferably, in view of difficulty and activity of biological coupling, R in the general structural formula (II) 3 preferably-COOH,
Figure BDA0002540013570000062
Any one of them.
The invention also provides a preparation method of the conductive polymer, which comprises the following steps:
the preparation is realized by homopolymerizing the conductive polymer monomer (III) containing the hydrophilic group or copolymerizing the conductive polymer monomer (III) containing the hydrophilic group and the conductive polymer monomer (IV) containing the biological coupling group.
Preferably, the polymerization method by homopolymerization of the hydrophilic group-containing conductive polymer monomer (iii) or copolymerization of the hydrophilic group-containing conductive polymer monomer (iii) and the bio-couplable group-containing conductive polymer monomer (iv) includes oxidative vapor deposition, solution oxidative deposition, and electrochemical deposition polymerization.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. PSS film, introducing bionic functional conductive polymer containing hydrophilic and biological coupling groups by using oxidation vapor deposition, solution oxidation deposition and electrochemical deposition polymerization methods, maintaining or even enhancing the conductivity of the material, realizing specific combination with target biomolecules under the background of maximum nonspecific adhesion resistance, and finally realizing the selective action, wherein the material is expected to provide a good idea for further development of a PSS device based on PEDOT;
2. the invention relates to a biomimetic functionalized material, in particular to a biomimetic functionalized PEDOT (polymer stabilized organic light emitting diode) film which contains hydrophilic groups and bio-coupling groups on the surface, wherein the PSS film can be integrated on the surface of a microelectrode or a channel of a transistor, so that nonspecific adhesion interference under complex biological environment conditions can be obviously inhibited, specific effects with cells, viruses and biomolecules can be further realized, and the selectivity and the accuracy of sensing or recording of a device can be improved to the greatest extent; the bionic functionalized material has strong non-specific adhesion resistance, excellent biomolecule coupling capacity and simple process, and is suitable for industrial production.
Drawings
FIG. 1 electrochemical polymerization curves of polymers VI-24 from example 24, monomers III-24 and IV-24, on PEDOT: PSS films;
FIG. 2 shows the relation between the actual compositions and the charge ratios of the copolymers VI-6, VI-14, VI-24 and VI-25 obtained in example 6/14/24/25;
FIG. 3 Polymer V-4 anti-protein BSA adhesion curves obtained in example 29;
FIG. 4 curves of the adhesion of the copolymers VI-6, VI-14 and VI-24 obtained in example 6/14/24 against the proteins BSA.
Detailed Description
In order that the invention may be more readily understood, preferred embodiments will now be described in detail.
Example 1:
by adopting electrochemical polymerization, 57mg of conductive high molecular monomer III-1 (3 mM) containing hydrophilic groups, 332mg of conductive high molecular monomer IV-1 (7 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (polymer electrolyte peroxide) PSS film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.26V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the bluish copolymer VI-1 can be obtained on a working electrode.
