CN112268945B - P-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material and preparation method and application thereof - Google Patents
P-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material and a preparation method and application thereof. The Schiff base material is obtained by performing an amino-aldehyde condensation reaction on p-phenylenediamine and 1, 10-phenanthroline-2, 9-diformaldehyde; the Schiff base material has the characteristics of large specific surface area, uniform pore channel distribution, good stability, stable electrical activity per se, rich nitrogen heteroatom and the like, has good adsorption and capacity on biological enzyme (such as glucose oxidase), and can be applied to construction of enzyme sensors.
Description
Technical Field
The invention relates to an electroactive Schiff base material, a preparation method and application thereof, in particular to a p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material, a preparation method and application thereof in construction of a biological enzyme ratio sensor, and belongs to the technical field of functional material synthesis.
Background
Although research in glucose sensors in the scientific community is currently progressing rapidly, the reproducibility and selectivity of the sensors is still a problem to be solved. For example, an enzyme-free sensor with excellent stability has a certain catalytic effect on glucose, but the selectivity is not satisfactory. In the construction of the traditional enzyme-based electrochemical biosensor, enzyme has excellent selectivity due to the specificity of the enzyme, but the difference of enzyme immobilization and the difference of effective surface areas of different electrodes cause the difference of measurement results, so that the reproducibility of the sensor is poor, and the application range of the sensor is greatly limited. In this case, the rate-type electrochemical sensor is distinguished by its advantages of rapid detection, easy portability of the apparatus, and low cost.
Disclosure of Invention
Compared with the defects in the prior art, the first purpose of the invention is to provide the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material which has the characteristics of large surface area, uniform pore channel distribution, good stability, stable self electrical activity, rich nitrogen heteroatom and the like, has good adsorption and immobilization capacities on biological enzyme protein, and can be applied to the construction of a biological enzyme ratio sensor by the self electrical activity.
The second purpose of the invention is to provide a method for preparing p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material, which has simple steps and mild reaction conditions and is beneficial to expanded production.
The third purpose of the invention is to provide an application of p-phenylenediamine-1, 10-phenanthroline-2, 9-diformylaldehyde electroactive Schiff base material in the construction of a glucose oxidase ratio sensor, the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformylaldehyde electroactive Schiff base material can be used as a glucose oxidase ratio sensor to realize glucose detection, the large surface area, the high porosity and the ordered pore structure of the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformylaldehyde electroactive Schiff base material are fully utilized, a large amount of nitrogen can be exposed on the surface of the p-phenylenediamine-phenanthroline-2, 9-diformylaldehyde electroactive Schiff base material, a large number of glucose oxidase adsorption sites are provided, the loading capacity of the material to enzyme is greatly improved, meanwhile, the redox activity of the Schiff base material is utilized to construct a ratio type sensor, and the stability and the reproducibility of the sensor are greatly improved.
In order to achieve the technical purpose, the invention provides a p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material which has the following repeated structural units:
the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material is characterized in that a polymer framework is constructed by two diamines and dialdehyde compounds with planar structures through ammonia-aldehyde condensation, the formed polymer framework has regular pores and uniform pore size, a large planar conjugated system exists in the whole polymer framework, good thermal stability is shown, the polymer is endowed with the self-redox electroactive through introducing a polymerized monomer p-phenylenediamine, and meanwhile, the phenanthroline structure of the 1, 10-phenanthroline in the polymer and a large number of carbon-nitrogen double bonds are formed through condensation, so that the polymer framework is endowed with polarity and abundant free electrons, and has strong adsorption and immobilization capacity on biological enzymes.
The invention also provides a preparation method of the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material, and the method is to perform amino-aldehyde condensation reaction on the p-phenylenediamine and the 1, 10-phenanthroline-2, 9-diformaldehyde to obtain the p-phenylenediamine and phenanthroline-2, 9-diformaldehyde electroactive Schiff base material.
As a preferable scheme, p-phenylenediamine and 1, 10-phenanthroline-2, 9-diformaldehyde are dissolved in an organic solvent, after ultrasonic mixing, an organic acid catalyst is added into the mixed solution, and the reaction is carried out for 2 to 4 days at the temperature of 90 to 120 ℃.
Preferably, the concentration of the p-phenylenediamine in the mixed solution is 1.8 to 7.3mg/mL.
As a preferable embodiment, the concentration of the 1, 10-phenanthroline-2, 9-dicarbaldehyde in the mixed solution is 4-16 mg/mL.
The invention adopts 1, 4-dioxane as an organic solvent, and controls the concentration within a certain range, so that the p-phenylenediamine and the 1, 10-phenanthroline-2, 9-dimethyl aldehyde monomer are fully dissolved and mixed, and the condensation reaction is favorably carried out.
The organic acid catalyst is mainly used for catalyzing the ammonia-aldehyde condensation reaction and providing hydrogen proton catalytic reaction. The preferred organic acid is acetic acid.
