CN112129822A - Solid-state electrochemical luminescence sensor and preparation method and application thereof - Google Patents
Solid-state electrochemical luminescence sensor and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
Abstract
The invention discloses a solid-state electrochemical luminescence sensor and a preparation method and application thereof, wherein the solid-state electrochemical luminescence sensor comprises an electrode, the surface of the electrode is provided with a modification layer of a thermal activation delayed fluorescent polymer.
Description
Technical Field
The invention belongs to the technical field of electrochemical luminescence detection, and particularly relates to a solid-state electrochemical luminescence sensor and a preparation method and application thereof.
Background
Electrochemiluminescence (ECL) refers to a process in which an ECL active substance is electrically excited to cause an electrochemical redox reaction on the surface of a working electrode, thereby generating radical ions, and then the radical ions generate an excited state through a high-energy electron transfer reaction, and when the radical ions transition back to a ground state, energy is radiated in the form of light. The electrochemical luminescence technology is an analysis technology combining an electrochemical method and a chemiluminescence method, and has the advantages of wide linear range, high sensitivity, good reproducibility, simple operation, easier control and the like. Through research and development in recent 60 years, the ECL theory and technology are gradually established at present, and the ECL theory and technology become a powerful modern analysis sensing and detection means and are used in the fields of immunoassay, ion analysis, nucleic acid detection, water quality detection and the like. Compared with chemiluminescence, electrochemiluminescence is combined with an electrochemical regulation and control means, so that the obtained background signal is lower, the information is richer, and the electrochemiluminescence has remarkable technical advantages in the aspects of obtaining high sensitivity, high signal-to-noise ratio, specificity identification and the like.
Compared with a liquid-phase ECL detection system, the solid-state ECL detection based on the surface modification of the working electrode has the advantages of simpler structure, more convenience and easiness in realizing miniaturization. In addition, based on the stable immobilization of the high-efficiency luminescent material system on the electrode, the ECL has higher luminous efficiency and is more stable. Therefore, solid-state ECL detection is a key research area for ECL application research and is receiving much attention. From the light-emitting system, the material system applied to the solid ECL mainly includes three major types, namely an inorganic system of an organic metal complex, a semiconductor nano material system and an organic polymer system. For organometallic complex systems, the most typical example involves the use of classical bipyridyl ruthenium complexes (Ru (bpy)3 2+) Immobilization to the working electrode by mixing with cation exchange electrolyte Nafion polymer (j.am. chem. soc.1980,102,6641) also involves chemically grafting a classical metal iridium complex to an organic polymeric side chain and then coating the whole onto the working electrode (chem. eur. j.2019,25, 12671-12683). Such solid ECL has the disadvantage that ECL luminescent materials are rich in expensive precious metals and are relatively costly. Semiconductor nanomaterial systems are of a wide variety, including, for example, classical silicon quantum dots, gold nanoclusters, perovskite nanocrystals, organic crystallites, and the like (Science 2002,296, 1293-1297; angelw.chem. -int.edit.2020,59, 9982-9985; chem.sci.2019,10, 4497-4501; j.am.chem.soc.2017,139, 8772-8776.). Such sodium saltThe ECL luminescent property of the rice material obviously depends on the structural morphology characteristics of the nano material, the control of surface defect state behaviors and the like, the material synthesis process is complex, the surface defect state behaviors obviously limit the electrochemistry and the ECL performance, and the structural stability is often poor. For solid-state ECL light emitting systems of organic polymers, organic polymer materials currently used for ECL research mainly include materials of PPV series (chem. phys.lett.1994,226, 115-120; j. phys. chem.b 2006,110,15719-15723.), P3HT (j. appl. phys.1997,82,1847-1852.), F8BT (j.am. chem.soc.2008,130,8906-8907), and recently developed silole-containing polymer dots (anal. chem.2016,88,845-850), D-a type conjugated polymer nanodots having aggregation-induced fluorescence enhancement effect (j.phys. chem.lett.2018,9,5296-5302), and the like. Compared with the first two materials, the organic polymer system takes the carbon-rich aromatic hydrocarbon as a framework, and has the advantages of no noble metal unit, easy adjustment of photoelectric properties, easy functional modification, good film forming property, low price, low toxicity and the like. The relevant literature not only studies the electrochemistry and ECL basic behaviors of the materials, but also successfully develops the application research of the materials in biosensing (chem.Sci.2019,10, 6815-6820). However, the above reported organic polymer solid-state ECL detection systems are all traditional fluorescent systems, and in essence, the triplet excitons in such materials returning to the ground state are usually forbidden to transit, regardless of the bulk material or the organic polymer nanomaterial subjected to subsequent nano-coating. According to the theory of spin quantum statistics, the generation ratio of excitons in singlet and triplet states under electric excitation is about 25%: 75%, neither annihilation ECL pathway nor co-reactant ECL pathway can be utilized, and only triplet excitons generated by recombination on these light emitting materials are converted back to ground state by 25% of singlet excitons (angelw.chem.int.ed.2014, 53, 6993-6996). For this reason, all existing organic polymer solid-state ECL detection systems are limited by their common traditional fluorescent physical properties, and their ECL efficiency levels and applications are limited by theory and practice.
