CN115322340B - Conjugated polymer biocatalysis material and preparation method and application thereof - Google Patents
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Abstract
The invention provides a conjugated polymer biocatalysis material, a preparation method and application thereof, and belongs to the field of biocatalysis. Compared with the existing small molecular iron-based biocatalyst iron (II) phthalocyanine, m-tetraphenylporphyrin iron (III) chloride, ferroferric oxide and hemin, the conjugated polymer provided by the invention has more excellent POD-like activity. The invention also finds that the conjugated polymer provided by the invention has excellent imitation POD activity and excellent imitation CAT, OXD, HPO and GPx activity. The preparation method of the conjugated polymer provided by the invention is simple, is suitable for large-scale production, and has wide application prospect in preparing the efficient multifunctional enzyme-like catalyst.
Description
Technical Field
The invention belongs to the field of biocatalysis, and in particular relates to a conjugated polymer biocatalysis material, a preparation method and application thereof.
Background
Porphyrin (porphyrins) is a conjugated framework macrocyclic compound formed by connecting four pyrrole rings through methine groups, and the central nitrogen atom is coordinated with a metal atom to form metalloporphyrin complex (metalloporphyrins). Natural porphyrin and metalloporphyrin complexes are widely present in animals and plants, such as heme, chlorophyll, vitamin B12, cytochrome P-450, which have specific physiological activities. As natural porphyrin and metalloporphyrin complex molecules have rigidity and flexibility, electronic buffering property, photoelectric magnetism and high chemical stability, porphyrin chemistry is studied by people in the 30 th century as early as 20 th century, and the porphyrin and metalloporphyrin complex molecules are widely used as photoconductors, semiconductors, superconductors, catalysts, anticancer drugs, color developers and the like.
Although natural porphyrin and metalloporphyrin compounds have many of the above-mentioned excellent properties, mass production is difficult. Therefore, the design of the synthetic porphyrin and metalloporphyrin complex has great significance. Phthalocyanines have also received considerable attention as an artificially synthesized porphyrin derivative because of having many properties similar to those of porphyrins. The phthalocyanine is similar to porphyrin in structure, and the complex formed by the phthalocyanine and the non-transition metal has photo-biological activity on tumors. In the 80 s of the 20 th century, a series of experimental results on the photo-inactivation effect of phthalocyanine on in vitro cultured human cancer cells and the photodynamic injury effect of animal transplantation tumor have been reported, wherein zinc phthalocyanine has entered phase I clinical test.
Although artificially synthesized small molecular metalloporphyrin compounds are reported to be applied to wound healing, anti-tumor, anti-inflammatory and other aspects in the field of biocatalysis at present, on the one hand, the mechanism of the small molecular metalloporphyrin compounds for exerting therapeutic effects in vivo has not been elucidated; on the other hand, the therapeutic effect of these small molecule metalloporphyrin compounds has yet to be further improved.
Disclosure of Invention
The invention aims to provide a conjugated polymer biocatalysis material, a preparation method and application thereof.
Conjugated polymers are high molecular weight compounds having conjugated structures formed from one or more types of repeating structural units joined together by covalent bonds.
The invention provides a conjugated polymer material, which is a polymer formed by connecting a repeated structural unit shown in a formula I or a formula II through covalent bonds:
wherein M is a metal atom.
Further, M is Fe.
Further, the polymer is formed by connecting a repeating structural unit shown in a formula I through a covalent bond, and is a product obtained by taking a porphyrin-based conjugated polymer and a metal salt as raw materials to react, wherein the porphyrin-based conjugated polymer is formed by connecting a repeating structural unit shown in a formula III through a covalent bond:
further, the mass ratio of the porphyrin-based conjugated polymer to the metal salt is (1.0-2.0): 1, preferably 1.2:1; the metal salt is ferric salt, preferably Fe 3+ A salt; the reaction temperature is 100-140 ℃, preferably 120 ℃, the reaction time is 8-16h, preferably 12h, and the reaction solvent is an organic solvent, preferably dimethylformamide.
Further, the preparation method of the porphyrin-based conjugated polymer comprises the following steps: adding polystyrene microspheres into water to form polystyrene microsphere suspension, adding acetic acid into the polystyrene microsphere suspension, uniformly mixing, then adding terephthalaldehyde and pyrrole, and reacting to obtain a polystyrene microsphere-loaded porphyrin polymer; adding a porphyrin polymer loaded by polystyrene microspheres into toluene, stirring for 10-14 hours, filtering, and retaining solids to obtain a porphyrin-based conjugated polymer;
preferably, the polystyrene microsphere suspension, the benzaldehyde and the pyrrole have the ratio of (4-6) mL: (50-55) mg: (50-60) μl, preferably 5mL:52.5mg: 54. Mu.L; the polystyrene microsphere suspension has a solid content of 4-6 wt.%, preferably 5wt.%; the reaction is carried out in the presence of trifluoroacetic acid and nitrobenzene; the temperature of the reaction is 60-100 ℃, preferably 80 ℃, for 10-14 hours, preferably 12 hours.