The invention relates to a p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material (SBP for short) PPDA-PDA ) The preparation method comprises the following specific steps:
(1) Dissolving p-phenylenediamine (PPDA) and 1, 10-phenanthroline-2, 9-dimethyl aldehyde (PDA) in a 1, 4-dioxane solvent, and performing ultrasonic mixing to obtain a mixed solution; the concentration of the p-phenylenediamine in the mixed solution is 1.8-7.3 mg/mL; the concentration of 1, 10-phenanthroline-2, 9-diformaldehyde in the mixed solution is 4-16 mg/mL.
(2) Adding acetic acid solution (catalytic amount) into the mixed solution, transferring the mixed solution into a reaction kettle, and carrying out an amino-aldehyde condensation reaction for 3 days under the sealed condition of 90-120 ℃;
(3) Washing the obtained precipitate with N, N-Dimethylformamide (DMF), soaking the precipitate in Tetrahydrofuran (THF) solution for 12 hr, exchanging high-boiling-point N, N-dimethylformamide with low-boiling-point tetrahydrofuran to remove organic monomer molecules and impurities adsorbed by the precipitate, vacuum freeze drying, and grinding to obtain yellow powder, i.e. SBP PPDA-PDA 。
The invention also provides application of the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material to construction of an enzyme type glucose ratio electrochemical sensor.
As a preferable scheme, p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base materials are modified on the surface of an electrode to construct a ratio type electrochemical sensor for detecting glucose.
The method for applying the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material to the construction of the sensor comprises the following steps:
(1) 2.5mg of SBP PPDA-PDA Dispersing in 1mL of ultrapure water, and performing ultrasonic treatment for 30min to obtain a uniform dispersion liquid;
(2) Dripping 10 mu L of the dispersion liquid on the surface of a polished glassy carbon electrode, and drying to obtain SBP PPDA-PDA /GCE；
(3) 10 μ L of 5mg/mL Glucose Oxidase (GOD) solution was dropped on SBP PPDA-PDA on/GCE, GOD/SBP were obtained PPDA-PDA /GCE。
In SBP PPDA-PDA Large surface area, high porosity, ordered pore structure of (A) exposes nitrogen to its surfaceTherefore, a large number of glucose oxidase adsorption sites are provided, and a theoretical basis is provided for the enzyme type glucose sensor.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) The p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material provided by the invention not only introduces p-phenylenediamine to endow the polymer with self redox electroactive, but also endows the polymer with polarity and abundant free electrons due to the phenanthroline structure of 1, 10-phenanthroline in the polymer and a large amount of carbon-nitrogen double bonds formed by condensation, shows strong adsorption and immobilization capacity on biological enzyme, and has a large specific surface area and a uniform pore structure, for example, the specific surface area is about 79.56m 2 g -1 And the Schiff base material has better stability, for example, the Schiff base material stably exists under different acid-base concentrations.
2) The synthesis method of p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material provided by the invention is realized through one-step reaction, the steps are simple, the reaction conditions are mild, and the expanded production is facilitated.
3) The p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material provided by the invention can be applied to the construction of an enzyme type glucose ratio electrochemical sensor, and has a good detection effect on glucose, such as a low detection limit: 6.58 μ M, broad linear range: 19.74nM to 8mM.
Drawings
FIG. 1 shows SBP PPDA-PDA Transmission electron microscopy images of (a).
FIG. 2 shows SBP PPDA-PDA Infrared spectrum of (1).
FIG. 3 is a SBP PPDA-PDA The isothermal profile of (1) is absorbed by nitrogen.
FIG. 4 is a SBP PPDA-PDA Cyclic voltammogram of/GCE.
FIG. 5 shows GOD/SBP PPDA-PDA the/GCE is used for detecting a differential pulse voltammogram of glucose.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
(1) Dissolving 11mg of p-phenylenediamine and 24mg of 1, 10-phenanthroline-2, 9-diformaldehyde in 3mL of solvent, and ultrasonically mixing for 30min;
(2) Adding 0.2mL of 6M acetic acid solution into the mixed solution, transferring the mixed solution into a reaction kettle, placing the reaction kettle in a 120 ℃ oven, and reacting for 3 days;
(3) Sequentially washing the obtained precipitate by using N, N-dimethylformamide as a washing agent until the supernatant is colorless, then placing the precipitate in a tetrahydrofuran solution for soaking and exchanging for 12 hours, exchanging high-boiling-point N, N-dimethylformamide by using low-boiling-point tetrahydrofuran, and more fully removing organic monomer molecules and impurities adsorbed by the precipitate; finally, drying the precipitate in a vacuum freeze dryer for 24 hours, and grinding to obtain the red brown powder SBP PPDA-PDA 。
SBP PPDA-PDA The transmission electron microscope image of (A) is shown in FIG. 1, from which it can be seen that SBP PPDA-PDA The structure is provided with a plurality of small slices on the surface, and the thickness is uniform.
SBP PPDA-PDA The infrared spectrum of (A) is shown in figure 2, wherein the infrared spectrum is 2854cm -1 And 2997cm -1 Aldehyde group at position and 3299cm -1 And 3372cm -1 Disappearance of stretching vibration peak at amino group, 1615cm -1 The newly appeared peak of stretching vibration of-C = N-proves SBP PPDA-PDA Have been successfully synthesized.