The thermally activated delayed fluorescence organic luminescent material is a new generation organic photoelectric material, which is different from the traditional fluorescence. Fluorescence in the conventional sense means excitation of the luminescent substanceSinglet (e.g. first excited singlet S)1) Direct deactivation to ground state (S)0) The radiative luminescence process in time, typically has a lifetime in the order of nanoseconds. Delayed fluorescence differs from that which arises from an excited triplet state (e.g., first excited triplet T)1) The transition generates an excited singlet state (e.g., the first excited singlet state S)1) The latter radiation transition process. Due to the accompanying T1To S1The fluorescence lifetime is significantly extended to the order of microseconds or even seconds by the slow conversion process of (1), and is therefore called delayed fluorescence. Delayed fluorescence is classified into P-type delayed fluorescence and E-type delayed fluorescence. The P-type delayed fluorescence is derived from the process of quenching two excited triplet states to generate one excited singlet state (TTA process). The E-type delayed fluorescence corresponds to the lowest excited singlet state (S) of the material1) And the lowest excited triplet state (T)1) Energy level difference (Δ E) therebetweenST) Very close to the situation (comparable to the thermal energy in the environment, typically not more than 0.3 eV). T in such luminescent substances by thermal activation of the environment1The triplet excitons will undergo reverse intersystem crossing (RISC) process and return to the lowest excited singlet S1Finally transitioning back to the ground state S0And the light is radiated. Since the delayed fluorescence of E type has the obvious characteristic of thermal activation, it is also called Thermal Activated Delayed Fluorescence (TADF). Under the condition of electric excitation, considering the generation ratio of singlet excitons and triplet excitons and the statistic characteristics of triplet state spin (25%/75%), the traditional fluorescent materials and the P-type delayed fluorescent materials have different degrees of triplet state exciton non-radiative recombination loss, the maximum exciton radiation utilization rate is respectively 25% and 62.5%, and the thermal activation delayed fluorescent TADF material can realize the radiation utilization of all singlet state excitons and triplet state excitons, so that the luminous efficiency can reach 100%. In 2014, Ishimat et al firstly reported the solution state ECL phenomenon of the small molecule TADF luminescent material 4CzIPN, and combined with photophysical analysis and annihilation type ECL characterization analysis, the effectiveness of TADF property in improving ECL luminescent efficiency is proved (Angew. chem. int. Ed.2014,53, 6993-6996). However, since the small-molecule TADF material cannot be applied to solid-state ECL detection analysis, the application of the solid-phase ECL based on the TADF mechanism is still in the fieldA blank state.
Disclosure of Invention
In view of the problems of the prior art, a first object of the present invention is to provide a solid-state electrochemical luminescence sensor, which fully utilizes all singlet and triplet excitons generated under an electrical excitation condition to realize ECL luminescence, and has excellent ECL performance and high luminescence efficiency.
The above object of the present invention is achieved by the following means:
a solid-state electrochemical luminescence sensor comprises an electrode, wherein the surface of the electrode is provided with a modification layer of a heat-activated delayed fluorescence polymer.
Compared with the prior art, the invention can be made into a solid-state electrochemical luminescence sensor by using the heat-activated delayed fluorescence polymer modified electrode, and can be used in the fields of analysis and detection such as immunoassay, ion analysis, nucleic acid detection, water quality detection and the like.
In a preferred embodiment, the heat-activated delayed fluorescence polymer is selected from conjugated polymers having triazine groups in side chains represented by formula (I):
wherein R is1、R3Independently selected from C1-C30 alkyl, C1-C30 alkoxy, C6-C35 unsubstituted aryl or C6-C35 substituted aryl;
R2selected from C1-C30 alkyl, C1-C30 alkoxy, C6-C35 unsubstituted aryl, C6-C35 unsubstituted phenol, C6-C35 substituted aryl or C6-C35 substituted phenol;
0.01≤x≤0.25；
n is an integer of 2 to 200.
In the prior art, the conjugated polymer with triazine group in the side chain shown in formula (1) is used as a luminescent layer in an electroluminescent device and is used for manufacturing an organic electroluminescent diode display or lighting device. The inventor finds that the conjugated polymer with the side chain containing the triazine group can be electrochemically oxidized under the action of electric excitationReaction and electrochemical reduction reaction, corresponding to the generation of cationic free radicals (R)·+) And an anionic radical (R)·-). Then, R·+And R·-The radical ions meet with each other to generate high-energy electron transfer reaction, thereby forming an excited state. The excited state is divided into singlet excitons S according to the spin properties1And triplet exciton T1. Singlet excitons S1Meaning that the spin direction of the electron pair forming the exciton is reversed. Triplet exciton T1Meaning that the spin direction of the electron pair forming the exciton is the same. According to the quantum spin statistical theory, under the condition of electric excitation, S1/T1The initial formation ratio of excitons is approximately 1: 3. Singlet S1The excitons will be excited to the ground state S by direct de-excitation0In a manner that achieves ECL luminescence (PF-ECL) characteristic of transient fluorescence. And a triplet state T1The exciton is based on reverse intersystem crossing (RISC) approach, and the spin is switched into S1Excitons in the state of being de-excited to the ground state S0And realizing the radiation recombination process. Since the rate of the RISC process is compared to S1To S0The internal conversion rate process of (a) is slower, so that the fluorescence lifetime of the final part based on the RISC process is longer, which is characterized by delayed fluorescence (DF-ECL), and the electrochemical luminescence principle is shown in FIG. 1. The S of the side chain triazine group-containing conjugated polymer represented by the formula (1)1And T1The energy difference between them is very small, so its RISC process is very efficient (the real corresponding RISC conversion efficiency is nearly 100%). Therefore, the conjugated polymer with the triazine group contained in the side chain shown in the formula (1) is used as an electrode modification material of the solid-state electrochemical luminescence sensor, and all S is finally excited under electric excitation1And T1Excitons will be 100% available, enabling efficient ECL luminescence. And theoretically the upper limit of the luminescence quantum efficiency of solid-state ECL based on this TADF mechanism would be 100%.