Further, it is a polymer formed by covalent bonding of the repeating structural units represented by formula II, which is a product obtained by reacting 1,2,4, 5-benzene tetra-carbonitrile with a metal salt as a raw material.
Further, the molar ratio of the 1,2,4, 5-benzene tetra-carbonitrile to the metal salt is (1.5-3.5): 1, preferably 2.5:1; the metal salt is ferric salt, preferably Fe 3+ A salt; the reaction temperature is 160-200 ℃, preferably 180 ℃, the reaction time is 5-15min, preferably 10min, and the reaction solvent is an organic solvent, preferably ethylene glycol;
and/or the reaction is carried out in a microwave reactor, the reaction being carried out in the presence of a catalyst which is an organic base, preferably 1, 8-diazacyclo (5, 4, 0) undec-7-ene.
The invention also provides application of the conjugated polymer material in preparing a simulated enzyme catalyst.
Further, the enzyme is POD enzyme, CAT enzyme, OXD enzyme, HPO enzyme and/or GPx enzyme.
Further, the enzyme-like catalyst is a medicament for preventing and/or treating bacterial infection and a medicament for accelerating wound healing.
The invention provides a polymer with a conjugated network structure: fe-PorBC and Fe-PcBC. Compared with the existing small molecular iron-based biocatalyst iron (II) phthalocyanine, iron (III) phthalocyanine, m-tetraphenylporphyrin iron (III) chloride, ferroferric oxide and hemin, the conjugated polymers Fe-PorBC and Fe-PcBC provided by the invention have more excellent POD-like activity.
The free radical generated by Fe-PorBC in the catalytic process is mainly OH, while the Fe-PcBC is mainly OH and O 2 · - . Compared with Fe-PorBC, fe-PcBC has better POD-like activity, better catalytic dynamics and stronger catalytic oxidation capability.
The conjugated polymer Fe-PorBC and Fe-PcBC provided by the invention have excellent imitation CAT, OXD, HPO and GPx activities besides excellent imitation POD activity, and can be used as a high-efficiency multifunctional imitation enzyme catalyst. Among them, fe-PcBC has better imitation POD, CAT, OXD, HPO and GPx activities than Fe-PorBC.
The preparation method of the conjugated polymer provided by the invention is simple, is suitable for large-scale production, and has wide application prospect in preparing the efficient multifunctional enzyme-like catalyst.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 structural characterization of Fe-PorBC and Fe-PcBC at the atomic scale. (a) Fe-PorBC structural schematic; (b, c) an AC-HAADF-STEM image of Fe-PorBC; (d) schematic structural diagram of Fe-PcBC; (e, f) AC-HAADF-STEM image of Fe-PcBC.
FIG. 2 (a) Fe-PorBC and (b) Fe-PcBC 13 C NMR spectrum; (c) raman spectra of Fe-PorBC and commercial TPPFe; (d) Raman spectra of Fe-PcBC and commercial PcFe.
FIG. 3 catalytic kinetics of Fe-PorBC and Fe-PcBC. (a) relative POD activity of different iron-based biocatalysts; (b) By H 2 O 2 And TMB as substrate, and V of Fe-PorBC and Fe-PcBC max And TON value.
FIG. 4 reactive oxygen species generated by Fe-PorBC and Fe-PcBC. Recording (a). OH Signal and (c) O 2 · - EPR spectrum of the signal; recording (b). OH Signal and (d) O 2 · - Fluorescence spectrum of the signal.
FIG. 5 (a) MB degradation test of Fe-PorBC and Fe-PcBC; (b) TBA quenching-OH, BQ quenching O during MB catalytic degradation 2 · - The method comprises the steps of carrying out a first treatment on the surface of the POD activity of Fe-PorBC and Fe-PcBC at different (c) pH conditions and (d) temperatures, absorbance at pH 4.5 being defined as 100%; * P<0.001. FIG. 6A plurality of simulated enzyme activities of Fe-PorBC and Fe-PcBC. (a) Catalytic production of O by Fe-PorBC and Fe-PcBC 2 Is a time dependent process of (1); (b) Ultraviolet-visible absorption spectra of Fe-PorBC and Fe-PcBC in HAc-NaAc buffer (0.1M, pH 4.5) to catalyze the oxidation of TMB (oxTMB); (c) For recording O 2 · - EPR spectrum of the signal; (d) Ultraviolet-visible absorption spectra of Fe-PorBC and Fe-PcBC in PBS buffer (pH 5.8) to catalyze oxidation of CB; (e) Recording OCl - Fluorescence spectrum of the signal; (f) Ultraviolet-visible absorption spectra of Fe-PorBC and Fe-PcBC in PBS buffer (pH 7.4) to catalyze the oxidation of DTNB; (g) A time-dependent curve of Fe-PorBC and Fe-PcBC catalytic degradation DTNB; * P<0.001。
FIG. 7 is a schematic representation of the Fe-Porbc synthesis route.