In this embodiment, the conductive polymer monomer containing hydrophilic group and the conductive polymer containing bio-couplable groupThe structural formula of the polymer monomer is shown in Table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhered was 1376ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 2:
adopting electrochemical polymerization, adding 2mg of conductive polymer monomer III-2 (0.1 mM) containing hydrophilic groups, 169mg of copolymerized conductive polymer monomer IV-2 (9.9 mM), 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile into an electrolytic bath, using PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.275V, the scanning speed is 150mV/s, and 2 circles are scanned, namely the blue-biased copolymer VI-2 can be obtained on the working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method of this example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of adhering sample was 1290ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 3:
by oxidative vapor deposition polymerization, 105mg of hydrophilic group-containing electroconductive polymer monomer III-3 (0.3 mmol), 133mg of copolymerized electroconductive polymer monomer IV-3 (0.7 mmol) and 194mg of FeCl 3 (1.2 mmol) was added to the crucible and the chamber was evacuated to less than 1X 10 before deposition -3 And (3) evaporating monomers from a resistance-heated crucible at 140 ℃ under the basic pressure of Torr, taking argon as a protective gas and PEDOT (PSS) film as a deposition object, and repeatedly washing the PEDOT (PSS) substrate by using methanol after the deposition is finished at 150 ℃ to obtain the copolymer VI-3.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 This implementationIn the examples, the amount of the adhered sample was 1204ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 4:
by adopting electrochemical polymerization, 43mg of conductive polymer monomer III-4 (2 mM) containing hydrophilic groups, 146mg of copolymerized conductive polymer monomer IV-4 (7 mM), 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.75V, the scanning speed is 20mV/s, and 5 circles are scanned, namely the blue-like copolymer VI-4 can be obtained on the working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhesion was 1032 ng/cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 5:
by adopting electrochemical polymerization, 48mg of conductive high molecular monomer III-5 (2 mM) containing hydrophilic groups, 110mg of copolymerized conductive high molecular monomer IV-5 (8 mM), 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate octyl ester (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PolysS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.25V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the blue copolymer VI-5 can be obtained on the working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of adhesion of the sample is 946ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 6:
by adopting electrochemical polymerization, 53mg of conductive polymer monomer III-6 (3 mM) containing hydrophilic groups, 130mg of copolymerized conductive polymer monomer IV-6 (7 mM), 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.25V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the blue-like copolymer VI-6 can be obtained on the working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the sample adhesion amount is 860ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 7:
adopting electrochemical polymerization, adding 84mg of conductive high molecular monomer III-7 (5 mM) containing hydrophilic groups, 107mg of copolymerized conductive high molecular monomer IV-7 (5 mM), 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate octyl ester (50 mM) and 50ml of acetonitrile into an electrolytic bath, using a PEDOT (PolysS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.3V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the blue copolymer VI-7 can be obtained on the working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of adhered sample is 774ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers
Example 8:
139mg of hydrophilic group-containing conductive polymer monomer III-8 (0.4 mmol), 329mg of copolymerized conductive polymer monomer IV-8 (0.6 mmol) and 194mg of FeCl were polymerized by oxidative vapor deposition 3 (1.2 mmol) was added to the crucible and depositedBefore, the chamber is vacuumized to the basic pressure lower than 1 x 10 < -3 > Torr, monomers are evaporated from a resistance-heated crucible at 140 ℃, argon is used as protective gas, a PEDOT (polymer ethylene terephthalate) PSS (Poly ethylene terephthalate) film substrate is used as a deposition object, and after the deposition is finished at 150 ℃, the copolymer VI-8 is obtained on the PEDOT (Poly ethylene terephthalate) PSS substrate by repeatedly washing with methanol.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhesion was 760ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 9:
by adopting electrochemical polymerization, 65mg of conductive polymer monomer III-9 (4 mM) containing hydrophilic groups, 59mg of conductive polymer monomer IV-9 (6 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (polymer electrolyte peroxide) PSS film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.35V, the scanning speed is 200mV/s, and 2 circles are scanned, namely the bluish copolymer VI-9 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the sample adhered amount was 750ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 10:
adopting solution oxidation deposition polymerization, dissolving 157mg of conductive polymer monomer III-10 (5 mM) containing hydrophilic groups, 71mg of conductive polymer monomer IV-10 (5 mM) copolymerized with bio-coupling groups and 99.4mg of ferrous chloride tetrahydrate (5 mM) in 95ml of ethanol, adding into a reaction tank carrying a PEDOT (PSS) film substrate, finally adding 476mg of sodium thiosulfate (20 mM) aqueous solution 5ml, stirring for reaction for 24h, respectively washing with methanol, ultrapure water, isopropanol and chloroform, and drying by nitrogen drying to obtain the conductive polymer copolymer VI-10 on the PEDOT (PSS) film substrate.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of adhesion of the sample was 720ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 11:
adopting solution oxidation deposition polymerization, dissolving 200mg of conductive high molecular monomer III-11 (5 mM) containing hydrophilic groups, 208mg of conductive high molecular monomer IV-11 (5 mM) copolymerized with bio-coupling groups and 99.4mg of ferrous chloride tetrahydrate (5 mM) in 95ml of ethanol, adding into a reaction tank carrying a PEDOT (PSS) film substrate, finally adding 476mg of sodium thiosulfate (20 mM) aqueous solution 5ml, stirring for reaction for 24h, respectively washing with methanol, ultrapure water, isopropanol and chloroform, and drying by nitrogen drying to obtain the conductive high molecular copolymer VI-11 on the PEDOT (PSS) film substrate.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 680ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 12:
by adopting electrochemical polymerization, 111mg of conductive polymer monomer III-12 (5 mM) containing hydrophilic groups, 109mg of conductive polymer monomer IV-12 (5 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.23V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the bluish copolymer VI-12 can be obtained on a working electrode.