Preferably, in formula (I), R is1And R3Independently selected from C3-C20 alkyl, C3-C20 alkoxy, C6-C20 unsubstituted aryl or C8-C25 substituted aryl, wherein the substituent on the substituted aryl is one or two of C1-C12 alkyl and C1-C12 alkoxy.
Preferably, said R is2Is C3-C25 alkyl, C2-C20 alkoxy, C6-C20 unsubstituted aryl, C6-C20 unsubstituted phenol, C8-C25 substituted aryl or C8-C25 substituted phenol. The substituent in the substituted phenol group is one or two of C1-C12 alkyl and C1-C12 alkoxy; the substituent in the substituted aryl is one or two of C1-C12 alkyl and C1-C12 alkoxy.
Preferably, the side chain triazine group-containing conjugated polymer represented by the formula (I) is represented by the formula (I-a), the formula (I-b), the formula (I-c), the formula (I-d), the formula (I-e), the formula (I-f) or the formula (I-g):
wherein n is an integer of 2 to 200.
In another preferred embodiment, the thermally activated delayed fluorescence polymer is selected from thermally activated delayed fluorescence polymers represented by formula (II):
wherein Ar1 is a 2, 7-fluorene derivative or a 2, 7-carbazole derivative;
ar2 is aryl of C6-C20;
R1、R2、R3、R4and R5Independently selected from hydrogen, alkyl of C1-C30, alkoxy of C1-C30 or substituted aryl of C6-C50;
0.0001≤x≤0.25；
n is an integer of 1 to 200.
Similarly, in the prior art, the thermally activated delayed fluorescence polymer of formula (II) is used as a light emitting layer in an organic electroluminescent diode device forAnd manufacturing the light-emitting diode display. The inventor finds that the polymer can generate electrochemical oxidation reaction and electrochemical reduction reaction under electric excitation to form S in an excited state1And T1The energy difference between the two elements is very small, the RISC conversion efficiency is high, and the method can be used for manufacturing electrochemical light-emitting devices.
Preferably, said R is1、R2、R3、R4And R5Independently selected from hydrogen, alkyl of C3-C25, alkoxy of C3-C25 or substituted aryl of C8-C30; the substituent on the substituted aryl is one or two of C1-C20 alkyl and C1-C20 alkoxy.
Preferably, Ar1 is a 2, 7-fluorene derivative of C15-C50 or a 2, 7-carbazole derivative of C15-C50.
Preferably, Ar1 is formula (II-1-a) or formula (II-1-b):
wherein R is6And R7Independently selected from alkyl of C1-C20, alkoxy of C1-C20 or substituted aryl of C6-C30.
Preferably, Ar2 is formula (II-2-a), formula (II-2-b) or formula (II-2-c),
preferably, the heat-activated delayed fluorescence polymer represented by formula (II) is of formula (II-a), formula (II-b), formula (II-c) or formula (II-d):
wherein n is an integer of 1 to 200.
The electrode adopts working electrodes commonly used in the field, such as a glassy carbon electrode, a graphite electrode, an ITO electrode and a noble metal electrode.
The second purpose of the invention is to provide a preparation method of the solid-state electrochemical luminescence sensor, which comprises the following steps: and coating the solution of the heat-activated delayed fluorescence polymer on the surface of the electrode, drying, and forming a modification layer of the heat-activated delayed fluorescence polymer on the surface of the electrode to obtain the solid-state electrochemical luminescence sensor.
The coating method is not limited and can be a method that is commonly used in the art, such as drop coating, spin coating, blade coating, and the like, and the thermally activated delayed fluorescence polymer can be formed into a film. Or the thermal activation delayed fluorescence polymer can be pretreated by adopting a nano-coating method, and then the film is formed on the surface of the electrode by adopting methods such as drop coating, spin coating, blade coating and the like.
The solvent used for preparing the solution of the thermally activated delayed fluorescence polymer is a general solvent as long as it can effectively dissolve the thermally activated delayed fluorescence polymer and does not react with the thermally activated delayed fluorescence polymer, for example, chlorobenzene, etc., and is not limited thereto.
The third purpose of the invention is to provide the application of the solid-state electrochemical luminescence sensor in immunoassay, ion analysis, nucleic acid detection or water quality detection.
In practical application, the solid-state electrochemical luminescence sensor can be used as a working electrode to form a solid-state electrochemical luminescence device (solid-state ECL device) together with a certain solvent and an electrolyte, and is used for testing the electrochemical luminescence performance of the solid-state electrochemical luminescence sensor or detecting a certain object to be tested.
The solid-state ECL device constructed may be an annihilation solid-state ECL device, an "oxidation-reduction" type coreactant solid-state ECL device, or a "reduction-oxidation" type coreactant solid-state ECL device.