FIG. 8A schematic representation of the synthetic route for Fe-PcBC.
SEM pictures and size distributions of Fe-PorBC (a, b) and Fe-PcBC (c, d) are shown in FIG. 9. Scale bar: 1 μm.
Fig. 10 (a) TEM, (b) high resolution TEM images of fe-PorBC.
FIG. 11 (a) TEM, (b) high resolution TEM, (c, d) HAADF-STEM image of Fe-PcBC.
FIG. 12 (a) FT-IR spectra and (b) UV-vis spectra of Fe-PcBC, pcFe and Pc.
Typical XRD patterns for Fe-PorBC and Fe-PcBC are shown in FIG. 13.
Detailed Description
The raw materials and equipment used in the invention are all known products and are obtained by purchasing commercial products.
Example 1: preparation of iron porphyrin based biocatalyst Fe-PorBC
The one-pot method is adopted to synthesize Fe-PorBC, and the synthetic route is shown in figure 7.
1. Synthetic porphyrin-based biocatalysts (PorBC)
1) Synthesis of monodisperse Polystyrene (PS) microspheres
Monodisperse PS microspheres were prepared according to the method described in reference (Shen, k.; zhang, l.; chen, x.; liu, l.; zhang, d.; han, y.; chen, j.; long, j.; luque, r.; li, y.; et al. The preparation method comprises the following steps: styrene (39 mL) was first washed with 12mL of aqueous NaOH (10 wt.%) and deionized water, respectively, to remove the stabilizer, and the washed styrene was then poured into a three-necked flask containing 300mL of deionized water. To a three-necked flask, 1.5g of polyvinylpyrrolidone (PVP) was added, and the mixed solution was bubbled with nitrogen for 15min and refluxed for 30min under magnetic stirring at 95 ℃. Finally, 0.5. 0.5g K was added to the three-necked flask 2 S 2 O 8 And 50mL deionized water to initiate styrene polymerization. Stirring was continued at this temperature for 24h (500 r/min) to give a suspension of monodisperse PS microspheres with a solids content of 5 wt.%.
2) PS@Por synthesized by taking monodisperse PS microspheres as templates
First, 5mL of a suspension of monodisperse PS microspheres having a solids content of 5wt.% was sonicated with 250mL of glacial acetic acid for 30min to form a homogeneous suspension. Then, 52.5mg of terephthalaldehyde (BDA) and 54. Mu.L of pyrrole were added to the suspension and sonicated for 30min, 1mL of trifluoroacetic acid (TFA) and 5mL of Nitrobenzene (NBZ) were further added as a catalyst and an oxidizing agent, respectively, and sonication was continued for 30min, and then the suspension was continuously stirred at 80℃for 12h, and cooled to room temperature after the completion of the reaction. And finally, filtering the reaction solution, washing a filter cake with ethanol for three times, and drying at 60 ℃ for 24 hours to obtain the black polystyrene microsphere supported porphyrin polymer named PS@Por.
3) Synthesis of PorBC
Adding PS@Por into 50mL of toluene, performing ultrasonic dispersion for 30min, continuously stirring at 60 ℃ for 12h, filtering the reaction solution, washing a filter cake with ethanol, and drying at 60 ℃ for 24h to obtain a hollow spherical porphyrin-based biocatalyst named PorBC.
2. Synthesis of Fe-PorBC
10mg of PorBC was added to a vial containing 2mL of Dimethylformamide (DMF). Subsequently, feCl is added 3 (8.1 mg,0.05 mM) was added to the solution and sonicated for 10min, and stirred continuously at 120℃for 12h. And then filtering the product, washing the filter cake with DMF, deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ for 24 hours to obtain the hollow spherical Fe-PorBC.
Example 2: preparation of iron phthalocyanine-based biocatalyst Fe-PcBC
Fe-PcBC was prepared by a rapid microwave heating process, and the synthetic route is schematically shown in FIG. 8. First, 1,2,4, 5-Benzenetetracarbonitrile (89 mg,0.5 mM) and FeCl were added 3 (32.4 mg,0.2 mM) in 10mL of ethylene glycol, the mixed solution was sonicated for 10min, and then 75. Mu.L of 1, 8-diazacyclo (5, 4, 0) undec-7-ene (DBU) was added as a catalyst. The whole system is put into a microwave reactor and reacted for 10min under the environment of 180 ℃ (320W). After the reaction is finished, filtering, washing filter cakes with glycol, 3% hydrochloric acid, deionized water and ethanol in sequence, and vacuum drying at 60 ℃ overnight to obtain Fe-PcBC.