SBP PPDA-PDA The nitrogen adsorption/desorption isotherm curves of (A) are shown in FIG. 3, and it was revealed that the specific surface area of the material was 79.56m 2 g -1 . FIG. 4 shows SBP PPDA-PDA Cyclic voltammogram of/GCE. It can be seen that SBP PPDA-PDA Has a pair of redox peaks with better reversibility, and can be found by comparing cyclic voltammograms of p-phenylenediamine and 1, 10-phenanthroline-2, 9-dicarbaldehyde, wherein the peaks are derived from the p-phenylenediamine.
Example 2
(1) Dissolving 22mg of p-phenylenediamine and 48mg of 1, 10-phenanthroline-2, 9-diformaldehyde in 6mL of solvent, and ultrasonically mixing for 30min;
(2) Adding 0.2mL of 6M acetic acid solution into the mixed solution, transferring the mixed solution into a reaction kettle, placing the reaction kettle in a 100 ℃ oven, and reacting for 3 days;
(3) Sequentially washing the obtained precipitate by using N, N-dimethylformamide as a washing agent until the supernatant is colorless, then placing the precipitate in a tetrahydrofuran solution for soaking and exchanging for 12 hours, exchanging high-boiling-point N, N-dimethylformamide by using low-boiling-point tetrahydrofuran, and more fully removing organic monomer molecules and impurities adsorbed by the precipitate; finally, drying the precipitate in a vacuum freeze dryer for 24 hours, and grinding to obtain the red brown powder SBP PPDA-PDA 。
Example 3
(1) Dissolving 22mg of p-phenylenediamine and 48mg of 1, 10-phenanthroline-2, 9-diformaldehyde in 3mL of solvent, and ultrasonically mixing for 30min;
(2) Adding 0.2mL of 6M acetic acid solution into the mixed solution, transferring the mixed solution into a reaction kettle, placing the reaction kettle in a 120 ℃ oven, and reacting for 3 days;
(3) Sequentially washing the obtained precipitate by using N, N-dimethylformamide as a washing agent until the supernatant is colorless, then placing the precipitate in a tetrahydrofuran solution for soaking and exchanging for 12 hours, exchanging high-boiling-point N, N-dimethylformamide by using low-boiling-point tetrahydrofuran, and more fully removing organic monomer molecules and impurities adsorbed by the precipitate; finally, drying the precipitate in a vacuum freeze dryer for 24 hours, and grinding to obtain the red brown powder SBP PPDA-PDA 。
Example 4
(1) 2.5mg of SBP prepared in example 1 PPDA-PDA Dispersing in 1mL of ultrapure water, and carrying out ultrasonic treatment for 30min to obtain a uniform dispersion liquid;
(2) Dripping 10 mu L of the dispersion liquid on the surface of a polished glassy carbon electrode, and drying to obtain SBP PPDA-PDA /GCE；
(3) 10 μ L of 5mg/mL Glucose Oxidase (GOD) solution was dropped on SBP PPDA-PDA on/GCE, GOD/SBP were obtained PPDA-PDA /GCE。
(4) Mixing GOD/SBP PPDA-PDA /GCE electricityThe method is extremely used for detecting glucose.
The specific detection method comprises the following steps: the glucose solution was continuously added to a 0.2M phosphate buffer solution at pH =7.0 and assayed using the DPV technique.
SBP PPDA-PDA The DPV curve of the/GCE for the detection of 8mM glucose solution is shown in FIG. 5, from which it can be seen that the GOD/SBP PPDA-PDA The reduction peak of oxygen becomes weaker in the presence of 8mM glucose for the/GCE, indicating that the detection range of the sensor is wider, and the SBP is used PPDA-PDA As a reference signal, an electrochemical ratio sensor was constructed.
Claims (3)
1. The application of the p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base material is characterized in that: the construction method is applied to construction of a bio-enzyme ratio sensor;
the Schiff base material has the following repeating structural unit:
dissolving p-phenylenediamine and 1, 10-phenanthroline-2, 9-dimethyl aldehyde in an organic solvent, ultrasonically mixing, adding an organic acid catalyst into a mixed solution, and reacting at the temperature of 90-120 ℃ for 2-4 days to obtain the Schiff base material;
the concentration of the p-phenylenediamine in the mixed solution is 1.8-7.3 mg/mL; the concentration of the 1, 10-phenanthroline-2, 9-diformaldehyde in the mixed solution is 4-16 mg/mL.
2. The use of p-phenylenediamine-1, 10-phenanthroline-2, 9-dialdehyde electroactive schiff base material according to claim 1, wherein: the organic acid catalyst is acetic acid.
3. The use of p-phenylenediamine-1, 10-phenanthroline-2, 9-dialdehyde electroactive schiff base material according to claim 1, wherein: modifying p-phenylenediamine-1, 10-phenanthroline-2, 9-diformaldehyde electroactive Schiff base materials on the surface of an electrode to construct a biological enzyme ratio sensor.
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