In this example, the polymer contains hydrophilic groupsThe structural formulas of the conductive polymer monomer of the group and the conductive polymer monomer of the biological coupling group are shown in the table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 670ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 13:
by adopting electrochemical polymerization, 84mg of conductive polymer monomer III-13 (5 mM) containing hydrophilic groups, 58mg of conductive polymer monomer IV-13 (5 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.245V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the bluish copolymer VI-13 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 650ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomer.
Example 14:
adopting electrochemical polymerization, adding 105mg of conductive high molecular monomer III-14 (5 mM) containing hydrophilic group, 145mg of conductive high molecular monomer IV-14 (5 mM) copolymerized with biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate octyl ester (50 mM) and 50ml of acetonitrile into an electrolytic bath, using PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, carrying out polymerization by using a scanning cyclic voltammetry, wherein the scanning range is-0.6-1.225V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the bluish copolymer VI-14 can be obtained on the working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 600ng cm -2 The anti-adhesion effect is generally due to hydrophilicityThe monomer content is low.
Example 15:
by adopting electrochemical polymerization, 98mg of conductive polymer monomer III-15 (5 mM) containing hydrophilic groups, 58mg of conductive polymer monomer IV-15 (8 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (polymer electrolyte peroxide) PSS film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.32V, the scanning speed is 100mV/s, and 3 circles are scanned, namely the bluish copolymer VI-15 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhered was 560ng cm -2 The anti-adhesion effect is common, because the content of the hydrophilic monomer is low.
Example 16:
by adopting electrochemical polymerization, 108mg of conductive polymer monomer III-16 (6 mM) containing hydrophilic groups, 46mg of conductive polymer monomer IV-16 (4 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (polymer electrolyte peroxide) PSS film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.23V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the bluish copolymer VI-16 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhered was 516ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 17:
adopting electrochemical polymerization, adding 122mg of conductive polymer monomer III-17 (6 mM) containing hydrophilic groups, 46mg of conductive polymer monomer IV-17 (4 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile into an electrolytic bath, taking PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.23V, the scanning speed is 100mV/s, and 5 circles are scanned, namely the blue-biased copolymer VI-17 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhesion was 480ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 18:
adopting electrochemical polymerization, adding 121mg of conductive polymer monomer III-18 (6 mM) containing hydrophilic groups, 42mg of conductive polymer monomer IV-18 (4 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM) and 50ml of acetonitrile into an electrolytic bath, using a PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.25V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the blue-biased copolymer VI-18 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The samples prepared by the method in the example were evaluated for their properties, and the protein adhesion amount of PEDOT/PSS film was 602ng cm -2 In this example, the amount of sample adhesion was 460ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 19:
adopting electrochemical polymerization, adding 120mg of conductive polymer monomer III-19 (6 mM) containing hydrophilic groups, 68mg of conductive polymer monomer IV-19 (4 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, using a PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.68V, the scanning speed is 100mV/s, and 2 circles are scanned, so that the bluish copolymer VI-19 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1.PEDOT PSS film protein adhesion amount 602ng cm -2 In this example, the amount of sample adhesion was 430ng cm -2 The anti-adhesion effect is generally due to the low content of hydrophilic monomers.
Example 20:
by adopting electrochemical polymerization, 90mg of conductive polymer monomer III-20 (7 mM) containing hydrophilic groups, 49mg of conductive polymer monomer IV-20 (3 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.28V, the scanning speed is 50mV/s, and 2 circles are scanned, so that the bluish copolymer VI-20 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 258ng cm -2 The anti-adhesion effect is better.