The following experiments prove the beneficial effects of the invention.
Fe-PorBC used in the following experimental examples was prepared from example 1 and Fe-PcBC was prepared from example 2; the control samples are shown in Table 1 and are commercially available products.
TABLE 1 control sample information
| Name of the name | Specification of specification | Manufacturer' s |
| Iron (II) phthalocyanine (PcFe) | 98％ | Aladdin |
| Phthalocyanine (Pc) | 93％ | Aladdin |
| M-tetraphenylporphyrin iron (III) chloride (TPPFe) | 95％ | Aladdin |
| Ferroferric oxide (Fe) 3 O 4 ) | 97％ | Alfa Aesar |
| Hemin (Hemin) | 96％ | Aladdin |
Experimental example 1: structural characterization of biocatalysts
1. Experimental method
Solid state nuclear magnetic resonance spectroscopy was measured on a Bruker AV400 spectrometer operating at 75.5MHz 13 C. Fe-PcBC and Fe-PorBC were subjected to 13 C cross polarization and magic angle spin spectroscopy studies. Fourier transform infrared (FT-IR) analysis of the sample using a Nicolet-560 spectrophotometer (Nicole, US) in the range 4000-500cm -1 Resolution of 2cm -1 . Raman spectra were recorded on Horiba Jobin Yvon LabRam HR, 800 with an excitation wavelength of 633nm. The ultraviolet-visible (UV-vis) absorption spectrum is carried out on Shimadzu V-2450 having a wavelength of 300 to 900 nm. Scanning Electron Microscope (SEM) images were obtained from Apreo S HiVoc (Thermo Fisher Scientific, FEI). Transmission Electron Microscope (TEM) images and EDS mapping images were obtained by operating a Talos F200 XTEM microscope (FEILtd., USA) at 200 kV. The crystalline phase state of the sample was observed with a Bruker D8 focus x-ray diffractometer under copper radiation at a voltage of 40 kV. The sample was scanned in the 2 theta range of 5 to 80. ESR experiments were performed on a JEOL-FA200ESR spectrophotometer. Fluorescence measurements were performed on a Hitachi F-4600 fluorescence spectrophotometer.
2. Experimental results
Table 2 atomic ratio of materials and weight ratio of Fe atoms measured by XPS
TABLE 3 fitting of C1s spectra in different materials
TABLE 4 fitting of N1s spectra to relative N content in different materials
TABLE 5 Fe K-edge EXAFS curve fitting parameters for each sample (S02=0.90)
a N: coordination number; b r: distance between absorber and backscattering atoms; c σ 2 : debye-Waller factor; d ΔE 0 : and (5) correcting internal potential. R factor: fitting degree. e Fitting range:
and->
f Fitting range: />
And->
g Fitting range: />
And
as shown by SEM observation (FIG. 9), the Fe-PorBC and the Fe-PcBC prepared by the invention are spherical in morphology, and the particle sizes are about 220nm and 141.7nm respectively. TEM shows (FIGS. 10 and 11) that Fe-PorBC and Fe-PcBC have disordered carbon structures, no Fe clusters or nanoparticles, indicating that the polymer is amorphous and no aggregation of metal atoms. The AC-HAADF-STEM further observed a large number of small bright spots in the carbon substrate, demonstrating that Fe in Fe-PorBC and Fe-PcBC are monoatomically dispersed, conforming to the theoretical structure (FIGS. 1 a-f).
By means of solids 13 C NMRRaman spectroscopy investigated the chemical structure of conjugated polymers. As shown in figure 2a of the drawings, 13 the 136.5ppm peak in the C NMR spectrum was attributed to C 2 、C meso 、C β The peak at 119.1ppm was attributed to C α And C 2 Successful construction of ferriporphyrin-based conjugated polymer was confirmed. 13 The three peaks at 164.5, 132.4, 114.9ppm of the C NMR spectrum were attributed to the phthalocyanine macrocycles in the iron phthalocyanine-based conjugated polymer network (FIG. 2 b). Furthermore, fe-PorBC at 1332cm -1 The raman spectrum at which shows a typical B 1g Mode, which is caused by symmetrical pyrrole ring vibration of porphyrin molecules (fig. 2 c). Likewise, the Raman spectrum of Fe-PcBC also yields A which is an in-plane vibration of the phthalocyanine molecule 1g 、B 1g And B 2g Verification of the mode was 677, 744, 1456cm respectively -1 (FIG. 2 d) indicating successful synthesis of two conjugated polymers.