The basic structure of the annihilation type solid ECL device comprises an electrolytic cell and an electrochemical test control power supply, wherein a working electrode (namely a solid-state electrochemical luminescence sensor) with a modification layer of a thermal activation delayed fluorescent polymer on the surface, a counter electrode, a reference electrode, a solvent and a supporting electrolyte are arranged or contained in the electrolytic cell, wherein the supporting electrolyte and the solvent are mutually dissolved to form a liquid-phase electrochemical environment.
The basic structure of an "oxidation-reduction" type co-reactant solid-state ECL device includes an electrolytic cell and an electrochemical test control power supply. The method comprises the steps of arranging or containing a working electrode (namely a solid-state electrochemical luminescence sensor) with a modification layer of a thermally activated delayed fluorescent polymer on the surface, a counter electrode, a reference electrode, a solvent, a supporting electrolyte and an oxidation-reduction type coreactant in an electrolytic cell, wherein the supporting electrolyte, the solvent and the oxidation-reduction type coreactant are mutually dissolved to form a liquid-phase electrochemical environment.
The basic structure of the solid ECL device of the reduction-oxidation co-reactant comprises an electrolytic cell and an electrochemical test control power supply. A working electrode (namely a solid-state electrochemical luminescence sensor) with a modification layer of a thermally activated delayed fluorescent polymer on the surface, a counter electrode, a reference electrode, a solvent, a supporting electrolyte and a reduction-oxidation type coreactant are arranged or contained in an electrolytic cell, wherein the supporting electrolyte, the solvent and the reduction-oxidation type coreactant are mutually dissolved to form a liquid-phase electrochemical environment.
The solvent, the supporting electrolyte, the co-reactant, the electrochemical test control power supply and the driving mode in the solid ECL structure have no special requirements, and the method has no special requirements for various procedures for preparing the solid ECL and the specific structural layout of the solid ECL component, and adopts general operation in the industry.
Compared with the prior art, the invention has the following beneficial effects:
the solid electrochemical luminescence sensor is constructed by utilizing the thermally activated delayed fluorescent polymer, spin forbidden resistance does not exist under electric excitation, all singlet excitons and triplet excitons generated under the condition of electric excitation can be completely utilized to realize ECL luminescence, the ECL performance is excellent, and the luminescence efficiency is high.
Drawings
FIG. 1 is a schematic diagram of the principle of luminescence based on electrochemical luminescence of a thermally activated delayed fluorescent material.
In fig. 2, a is a basic structure of an annihilation-type solid ECL device, b is a basic structure of an "oxidation-reduction" type coreactant solid ECL device, and c is a basic structure of a "reduction-oxidation" type coreactant solid ECL device.
FIG. 3 is a graph of the fluorescence lifetime of the PCzAPT10 modified electrode of example 1;
FIG. 4 is a graph of the signal from the electrochemiluminescence reaction test of the annihilation solid-state ECL of example 1.
FIG. 5 is a graph of the signals obtained from the electrochemiluminescence reaction test of the "oxidation-reduction" type co-reactant solid ECL of example 1.
FIG. 6 is an electrochemiluminescence spectrum of the "oxidation-reduction" type co-reactant solid ECL in example 1 at a positive voltage of 1.5V.
FIG. 7 is a plot of the signals obtained from the electrochemiluminescence reaction test of the "reduction-oxidation" type co-reactant solid ECL of example 1.
FIG. 8 is a signal curve obtained from an electrochemiluminescence reaction test of the annihilation solid-state ECL of example 2.
FIG. 9 is a graph of the signals obtained from the electrochemiluminescence reaction test of the "oxidation-reduction" type co-reactant solid ECL of example 2.
FIG. 10 is a plot of the signals obtained from the electrochemiluminescence reaction test of the "reduction-oxidation" type co-reactant solid ECL of example 2.
FIG. 11 is a signal curve obtained from an electrochemiluminescence reaction test of the annihilation solid-state ECL of example 3.
FIG. 12 is a graph of the signals obtained from the electrochemiluminescence reaction test of the "oxidation-reduction" type co-reactant solid ECL in example 3.
In fig. 2,1 is an electrolytic cell, 2 is a working electrode, 3 is a counter electrode, 4 is a reference electrode, 5 is a solvent, 6 is a supporting electrolyte, 7 is an electrochemical test control power supply, 8 is a modification layer of a thermally activated delayed fluorescence polymer, 9 is an "oxidation-reduction" type coreactant, and 10 is a "reduction-oxidation" type coreactant; in fig. 4,5, and 7 to 12, the bare working electrode is a bare electrode, and the polymer modified electrode represents a thermally activated delayed fluorescence polymer modified electrode in the corresponding embodiment.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It is to be understood that the present invention is not limited to the embodiments described below, which are merely illustrative embodiments of the present invention.