Example 21:
by adopting electrochemical polymerization, 177mg of conductive high molecular monomer III-21 (7 mM) containing hydrophilic groups, 71mg of conductive high molecular monomer IV-21 (3 mM) copolymerized with bio-coupling groups, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate octyl ester (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PEDOT: PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.65V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the copolymer VI-21 with the color of blue can be obtained on a working electrode.
In this embodiment, the conductive polymer monomer containing hydrophilic group and the conductive polymer monomer containing bio-coupling groupThe structural formula is shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 137ng cm -2 The anti-adhesion effect is good.
Example 22:
by adopting electrochemical polymerization, 200mg of conductive polymer monomer III-22 (7 mM) containing hydrophilic groups, 65mg of conductive polymer monomer IV-22 (3 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile are added into an electrolytic bath, a PEDOT (PSS) film is taken as a counter electrode, ag/Ag + is taken as a reference electrode, the polymerization is carried out by applying a scanning cyclic voltammetry, the scanning range is-0.6-1.2V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the bluish copolymer VI-22 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1.PEDOT PSS film protein adhesion amount 602ng cm -2 In this example, the amount of sample stuck was 120ng cm -2 And the anti-adhesion effect is good.
Example 23:
adopting electrochemical polymerization, adding 167mg of conductive polymer monomer III-23 (9.9 mM) containing hydrophilic groups, 1mg of conductive polymer monomer IV-23 (0.1 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, taking a PEDOT (polymer dispersed solid state imaging) PSS film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.2V, the scanning speed is 50mV/s, and 2 circles are scanned, namely the blue copolymer VI-23 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 90ng cm -2 The anti-adhesion effect is very good.
Example 24:
adopting electrochemical polymerization, adding 118mg of conductive polymer monomer III-24 (7 mM) containing hydrophilic groups, 35mg of conductive polymer monomer IV-24 (3 mM) copolymerized with a biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, using PEDOT: PSS film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.225V, the scanning speed is 100mV/s, and 2 circles are scanned, namely the blue-biased copolymer VI-24 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 86ng cm -2 The anti-adhesion effect is very good.
Example 25:
adopting electrochemical polymerization, adding 143mg of conductive polymer monomer III-25 (8.5 mM) containing hydrophilic group, 17mg of conductive polymer monomer IV-25 (1.5 mM) copolymerized with biological coupling group, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, taking PEDOT: PSS film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.185V, the scanning speed is 100mV/s, and 5 circles are scanned, namely the blue-like copolymer VI-25 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of adhesion of the sample was 77ng cm -2 The anti-adhesion effect is very good.
Example 26:
adopting electrochemical polymerization, adding 143mg of conductive polymer monomer III-26 (10 mM) containing hydrophilic groups, 32mg of lithium perchlorate (100 mM) and 50ml of acetonitrile into an electrolytic bath, taking PEDOT (PolyEthylenediamine) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.2V, the scanning speed is 100mV/s, and the scanning is 1 circle, namely the bluish copolymer V-1 can be obtained on the working electrode.
The hydrophilic group-containing derivatives in this exampleThe structural formulas of the electric polymer monomer and the conductive polymer monomer of the biological coupling group are shown in the table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of adhesion of the sample was 77ng cm -2 The anti-adhesion effect is very good.
Example 27:
adopting electrochemical polymerization, adding 204mg of conductive polymer monomer III-27 (10 mM) containing hydrophilic groups, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, taking a PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.22V, the scanning speed is 100mV/s, and 5 circles are scanned, namely the blue-biased copolymer V-2 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1.PEDOT PSS film protein adhesion amount 602ng cm -2 In this example, the amount of sample adhesion was 68ng cm -2 The anti-adhesion effect is very good.
Example 28:
adopting electrochemical polymerization, adding 186mg of conductive polymer monomer III-28 (10 mM) containing hydrophilic groups, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, taking a PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.23V, the scanning speed is 100mV/s, and the scanning is 1 circle, namely the blue-biased copolymer V-3 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1.PEDOT PSS film protein adhesion amount 602ng cm -2 In this example, the amount of sample adhesion was 68ng cm -2 The anti-adhesion effect is very good.