FT-IR and UV-vis further investigated the Fe-PcBC extended conjugated structure. FT-IR spectrum (FIG. 12 a) shows that C-H of Fe-PcBC is 1118cm compared with PcFe small molecule -1 The signal at the position is obviously reduced, which indicates that the in-plane bending vibration of the periphery C-H of the benzene ring is reduced, and the polymerization of the phthalocyanine monomer is proved. The UV-vis further found that the B and Q bands of Fe-PcBC had a significant red shift compared to PcFe, indicating that Fe-PcBC produced an extended conjugated structure through the attachment of the benzene ring (FIG. 12B). Furthermore, XRD showed that both Fe-PcBC and Fe-PorBC exhibited a typical conjugated polymer peak at around 26 ° (FIG. 13), and no crystalline peaks of Fe or ferric oxide, demonstrating that both are amorphous structures free of metal elements, which is also consistent with STEM data.
The experiment shows that the Fe-PorBC and the Fe-PcBC provided by the invention are conjugated polymers with conjugated network structures.
Experimental example 2: performance test and catalytic mechanism research of biocatalyst simulated peroxidase
1. Experimental method
(1) Assay for peroxidase-like catalytic Activity
Monitoring H with TMB as substrate 2 O 2 The peroxidase activity of the biocatalyst was measured. 1.926mL of acetic acid-vinegarAdding biocatalyst (4 mg/mL, 25. Mu.L) to sodium acid buffer (HAc-NaAc) (0.1M, pH 4.5), H 2 O 2 (100 mM, 25. Mu.L) and TMB (41.6 mM, 24. Mu.L in DMF) were mixed thoroughly. After incubation at 25℃for 10min, the absorbance of the reaction solution at 652nm was recorded with a microplate reader. In addition, the pH stability and thermal stability of the biocatalyst were determined by measuring its absorbance at 652nm after standing at pH 2.5-10.5 and 25-90℃for 2h.
(2) Steady state dynamics calculation
Steady state kinetic testing was performed at 25℃with 2mL of biocatalyst (4 mg/mL, 25. Mu.L), H 2 O 2 (100 mM, 25. Mu.L) and HAc-NaAc buffer solutions (0.1M, pH 4.5) of TMB at different concentrations were mixed and the absorbance of the reaction solution at 652nm was recorded with a microplate reader. To study biocatalyst pair H 2 O 2 Using TMB at constant concentration and H at different concentrations 2 O 2 As a substrate. Likewise, the kinetics of the biocatalyst reaction to TMB is also achieved by using a constant concentration of H 2 O 2 And different concentrations of TMB as substrates. The reaction rate and substrate concentration were fitted in Michaelis-Menten equation and kinetic constants were calculated (V max And K m ) The Michaelis-Menten equation is as follows:
wherein V is 0 For the initial reaction rate, V max Is the maximum reaction rate. Wherein V is max Obtained under saturated substrate conditions. [ S ]]Is the substrate concentration. K (K) m The Miq constant, indicates the substrate concentration at which the initial reaction rate reaches half of its maximum reaction rate.
The catalytic activity of the biocatalyst is defined as follows:
K cat ＝V max /[E 0 ] (2-2)
wherein K is cat The reaction constant is expressed as the maximum amount of conversion substrate (TON) per active catalytic center. E (E) 0 Is metalMolar concentration of active centers.
(3) Detection of reactive oxygen radicals
3.1 Fluorescent probe test)
TA as fluorescent Probe (lambda) ex ＝315nm，λ em =440 nm) detection of biocatalyst catalysis H 2 O 2 And decomposing the generated OH. Biocatalyst (4 mg/mL, 30. Mu.L), 4mM NaTA (reactant of NaOH and TA) and 60mM H were added to 1.5mL of HAc-NaAc buffer (0.1M, pH 4.5) 2 O 2 The mixed solution was then incubated at 37℃for 12 hours, and the fluorescence spectrum of the reaction solution was measured by a fluorescence spectrometer. HE as fluorescent probe (lambda) ex ＝470nm，λ em =624 nm) detection of biocatalyst catalysis H 2 O 2 O produced by decomposition 2 -is. First, HAc-NaAc buffer solution (pH 4.5, 100. Mu.g/mL, 1.5 mL) of biocatalyst was reacted with H 2 O 2 (100 mM, 1.5. Mu.L) was mixed and incubated at 37℃for 30min. Then HE-ethanol solution (1 mg/mL,1.5 mL) was added, and after incubation was continued for 30min, the fluorescence spectrum of the reaction solution was measured with a fluorescence spectrometer.