Example 1
The embodiment provides a solid-state electrochemical luminescence sensor which comprises a glassy carbon electrode, wherein the surface of the glassy carbon electrode is provided with a modification layer of a thermal activation delayed fluorescence polymer. The heat-activated delayed fluorescence polymer is as follows: poly-3,6-carbazole-9, 9-dihexyl-10- (4- (4,6-di-tert-butyl-1,3,5-triazin-2-yl) phenyl) -9,10-dihydroacridine (poly-3,6-carbazole-9, 9-dihydroacridine-10- (4- (4,6-di-tert-butyl-1,3,5-triazin-2-yl) phenyl) -9,10-dihydroacridine, abbreviated as PCzAPT), wherein the mol ratio of APT unit (9,9-dihexal-10- (4- (4,6-di-tert-butyl-1,3,5-triazin-2-yl) phenyl) -9,10-dihydroacridine) is 10, so the PCzAPT10 is abbreviated as PCzAPT. The material is a TADF organic polymer material which does not contain any metal element, is cheap and easy to obtain, has low toxicity and good chemical stability, and has good film forming property. After the solution is prepared, a film can be formed by blade coating, drop coating, spin coating, and the like. Until now, no one has studied the electrochemiluminescence properties of the PCzAPT10 polymer. The material is synthesized in the literature and the patent reports (adv. Opt. Mater.2018,6,1701320; ZL201710115395.3.) and can be synthesized and prepared by referring to the corresponding literature and the corresponding patent.
The chemical structural formula of PCzAPT10 is shown below:
wherein n is an integer of 2 to 200.
The preparation method of the solid-state electrochemical luminescence sensor of the embodiment comprises the following steps:
(1) preparation of stock solution: 0.010g of PCzAPT10 was weighed into 10mL of chlorobenzene and ultrasonically dispersed for 30min to complete dissolution to give 1mg/mL of a mother liquor. 1mL of the mother liquor was aspirated and diluted to 10mL with chlorobenzene to obtain a stock solution of 0.1mg/mL of PCzAPT10 chlorobenzene, which was stored away from light.
(2) Pretreating a glassy carbon electrode: polishing the glassy carbon electrode by using 0.3 mu m and 0.05 mu m aluminum oxide powder, then performing ultrasonic cleaning by using ultrapure water, ethanol and ultrapure water in sequence, and drying the surface of the electrode by using nitrogen.
(3) Preparation of PCzAPT10 modified working electrode: and moving 5 mu L of PCzAPT10 chlorobenzene stock solution to the surface of the treated glassy carbon electrode by a liquid-moving gun each time, dripping 20 mu L of the solution totally, and carrying out vacuum drying at 37 ℃ for 30min to form a film, thus obtaining the PCzAPT10 modified electrode which is used as a solid electrochemical luminescence sensor.
The solid-state electrochemiluminescence sensor is used as a working electrode to form an annihilation type solid ECL device, an oxidation-reduction type coreactant solid ECL device or a reduction-oxidation type coreactant solid ECL device, and the electrochemiluminescence performance of the annihilation type solid ECL device is tested, wherein the structures of various ECL devices are shown in FIG. 2.
1) Annihilation solid-state ECL device:
a three-electrode working system, a PCzAPT10 modified electrode, a silver wire electrode, a platinum wire electrode, a counter electrode and tetrabutylammonium perchlorate (TBAP) serving as a supporting electrolyte are used as working electrodes, the three-electrode system is immersed in acetonitrile solution containing 0.1M TBAP, the electrochemiluminescence performance of the three-electrode working system is detected by an MPI-EII type electrochemiluminescence analyzer under the nitrogen atmosphere, the initial voltage is set to be 0V, the low voltage is set to be-1.6V, the high voltage is set to be 1.4V, and the sweep rate is 0.1V/s.
FIG. 3 is a fluorescence lifetime curve of a PCzAPT10 modified electrode, and it can be seen that the material shows typical thermally activated delayed fluorescence characteristics, and besides a nanosecond short lifetime interval, the material also has a subtle long lifetime characteristic.
Figure 4 is a graph of ECL signal for a PCzAPT10 modified electrode for comparison while also testing ECL signal with a bare electrode as the working electrode under the same conditions. As shown in the figure, no ECL signal appears on the bare electrode, and after the polymer modification of PCzAPT10, an obvious ECL signal appears from a negative voltage of-1.1V.
2) "Oxidation-reduction" type coreactant solid-state ECL device:
a three-electrode working system is adopted, a PCzAPT10 modified electrode is used as a working electrode, a silver wire electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, tetrabutylammonium perchlorate (TBAP) is used as a supporting electrolyte, tripropylamine (TPrA) is used as an oxidation-reduction type co-reactant, the three-electrode system is immersed in an acetonitrile solution containing 0.1M TBAP and 40mM tripropylamine, the initial voltage and the low voltage are set to be 0V, the high voltage is set to be 1.7V, the sweep rate is 0.1V/s, and the ECL signal is detected. For comparison, ECL signals were also tested under the same conditions with the bare electrode as the working electrode.
FIG. 5 is a signal curve obtained from the solid ECL electrochemiluminescence reaction test of the "oxidation-reduction" co-reactant of this example, and the test result reflects that ECL gradually appears from a positive potential of 1.2V and reaches a peak value around 1.6V after the working electrode is modified with PCzAPT10 polymer. This was done with a solid ECL based on a co-reactant of the "oxidation-reduction" type of thermally activated delayed fluorescence material (shown in figure 2 b).
FIG. 6 shows the ECL luminescence spectrum of the "oxidation-reduction" co-reactant solid ECL at 1.5V potential test, with a peak wavelength at 587nm, which is the luminescence of PCzAPT10, but not the luminescence of other substances in the test environment.