Example 29:
adopting electrochemical polymerization, adding 169mg of conductive polymer monomer III-29 (10 mM) containing hydrophilic groups, 532mg of lithium perchlorate (100 mM), 1.11g of sodium sulfosuccinate (50 mM) and 50ml of acetonitrile into an electrolytic bath, taking a PEDOT (PSS) film as a counter electrode and Ag/Ag + as a reference electrode, and carrying out polymerization by using a scanning cyclic voltammetry method, wherein the scanning range is-0.6-1.16V, the scanning speed is 100mV/s, and the scanning is 1 circle, namely the blue-like copolymer V-4 can be obtained on a working electrode.
The structural formulas of the hydrophilic group-containing conductive polymer monomer and the bio-couplable group-containing conductive polymer monomer in this embodiment are shown in table 1. The protein adhesion amount of PEDOT to PSS film is 602ng cm -2 In this example, the amount of sample adhesion was 68ng cm -2 The anti-adhesion effect is very good.
In summary, the structural formulas of the conductive polymer monomers containing bio-couplable functionalized groups and the hydrophilic groups used in examples 1-29 are shown in table 1.
TABLE 1 information of monomers and structural formulae used in examples 1 to 29 of the present invention
Figure BDA0002540013570000171
Figure BDA0002540013570000181
Figure BDA0002540013570000191
Figure BDA0002540013570000201
Figure BDA0002540013570000211
Figure BDA0002540013570000221
From the above table 1 and the examples 1 to 29 of the present invention, it can be seen that the non-specific adhesion resistance of the biomimetic functionalized PEDOT/PSS film containing a hydrophilic group or both a hydrophilic group and a bio-couplable group, prepared according to the sequence of the examples, is generally good, and in the copolymer, when the content of the non-specific adhesion resistant monomer is not less than 70% (from example 20 to PSS film, the monomer content is 70% or more), the non-specific adhesion resistance of the biomimetic functionalized film is significantly improved compared to the initial PEDOT/PSS film, the amount of the adhesive protein is reduced by about 10 times, and the presence of the bio-couplable functional group (content is 30%) can ensure the smooth coupling of the functionalized film and the target recognition molecule. In particular, the zwitterionic phosphorylcholine functionalized conductive polymer (III-29) material has the most excellent anti-adhesion performance among four anti-adhesion monomers, and in addition, the monomers III-26, III-27, III-28, III-29 containing hydrophilic groups such as zwitterions can realize good non-specific adhesion resistance only by polymerizing one circle on the PEDOT: PSS film (examples 26, 27, 28, 29). In some embodiments, the bionic functional conductive polymer containing hydrophilic groups and bio-coupling groups is introduced through the copolymerization of conductive polymers on PEDOT and PSS films, so that the specific binding with a detected object is realized under the background of maximum nonspecific adhesion resistance while the conductivity of the material is maintained or even enhanced, and finally the selective effect is realized. The bionic functionalized PEDOT/PSS film which only contains hydrophilic groups or contains both hydrophilic groups and bio-couplable groups and is prepared by the embodiment of the invention has stronger non-specific adhesion resistance, can also have the capability of coupling with biomolecules, further has the capability of identifying cells, viruses and biomolecules, can be applied to various bioelectronic devices based on PEDOT/PSS, and particularly can be integrated in surface electrode devices or transistor devices, thereby having very wide application prospect. The preparation method of the bionic polymer in the embodiment has strong operability and is simple and feasible.