3.2 EPR test)
Detection of biocatalyst catalysis H with DMPO as spin-trap 2 O 2 And decomposing the generated OH. Biocatalyst (4 mg/mL, 50. Mu.L) and H were added to 0.5mL of HAc-NaAc buffer (0.1M, pH 4.5) 2 O 2 (10M, 10. Mu.L) and mixed well 10. Mu.L DMPO was added. After incubation at 25℃for 10min, the reaction solution was drawn up by capillary for EPR testing. Substitution of DMSO for HAc-NaAc buffer solution, and production of O with DMPO as Capture agent 2 · - The detection is performed in the same step.
2. Experimental results
TABLE 6 relative POD Activity of different iron-based biocatalysts
Note that: fe content (wt%) represents the mass fraction of iron, intensity of oxTMB represents the intensity of oxidized TMB, normalized intensity of oxTMB represents the intensity of oxidized TMB after normalization (i.e., the intensity at the same Fe content), and Relative intensity ratio (%) represents the relative intensity ratio.
TABLE 7H 2 O 2 POD-like catalytic Activity kinetics comparison as substrate
Note that: k (K) m Is Michaelis constant, V max At maximum reaction rate, V 0 Is the initial reaction rate. [ E 0 ]The Michaelis-Menten plot was fit by varying the substrate concentration for the molar concentration of the metal active site. Conversion number (TON) is the maximum amount of conversion substrate per active catalytic center, K cat Is a catalytic constant. K (K) cat /K m The values represent catalytic efficiency.
TABLE 8 comparison of POD-like catalytic Activity kinetics Using TMB as substrate
First, the POD performance of Fe-PorBC and Fe-PcBC was evaluated by TMB color reaction. As shown in FIG. 3a and Table 6, the absorbance of the oxTMB produced by the catalysis of Fe-PorBC and Fe-PcBC is highest under the condition that the content of Fe is the same, which shows that the catalytic activity of the oxTMB and the oxTMB is better than that of other small molecule iron-based catalysts. In addition, fe-PcBC has a higher absorbance than Fe-PorBC, indicating that Fe-PcBC has better POD performance. The steady state kinetic test results indicate (FIG. 3b, table 7 and Table 8) that for substrate H 2 O 2 V of Fe-PcBC max (88.2) is about 1.7 times that of Fe-PorBC (52.4). V for the substrate TMB, fe-PcBC max (130.0) is about 13.5 times that of Fe-PorBC (9.06). TON value of Fe-PcBC (H 2 O 2 27.0, TMB 39.8) higher than Fe-PorBC (H) 2 O 2 18.5，TMB 3.19)，K m Value (H) 2 O 2 0.106, TMB 0.165) is much lower than Fe-PorBC (H) 2 O 2 10.6, TMB 1.2). That is, the catalytic rate of Fe-PcBCFaster, faster substrate turnover rate and better affinity for the substrate, ultimately leading to its catalytic efficiency (K cat /K m ) Extremely high, far higher than Fe-PorBC (H) 2 O 2 146 times TMB 90 times).
To elucidate the catalytic mechanism of Fe-PorBC and Fe-PcBC, EPR spectra and fluorescent probes were used to explore the ROS generated during catalysis. As shown in fig. 4a, the DMPO/·oh adduct has a characteristic peak signal intensity of significantly 1:2:2:1, description of Fe-PorBC and Fe-PcBC in catalyzing H 2 O 2 OH is generated during the decomposition. TA was detected as an OH-specific fluorescent probe and both produced OH, with Fe-PorBC having a slightly higher fluorescence intensity than Fe-PcBC, indicating that more OH was produced by Fe-PorBC (FIG. 4 b). Furthermore, EPR analysis showed that the signal intensity of Fe-PcBC was 1 when the reaction solution was replaced with DMSO: 1:1:1:1 (FIG. 4 c), which is a typical DMPO/O 2 · - Characteristic peaks of adducts, indicating that Fe-PcBC catalyzes H 2 O 2 O is also produced during the decomposition process 2 · - . Further capturing O by a specific probe HE 2 · - Intermediate (FIG. 4 e), the result shows that the absorbance of the Fe-PcBC group at 623nm is higher, indicating that Fe-PcBC is capable of producing more O 2 · - This is consistent with EPR results.
The invention further explores the catalytic oxidation capacities of Fe-PorBC and Fe-PcBC by utilizing MB degradation experiments. As shown in FIG. 5a, the catalytic degradation rate of Fe-PcBC to MB after 30min reaches 74.8% compared with Fe-PorBC (13.5%), which is far higher than that of Fe-PorBC, showing excellent catalytic oxidation performance of Fe-PcBC. To investigate the OH and O produced by Fe-PcBC 2 · - Tertiary Butanol (TBA) and p-Benzoquinone (BQ) are used as OH and O, respectively 2 · - Is a scavenger of (a). As shown in FIG. 5b, the absorbance of the oxTMB decreased rapidly regardless of the addition of TBA or BQ, indicating OH and O 2 · - The intermediate product plays an important role in the ROS formation process of Fe-PcBC. Wherein BQ has a large influence on absorbance, indicating that ROS produced by Fe-PcBC are mainly O 2 · - 。
In addition, the present invention also investigated the effect of pH and temperature on POD activity, as shown in fig. 5c, d, fe-PorBC and Fe-PcBC showed optimal POD activity at ph=4, and maintained high catalytic activity over a wide temperature range, showing catalytic stability of Fe-PorBC and Fe-PcBC under severe environment.