3) "reduction-oxidation" type coreactant solid-state ECL device:
adopting a three-electrode working system, taking a PCzAPT10 modified electrode as a working electrode, a silver wire electrode as a reference electrode, a platinum wire electrode as a counter electrode, tetrabutylammonium perchlorate (TBAP) as a supporting electrolyte, and potassium persulfate (K)2S2O8) As a ` reduction-oxidation ` type co-reactant, the three-electrode system was immersed in an acetonitrile solution containing 0.1M TBAP and 10mM persulfate, with an initial voltage and a high voltage set at 0V, a low voltage set at-1.6V, a sweep rate of 0.1V/s, under a nitrogen atmosphereThe electrochemiluminescence intensity of the sample is measured. For comparison, ECL signals were also tested under the same conditions with the bare electrode as the working electrode.
FIG. 7 shows the signal curve obtained from the solid-state ECL test of the "reducing-oxidizing" type co-reactant of PCzAPT10 macromolecule. As shown, the bare electrode only had a weak ECL signal after the potential exceeded-1.3V. For the PCzAPT10 macromolecule modified working electrode, after the potential exceeds-1.3V, obviously enhanced ECL signal appears. This was done based on a "reduction-oxidation" type co-reactant solid ECL (shown in fig. 2 c) of a thermally activated delayed fluorescence material.
Example 2
The embodiment provides a solid-state electrochemical luminescence sensor which comprises a glassy carbon electrode, wherein the surface of the glassy carbon electrode is provided with a modification layer of a thermal activation delayed fluorescence polymer. The heat-activated delayed fluorescence polymer is as follows: poly-fluorene-2, 8-dioctyl-S, S-dioxo-dibenzothiophene-2- (4- (diphenylamino) phenyl) -10,10, -dioxo-9H-thioxanthone (poly-fluoro-dibenzothiophene-S, S-dioxide-2- (4- (diphenylamino) -phenyl) -9H-thioxanthon-9-one-10, 10-dioxide, PFSOTT for short), wherein the molar ratio of the TT unit (2- (4- (diphenylamino) -phenyl) -9H-thioxanthon-9-one-10, 10-dioxide) is 5, and thus PFSOTT5 for short. The material is a TADF organic polymer material which does not contain any metal element, is cheap and easy to obtain, has low toxicity and good chemical stability, and has good film forming property. After the solution is prepared, a film can be formed by blade coating, drop coating, spin coating, and the like. No one has studied the electrochemiluminescence properties of PFSOTT5 polymer so far. The synthesis of the material has been reported in documents and patents (J.Mater.chem.C 2017,5,10715-10720; ZL201711291518.5), and the material can be synthesized and prepared by referring to corresponding documents and patents.
The chemical structural formula of PFSOTT5 is shown below:
wherein n is an integer of 2 to 200.
The preparation method of the solid-state electrochemical luminescence sensor of the embodiment comprises the following steps:
(1) preparation of stock solution: weighing 0.010g PFSOTT5 in 10mL chlorobenzene, ultrasonic dispersing for 30min until complete dissolution to obtain 1mg/mL mother liquor, sucking 1mL mother liquor, adding chlorobenzene to dilute to 10mL to obtain 0.1mg/mL PFSOTT5 chlorobenzene stock solution, and storing away from light.
(2) Pretreating a glassy carbon electrode: polishing the glassy carbon electrode by using 0.3 mu m and 0.05 mu m aluminum oxide powder, then performing ultrasonic cleaning by using ultrapure water, ethanol and ultrapure water in sequence, and drying the surface of the electrode by using nitrogen.
(3) Preparation of PFSOTT5 modified working electrode: and (3) moving 5 mu L of PFSOTT5 chlorobenzene stock solution to the surface of the treated glassy carbon electrode by a liquid-moving gun each time, dripping 20 mu L of the solution totally, and carrying out vacuum drying at 37 ℃ for 30 minutes to form a film, thus obtaining a PFSOTT5 modified electrode which is used as a solid-state electrochemical luminescence sensor.
The solid-state electrochemical luminescence sensor is used as a working electrode to form an annihilation type solid ECL device, an oxidation-reduction type coreactant solid ECL device or a reduction-oxidation type coreactant solid ECL device, and the electrochemical luminescence performance of the annihilation type solid ECL device is tested.
1) Annihilation solid-state ECL device:
a three-electrode working system is adopted, a PFSOTT5 modified electrode is used as a working electrode, a silver wire electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, tetrabutylammonium perchlorate (TBAP) is used as a supporting electrolyte, the three-electrode system is immersed into acetonitrile solution containing 0.1M TBAP, the electrochemical luminescence property of the three-electrode system is detected by an MPI-EII type electrochemical luminescence analyzer under the nitrogen atmosphere, the initial voltage is set to be 0V, the low voltage is set to be-2V, the high voltage is set to be 2V, and the sweep rate is 0.1V/s. The signals were also tested under the same conditions with the bare electrode as the working electrode for comparison.
FIG. 8 shows the signal curve obtained from the annihilation electrochemiluminescence reaction test. FIG. 8 reflects that no ECL signal appears in the bare electrode, but a significant ECL signal appears after PFSOTT5 polymer modification, starting from a negative voltage of-1.2V.
2) "Oxidation-reduction" type coreactant solid-state ECL device:
a three-electrode working system is adopted, a PFSOTT5 modified electrode is used as a working electrode, a silver wire electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, tetrabutylammonium perchlorate (TBAP) is used as a supporting electrolyte, tripropylamine (TPrA) is used as a co-reactant, the three-electrode system is immersed in acetonitrile solution containing 0.1M TBAP and 40mM tripropylamine, the initial voltage and the low voltage are set to be 0V, the high voltage is set to be 1.6V, the sweep rate is 0.1V/s, and the electrochemical luminescence intensity is detected. Meanwhile, the signal when the bare electrode was used as the working electrode was tested under the same conditions.