The biomimetic functionalized PEDOT PSS film has a double-layer structure, the PEDOT PSS film is arranged on the bottom layer, the biomimetic functionalized conductive polymer is arranged on the upper layer, the conductive polymer can be formed by homopolymerization of a monomer containing a hydrophilic group or copolymerization of the monomer containing the hydrophilic group and a monomer containing a biological coupling group, and the polymerization methods comprise solution oxidation deposition, oxidation vapor deposition and electrochemical deposition polymerization. The bionic functionalized PEDOT/PSS film prepared by the invention can be integrated on the surface of a microelectrode or a channel of a transistor, can obviously inhibit nonspecific adhesion interference under complex biological environment conditions, can further realize specific action with cells, viruses and biomolecules, can realize specific binding with target biomolecules under the background of maximum nonspecific adhesion resistance, and can effectively improve the selectivity and accuracy of device sensing or recording. The bionic functionalized material has strong non-specific adhesion resistance, excellent biomolecule coupling capacity and simple process, and is suitable for industrial production.
While the embodiments of the invention have been described with reference to the drawings, the invention is not limited to the above embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the invention shall be equivalent substitutions, as long as the purpose of the invention is met, and the invention shall fall within the protection scope of the invention as long as the technical principle and inventive concept of the biomimetically functionalized PEDOT, PSS film and the preparation method thereof are not departed from the technical principle and inventive concept of the invention.

Claims (8)

1. A bionically functionalized PEDOT PSS film is characterized in that: the film has a double-layer structure, wherein the bottom layer is PEDOT (poly ethylene terephthalate) (PSS) film, and the upper layer is bionic functionalized conductive high polymer material; wherein the upper layer conductive polymer contains hydrophilic group, and can repel adhesion of cell, virus, fungus, bacteria and biomolecule,
the conductive polymer material contains a monomer unit represented by the structural formula (I):
Figure FDA0003914311620000011
in formula (I):
Figure FDA0003914311620000012
the repeating unit constituting the main chain of the conductive polymer is
Figure FDA0003914311620000013
Figure FDA0003914311620000014
And derivatives thereof;
-L 1 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -wherein x, y are integers and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 2 is- (CH) 2 ) x -、-(CH 2 ) x -O-、-CO-O-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、-C(CH 3 ) 2 -CO-O-(CH 2 ) x 、-CH(CH 3 )-O-(CH 2 ) x 、-S-CH 2 -CH 2 -O-(CH 2 ) x 、-S-CH 2 -CH(CH 3 )-CO-O-(CH 2 ) x Wherein x is an integer and is more than or equal to 0 and less than or equal to 20;
-R 2 is composed of
Figure FDA0003914311620000015
Wherein p is a positive integer, and 1. Ltoreq. P.ltoreq.30,
the conductive polymer contains a monomer unit shown in a formula (II) in addition to the monomer unit shown in the formula (I):
Figure FDA0003914311620000016
in formula (II):
Figure FDA0003914311620000021
the repeating unit constituting the main chain of the conductive polymer is
Figure FDA0003914311620000022
Figure FDA0003914311620000023
And derivatives thereof;
-L 3 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -NH-CO-O-、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y-, wherein x and y are integers, and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 4 -is-O-, -CO-O-, -O-CH 2 -CO-O-、-S-(CH 2 ) x -CO-O-(CH 2 ) y -、-CO-NH-(CH 2 ) x -、-NH-(CH 2 ) x -、-NH-CO-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、
Figure FDA0003914311620000024
Figure FDA0003914311620000025
Wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 20,0 and less than or equal to 20;
-R 3 is-COOH, -NH 2 、-O-NH 2 、-N 3 、
Figure FDA0003914311620000026
Any one of the above-mentioned (b) and (c),
wherein the content of the monomer unit of the formula (I) is 70% by weight or more.
2. PSS film according to claim 1, characterized in that it is biomimetically functionalized PEDOT
Figure FDA0003914311620000027
Independently of each other are
Figure FDA0003914311620000028
And derivatives thereof.
3. PSS film according to claim 1, characterized in that: -L 1 Is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -wherein x, y are integers and 0 ≦ x ≦ 10,0 ≦ y ≦ 10; -L 2 Is- (CH) 2 ) x -、-(CH 2 ) x -O-、-CO-O-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、-C(CH 3 ) 2 -CO-O-(CH 2 ) x 、-CH(CH 3 )-O-(CH 2 ) x 、-S-CH 2 -CH 2 -O-(CH 2 ) x 、-S-CH 2 -CH(CH 3 )-CO-O-(CH 2 ) x Wherein x is an integer and is more than or equal to 0 and less than or equal to 10.