The above results show that the Fe-based catalyst has the same Fe content as that of the existing iron-based biocatalyst 3 O 4 Compared with TPPFe, hemin, pcFe, the conjugated polymers Fe-PorBC and Fe-PcBC provided by the invention have more excellent POD activity. In addition, fe-PcBC has better POD activity, better catalytic kinetics and stronger catalytic oxidation capability than Fe-PorBC.
Experimental example 3: performance test of biocatalyst Multi-enzyme Activity
1. Experimental method
(1) Test of the Activity of the Oxidation enzyme (OXD)
The OXD activity of the material was studied using TMB as a substrate. To 1.951mL of HAc-NaAc buffer (0.1M, pH 4.5) was added the material (4 mg/mL, 25. Mu.L) and TMB (41.6 mM, 24. Mu.L in DMF) and mixed thoroughly. After incubation at 25℃for 10min, the absorbance of the reaction solution at 652nm was recorded with a microplate reader. Oxygen, air and nitrogen are introduced to compare the activity of the simulated OXD.
(2) Catalase-like (CAT) Activity assay
To examine the material decomposition H 2 O 2 To 20mL of HAc-NaAc buffer solution (0.1M, pH 4.5) was added material (10 mg/mL, 20. Mu.L) and H 2 O 2 (10M, 200. Mu.L) was measured for oxygen production at various time points using a dissolved oxygen meter.
(3) Haloperoxidase (HPO) activity assay
Hypochlorite ion (ClO) - ) Can specifically bind to CB, thereby oxidizing blue CB to pink, such that the ultraviolet absorbance of CB decreases from 640nm, increases at 520nm, and assumes an equivalent point at about 540 nm. To a PBS solution (0.1M, pH5.8, final concentration of CB: 200. Mu.M) of 1.84mL of CB were added the material (4 mg/mL, 150. Mu.L) and H 2 O 2 (100 mM, 10. Mu.L). After incubation at 25℃for 30min, the absorbance of the reaction solution at 640nm and 520nm was recorded with an ELISA readerLuminosity.
APF is used as fluorescent probe (lambda) ex ＝485nm，λ em =514 nm) detection of OCl produced in a catalytic reaction of a material - . To 100. Mu.L of the material solution (0.1M, pH5.8, final concentration of material 300. Mu.g/mL) was added H 2 O 2 (100 mM, 10. Mu.L) and APF (0.5 mM, 2. Mu.L). After incubation at 25℃for 30min, the absorbance at 514nm was measured with a fluorescence microplate reader.
(4) Glutathione peroxidase (GPx) mimetic Activity assay
5,5' -dithiobis (2-nitrobenzoic acid) (DTNB) is a sulfhydryl indicator. The disulfide bond thereof breaks to produce 2-nitro-5-thiobenzoic acid, the characteristic absorbance at 408nm decreasing with time. The change in UV absorbance spectra at different time points was monitored by adding material (4 mg/mL, 25. Mu.L) and 5mM GSH to 2mL PBS (0.1M, pH 7.4), followed by DTNB (3 mg/mL, 30. Mu.L).
2. Experimental results
Under different catalytic conditions, enzymes can exhibit a wide variety of catalytic activities on different substrates, which is known as multi-enzyme activity. After verifying that Fe-PorBC and Fe-PcBC have POD-like activity, the invention also investigates the properties of both imitation CAT, OXD, HPO and GPx. As shown in FIG. 6a, when used in CAT enzyme catalytic reaction, fe-PcBC reached 22.07mg/L in 5min of oxygen yield, 5.9 times that of Fe-PorBC (3.72 mg/L), showing good H 2 O 2 Decomposing ability. In addition, at O 2 As a substrate, the oxTMB of Fe-PcBC had a higher absorbance at 652nm, indicating that its OXD activity was far superior to that of Fe-PorBC (FIG. 6 b), O being produced in the reaction 2 · - Also detected by EPR (fig. 6 c). HPO enzyme can catalyze H 2 O 2 Oxidizing halides to form ClO - And thus specifically recognized by CB and APF. As can be seen from FIG. 6d, the CB ultraviolet absorption spectrum of Fe-PcBC drops rapidly at 640nm compared to Fe-PorBC, indicating that more ClO is produced - . In addition, APF also detected ClO produced by Fe-PorBC and Fe-PcBC - The higher fluorescence intensity also demonstrated that Fe-PcBC had better HPO-like activity (FIG. 6 e). GPx enzymes can also scavenge free radicals by redox reactionsPrototype Glutathione (GSH) was converted to oxidized glutathione (GSSG), so the imitation GPx activity of Fe-PorBC and Fe-PcBC was studied using DTNB as a sulfhydryl indicator. As shown in FIGS. 6f, g, fe-PcBC showed 77.34% high GSH consumption over a 30min reaction time, while Fe-PorBC had only 8.4% GSH consumption, indicating that Fe-PcBC has better GPx-like activity.