The test results are shown in fig. 9. Figure 9 reflects that ECL gradually appeared and the ECL intensity gradually increased starting from a positive potential of 1.1V after the working electrode modified PFSOTT5 polymer. For this purpose, solid-state ECL based on a co-reactant of the "oxidation-reduction" type of thermally activated delayed fluorescence material was implemented.
3) "reduction-oxidation" type coreactant solid-state ECL device:
adopting a three-electrode working system, adopting a PFSOTT5 modified electrode as a working electrode, a silver wire electrode as a reference electrode, a platinum wire electrode as a counter electrode, tetrabutylammonium perchlorate (TBAP) as a supporting electrolyte, and using potassium persulfate (K)2S2O8) As a co-reactant, the three-electrode system was immersed in an acetonitrile solution containing 0.1M TBAP and 10mM potassium persulfate, and the intensity of electrochemiluminescence was measured under a nitrogen atmosphere with an initial voltage set at 0V and a high voltage set at-1.8V and a sweep rate of 0.1V/s. Meanwhile, the signal when the bare electrode was used as the working electrode was tested under the same conditions.
As shown in FIG. 10, the bare electrode had a weak ECL signal after the potential exceeded-1.4V. For the PFSOTT5 macromolecule modified working electrode, after the potential exceeds-1.6V, a obviously enhanced ECL signal appears. This was done with a solid ECL based on a "reduction-oxidation" type co-reactant of thermally activated delayed fluorescent material.
Example 3
The embodiment provides a solid-state electrochemical luminescence sensor which comprises a glassy carbon electrode, wherein the surface of the glassy carbon electrode is provided with a modification layer of a thermal activation delayed fluorescence polymer. The heat-activated delayed fluorescence polymer is as follows:
poly-3,6-carbazole-9, 9-dihexyl-10- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9,10-dihydroacridine (poly-3,6-carbazole-9,9-dihexal-10- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9, 10-diazeparidine, abbreviated as pcztd), in which the molar ratio of ATD units (9,9-dihexal-10- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9,9-dimethyl-9, 10-diazeparidine) is 10, hence abbreviated as pcztd 10. The material is a TADF organic polymer material which does not contain any metal element, is cheap and easy to obtain, has low toxicity and good chemical stability, and has good film forming property. After the solution is prepared, a film can be formed by blade coating, drop coating, spin coating, and the like. Until now, no one has studied the electrochemiluminescence properties of the polymer pcztd 10. The material is synthesized in the literature and the patent reports (adv. Opt. Mater.2018,6,1701320; ZL201710115395.3.) and can be synthesized and prepared by referring to the corresponding literature and the corresponding patent.
The chemical structure of pcztd 10 is shown below:
wherein n is an integer of 2 to 200.
The preparation method of the solid-state electrochemical luminescence sensor of the embodiment comprises the following steps:
(1) preparation of stock solution: 0.010g of PCzATD10 was weighed and dissolved in 10mL of chlorobenzene, and ultrasonic dispersion was carried out for 30 minutes until complete dissolution to obtain 1mg/mL of mother liquor, and 1mL of the mother liquor was aspirated and diluted to 10mL with chlorobenzene to obtain 0.1mg/mL of PCzATD10 chlorobenzene stock solution, which was stored away from light.
(2) Pretreating a glassy carbon electrode: polishing the glassy carbon electrode by using 0.3 mu m and 0.05 mu m aluminum oxide powder, then performing ultrasonic cleaning by using ultrapure water, ethanol and ultrapure water in sequence, and drying the surface of the electrode by using nitrogen.
(3) Preparation of pczttd 10 modified working electrode: and transferring 5 mu L of PCzATD10 chlorobenzene stock solution to the surface of the treated glassy carbon electrode by a liquid transfer gun, dripping 20 mu L of the PCzATD10 chlorobenzene stock solution in total, and drying in vacuum at 37 ℃ for 30 minutes to form a film, thereby obtaining the PCzATD10 modified electrode as the solid-state electrochemical luminescence sensor. .
The solid electrochemical luminescence sensor is used as a working electrode to form an annihilation type solid ECL device or an oxidation-reduction type coreactant solid ECL device to test the electrochemical luminescence property of the solid electrochemical luminescence sensor.
1) Annihilation solid-state ECL device:
a three-electrode working system is adopted, a PCzATD10 modified electrode is used as a working electrode, a silver wire electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, tetrabutylammonium perchlorate (TBAP) is used as a supporting electrolyte, the three-electrode system is immersed into acetonitrile solution containing 0.1M TBAP, the electrochemiluminescence performance of the three-electrode system is detected by an MPI-EII type electrochemiluminescence analyzer under the nitrogen atmosphere, the initial voltage is set to be 0V, the low voltage is set to be-1.6V, the high voltage is set to be 1.6V, and the sweep rate is 0.1V/s. Meanwhile, the signal when the bare electrode was used as the working electrode was tested under the same conditions.
The test results are shown in fig. 11. It can be seen from fig. 11 that no ECL signal appears in the bare electrode, but an ECL signal appears after the polymer modification by pcztd 10, starting from a negative voltage of-1.4V.