4. PSS film according to claim 1, characterized in that: -L 3 Is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -NH-CO-O-、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y-, wherein x and y are integers, and 0. Ltoreq. X.ltoreq. 20,0. Ltoreq. Y.ltoreq.20; -L 4 -is-O-, -CO-O-, -O-CH 2 -CO-O-、-S-(CH 2 ) x -CO-O-(CH 2 ) y -、-CO-NH-(CH 2 ) x -、-NH-(CH 2 ) x -、-NH-CO-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、
Figure FDA0003914311620000031
Figure FDA0003914311620000032
Wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 10,0 and less than or equal to 10.
5. PSS film according to any of claims 1 to 4, characterized in that: the biomimetic functionalized PEDOT: PSS film can be used as an interface for contacting devices with cells, viruses and biomolecules.
6. PSS film according to any of claims 1-4, characterized in that: the bionic functionalized PEDOT/PSS film can reject adhesion of cells, viruses, fungi, bacteria and biomolecules and also has a specific effect on the cells, the viruses and the biomolecules.
7. PSS film according to any of claims 1-4, characterized in that: the bionic functionalized PEDOT/PSS film can be integrated on the surface of an electrode or a channel of a transistor, so that nonspecific adhesion interference under complex biological environment conditions is inhibited, and the sensing or recording selectivity and accuracy of a device are improved.
8. The preparation method of the biomimetic functionalized PEDOT: PSS film according to claim 1, characterized in that the preparation method of the conductive polymer is copolymerization:
a monomer of formula (I):
Figure FDA0003914311620000041
in formula (I'):
-R 1' the repeating unit constituting the main chain of the conductive polymer is
Figure FDA0003914311620000042
Figure FDA0003914311620000043
And derivatives thereof;
-L 1 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -wherein x, y are integers and 0 ≦ x ≦ 20,0 ≦ y ≦ 20;
-L 2 is- (CH) 2 ) x -、-(CH 2 ) x -O-、-CO-O-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、-C(CH 3 ) 2 -CO-O-(CH 2 ) x 、-CH(CH 3 )-O-(CH 2 ) x 、-S-CH 2 -CH 2 -O-(CH 2 ) x 、-S-CH 2 -CH(CH 3 )-CO-O-(CH 2 ) x Wherein x is an integer and is more than or equal to 0 and less than or equal to 20;
-R 2 is composed of
Figure FDA0003914311620000044
Wherein p is a positive integer, and 1. Ltoreq. P.ltoreq.30.
With a monomer of formula (II):
Figure FDA0003914311620000045
in formula (II'):
-R 1” the repeating unit constituting the main chain of the conductive polymer is
Figure FDA0003914311620000046
Figure FDA0003914311620000051
And derivatives thereof;
-L 3 is- (CH) 2 ) x -、-(CH 2 ) x -O-(CH 2 ) y -、-(CH2) x -O-CO-(CH 2 ) y -、-(CH 2 ) x -NH-CO-O-、-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-(CH 2 ) x -O-(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -(CH 2 -CH 2 -O) y -、-O-(CH 2 ) x -O-(CH 2 -CH 2 -O) y-, wherein x and y are integers, and 0. Ltoreq. X.ltoreq. 20,0. Ltoreq. Y.ltoreq.20;
-L 4 -is-O-, -CO-O-, -O-CH 2 -CO-O-、-S-(CH 2 ) x -CO-O-(CH 2 ) y -、-CO-NH-(CH 2 ) x -、-NH-(CH 2 ) x -、-NH-CO-(CH 2 ) x -、-O-CO-(CH 2 ) x -、-CO-NH-(CH 2 ) x -、
Figure FDA0003914311620000052
Figure FDA0003914311620000053
Figure FDA0003914311620000054
Wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 20,0 and less than or equal to 20;
-R 3 is-COOH, -NH 2 、-O-NH 2 、-N 3 、
Figure FDA0003914311620000055
Any one of them.
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