The results show that the conjugated polymers Fe-PorBC and Fe-PcBC provided by the invention have excellent POD-like activity, excellent CAT, OXD, HPO-like and GPx-like activities, and can be used as high-efficiency multifunctional enzyme-like catalysts. In addition, fe-PcBC has better imitation POD, CAT, OXD, HPO and GPx activity than Fe-PorBC.
In summary, the invention provides a conjugated polymer biocatalysis material, a preparation method and application thereof, and belongs to the field of biocatalysis. The invention discovers for the first time that the Fe-based biocatalyst is Fe with the existing small molecule iron-based biocatalyst 3 O 4 Compared with TPPFe, hemin, pcFe, the conjugated polymer provided by the invention has more excellent POD-like activity. The invention also finds that the conjugated polymer provided by the invention has excellent imitation POD activity and excellent imitation POD, CAT, OXD, HPO and GPx activity. The preparation method of the conjugated polymer provided by the invention is simple, is suitable for large-scale production, and has wide application prospect in preparing the efficient multifunctional enzyme-like catalyst.
Claims (9)
1. Use of a conjugated polymer material in the preparation of a enzyme-like catalyst, characterized in that: the conjugated polymer material is formed by connecting a repeated structural unit shown in a formula I through a covalent bond:
i is a kind of
Wherein M is Fe.
2. Use according to claim 1, characterized in that: the conjugated polymer material is a polymer formed by connecting a repeating structural unit shown in a formula I through a covalent bond, and is a product obtained by taking a porphyrin-based conjugated polymer and a metal salt as raw materials to react, wherein the porphyrin-based conjugated polymer is a polymer formed by connecting a repeating structural unit shown in a formula III through a covalent bond:
formula III.
3. Use according to claim 2, characterized in that: the mass ratio of the porphyrin-based conjugated polymer to the metal salt is (1.0-2.0): 1; the metal salt is ferric salt; the temperature of the reaction is 100-140 DEG C o And C, reacting for 8-16h, wherein the solvent for the reaction is an organic solvent.
4. Use according to claim 3, characterized in that: the mass ratio of the porphyrin-based conjugated polymer to the metal salt is 1.2:1; the metal salt is Fe 3+ A salt; the temperature of the reaction is 120 o And C, reacting for 12-h, wherein the solvent for the reaction is dimethylformamide.
5. Use according to any one of claims 2-4, characterized in that: the preparation method of the porphyrin-based conjugated polymer comprises the following steps: adding polystyrene microspheres into water to form polystyrene microsphere suspension, adding acetic acid into the polystyrene microsphere suspension, uniformly mixing, then adding terephthalaldehyde and pyrrole, and reacting to obtain a polystyrene microsphere-loaded porphyrin polymer; adding the porphyrin polymer loaded by the polystyrene microsphere into toluene, stirring for 10-14 hours, filtering, and retaining the solid to obtain the porphyrin-based conjugated polymer.
6. Use according to claim 5, characterized in that: the proportion of the polystyrene microsphere suspension to the benzaldehyde to the pyrrole is (4-6) mL: (50-55) mg: (50-60) μL; in the polystyrene microsphere suspension, the solid content of the polystyrene microspheres is 4 wt-6 wt percent; the reaction is carried out in the presence of trifluoroacetic acid and nitrobenzene; the reaction temperature is 60-100 ℃ and the reaction time is 10-14 hours.
7. Use according to claim 6, characterized in that: the proportion of the polystyrene microsphere suspension, the benzaldehyde and the pyrrole is 5mL:52.5mg: 54. mu L; in the polystyrene microsphere suspension, the solid content of the polystyrene microspheres is 5wt percent; the temperature of the reaction was 80℃for 12 hours.
8. Use according to claim 1, characterized in that: the enzyme is POD enzyme, CAT enzyme, OXD enzyme, HPO enzyme and/or GPx enzyme.
9. Use according to claim 1 or 8, characterized in that: the enzyme-like catalyst is used as a medicament for preventing and/or treating bacterial infection and a medicament for accelerating wound healing.
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