2) "Oxidation-reduction" type coreactant solid-state ECL device:
a three-electrode working system is adopted, a PCzATD10 modified electrode is used as a working electrode, a silver wire electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, tetrabutylammonium perchlorate (TBAP) is used as a supporting electrolyte, tripropylamine (TPrA) is used as a co-reactant, the three-electrode system is immersed in acetonitrile solution containing 0.1M TBAP and 40mM tripropylamine, the initial voltage and the low voltage are set to be 0V, the high voltage is set to be 1.6V, the electrochemiluminescence intensity is detected, and the sweep rate is 0.1V/s. Meanwhile, the signal when the bare electrode was used as the working electrode was tested under the same conditions.
The test results are shown in fig. 12. Figure 12 reflects that ECL gradually appeared and the ECL intensity gradually increased starting from a positive potential of 1.3V after the working electrode was modified with PCzAPT10 macromolecule. For this purpose, solid-state ECL based on a co-reactant of the "oxidation-reduction" type of thermally activated delayed fluorescence material was implemented.
Claims (10)
1. A solid-state electrochemiluminescence sensor, comprising: comprises an electrode, wherein the surface of the electrode is provided with a modification layer of a heat-activated delayed fluorescence polymer.
2. The solid-state electrochemical luminescence sensor of claim 1, wherein: the heat-activated delayed fluorescence polymer is selected from conjugated polymers with triazine groups on side chains shown in a formula (I):
wherein R is1、R3Independently selected from C1-C30 alkyl, C1-C30 alkoxy, C6-C35 unsubstituted aryl or C6-C35 substituted aryl;
R2selected from C1-C30 alkyl, C1-C30 alkoxy, C6-C35 unsubstituted aryl, C6-C35 unsubstituted phenol, C6-C35 substituted aryl or C6-C35 substituted phenol;
0.01≤x≤0.25；
n is an integer of 2 to 200.
3. The solid-state electrochemical luminescence sensor of claim 2, wherein: in the formula (I), R is1And R3Independently selected from C3-C20 alkyl, C3-C20 alkoxy, C6-C20 unsubstituted aryl or C8-C25 substituted aryl, wherein the substituent on the substituted aryl is one or two of C1-C12 alkyl and C1-C12 alkoxy.
4. The solid-state electrochemical luminescence sensor of claim 2, wherein: the R is2Is one or two of C3-C25 alkyl, C2-C20 alkoxy, C6-C20 unsubstituted aryl, C6-C20 unsubstituted phenol, C8-C25 substituted aryl or C8-C25 substituted phenol, wherein the substituent in the substituted phenol is one or two of C1-C12 alkyl and C1-C12 alkoxySeed growing; the substituent in the substituted aryl is one or two of C1-C12 alkyl and C1-C12 alkoxy.
5. A solid state electrochemiluminescence sensor according to any of claims 1 to 4, wherein: the side chain triazine group-containing conjugated polymer shown in the formula (I) is shown in the formula (I-a), the formula (I-b), the formula (I-c), the formula (I-d), the formula (I-e), the formula (I-f) or the formula (I-g):
wherein n is 2-200.
6. The solid-state electrochemical luminescence sensor of claim 1, wherein: the heat-activated delayed fluorescence polymer is selected from heat-activated delayed fluorescence polymers shown as a formula (II):
wherein Ar1 is a 2, 7-fluorene derivative or a 2, 7-carbazole derivative;
ar2 is aryl of C6-C20;
R1、R2、R3、R4and R5Independently selected from hydrogen, alkyl of C1-C30, alkoxy of C1-C30 or substituted aryl of C6-C50;
0.0001≤x≤0.25；
n is an integer of 1 to 200.
7. The solid state electrochemical luminescence sensor of claim 6, wherein: the R is1、R2、R3、R4And R5Independently selected from hydrogen, alkyl of C3-C25, alkoxy of C3-C25 or substituted aryl of C8-C30; the substituent on the substituted aryl is one or two of C1-C20 alkyl and C1-C20 alkoxy.
8. The solid state electrochemical luminescence sensor of claim 6, wherein: ar1 is a 2, 7-fluorene derivative of C15-C50 or a 2, 7-carbazole derivative of C15-C50.
9. A method for manufacturing a solid-state electrochemical luminescence sensor according to any one of claims 1 to 8, characterized in that: the method comprises the following steps: and coating the solution of the heat-activated delayed fluorescence polymer on the surface of the electrode, drying, and forming a modification layer of the heat-activated delayed fluorescence polymer on the surface of the electrode to obtain the solid-state electrochemical luminescence sensor.
10. Use of the solid-state electrochemiluminescence sensor according to any of claims 1 to 8 in immunoassay, ion analysis, nucleic acid detection or water quality detection.
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| CN113307953A (en) * | 2021-05-26 | 2021-08-27 | 齐鲁工业大学 | Solid-phase polycarbazole derivative electroluminescent system and construction method and application thereof |
| CN113930234A (en) * | 2021-10-26 | 2022-01-14 | 广州大学 | Nano material and preparation method and application thereof |
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| CN113307953A (en) * | 2021-05-26 | 2021-08-27 | 齐鲁工业大学 | Solid-phase polycarbazole derivative electroluminescent system and construction method and application thereof |
| CN113930234A (en) * | 2021-10-26 | 2022-01-14 | 广州大学 | Nano material and preparation method and application thereof |
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