CN115322340A - Conjugated polymer biocatalytic material and preparation method and application thereof - Google Patents
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Abstract
The invention provides a conjugated polymer biocatalysis material and a preparation method and application thereof, belonging to the field of biocatalysis. Compared with the existing micromolecule iron-based biocatalyst iron phthalocyanine (II), phthalocyanine, m-tetraphenylporphyrin iron chloride (III), ferroferric oxide and hemin, the conjugated polymer provided by the invention has more excellent POD-like activity for the first time. The invention also finds that, in addition to having excellent pseudo-POD activity, the conjugated polymer provided by the invention also has excellent pseudo-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 preparation of high-efficiency multifunctional enzyme-like catalysts.
Description
Technical Field
The invention belongs to the field of biocatalysis, and particularly relates to a conjugated polymer biocatalysis material, and a preparation method and application thereof.
Background
Porphyrins (porphyrins) are conjugated skeleton macrocyclic compounds formed by connecting four pyrrole rings through methine, and a nitrogen atom in the center of the macrocyclic compound is coordinated with a metal atom to form a metalloporphyrin complex (metalloporphyrin). Natural porphyrin and metalloporphyrin complex are widely present in animals and plants, such as heme, chlorophyll, vitamin B12 and cytochrome P-450, and have special physiological activity. Because natural porphyrin and metalloporphyrin complex molecules have rigidity, flexibility, electronic buffering property, photoelectromagnetism and high chemical stability, porphyrin chemistry research has been carried out as early as the 30 s in the 20 th century, and the natural porphyrin and metalloporphyrin complex molecules are widely used as photoconductors, semiconductors, superconductors, catalysts, anti-cancer drugs, color developing agents and the like.
Although natural porphyrins and metalloporphyrin compounds have many of the above excellent properties, mass production is difficult. Therefore, the design of artificially synthesized porphyrin and metalloporphyrin complexes is of great significance. Phthalocyanines have also received much attention as an artificially synthesized porphyrin derivative because they have 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 photobiological activity on tumors. Since the 80's of the 20 th century, a series of experimental results on the photoinactivation of human cancer cells cultured in vitro and the photodynamic damage of animal transplanted tumors by phthalocyanine have been reported in sequence, wherein zinc phthalocyanine has entered phase I clinical trials.
Although the application of artificially synthesized small-molecule metalloporphyrin compounds to wound healing, anti-tumor, anti-inflammatory and other aspects has been reported in the field of biocatalysis at present, on the one hand, the mechanism of the small-molecule metalloporphyrin compounds playing a therapeutic role in vivo is not elucidated; on the other hand, the therapeutic effects of these small-molecule metalloporphyrin compounds are yet to be further improved.
Disclosure of Invention
The invention aims to provide a conjugated polymer biocatalytic material as well as a preparation method and application thereof.
The conjugated polymer is a high molecular weight compound having a conjugated structure formed by connecting one or more kinds of repeating structural units by covalent bonds.
The invention provides a conjugated polymer material, which is a polymer formed by connecting repeating structural units shown in formula I or formula II through covalent bonds:
wherein M is a metal atom.
Further, M is Fe.
Further, the polymer is formed by connecting the repeating structural units shown in the formula I through covalent bonds, 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 the repeating structural units shown in the formula III through covalent bonds:
further, the mass ratio of the porphyrin-based conjugated polymer to the metal salt is (1.0-2.0): 1, preferably 1.2; the metal salt is iron salt, preferably Fe 3+ 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 porphyrin polymer loaded with the polystyrene microspheres; adding the porphyrin polymer loaded by the polystyrene microspheres into toluene, stirring for 10-14 hours, filtering, and retaining the solid to obtain a porphyrin-based conjugated polymer;
preferably, the proportion of the polystyrene microsphere suspension, the benzene dicarbaldehyde and the pyrrole is (4-6) mL: (50-55) mg: (50-60) μ L, preferably 5mL:52.5mg:54 mu L of the solution; in the polystyrene microsphere suspension, the solid content of the polystyrene microspheres is 4-6 wt.%, preferably 5wt.%; the reaction is carried out in the presence of trifluoroacetic acid and nitrobenzene; the reaction temperature is 60-100 ℃, preferably 80 ℃ and the reaction time is 10-14 hours, preferably 12 hours.
Furthermore, the polymer is formed by connecting the repeating structural units shown in the formula II through covalent bonds, and is a product obtained by reacting 1,2,4, 5-benzene tetracyanonitrile and metal salt serving as raw materials.
Further, the molar ratio of the 1,2,4, 5-benzenetetracarboxylic nitrile to the metal salt is (1.5-3.5): 1, preferably 2.5; the metal salt is iron salt, preferably Fe 3+ Salt; the reaction temperature is 160-200 ℃, preferably 180 ℃ and the reaction is carried outThe time is 5-15min, preferably 10min, the solvent for reaction is organic solvent, preferably ethylene glycol;
and/or the reaction is carried out in a microwave reactor, the reaction is carried out in the presence of a catalyst, the catalyst is an organic base, and the organic base is preferably 1, 8-diazacyclo (5, 4, 0) undec-7-ene.
The invention also provides application of the conjugated polymer material in preparation of a biomimetic catalyst.
Further, the enzyme is a POD enzyme, a CAT enzyme, an OXD enzyme, an HPO enzyme and/or a 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 micromolecule iron-based biocatalyst iron phthalocyanine (II), phthalocyanine, m-tetraphenylporphyrin iron chloride (III), ferroferric oxide and hemin, the conjugated polymer Fe-PorBC and Fe-PcBC provided by the invention has more excellent POD-like activity for the first time.
The free radical generated by Fe-PorBC in the catalytic process is mainly OH, while Fe-PcBC is mainly OH and O 2 · - . Compared with Fe-PorBC, fe-PcBC has better POD activity, better catalytic dynamics and stronger catalytic oxidation capability.
The invention also finds that the conjugated polymers Fe-PorBC and Fe-PcBC provided by the invention have excellent CAT, OXD, HPO and GPx imitating activities in addition to excellent POD imitating activity, and can be used as high-efficiency multifunctional enzyme imitating catalysts. Wherein Fe-PcBC has better activities of imitating POD, CAT, OXD, HPO and GPx compared with 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 preparation of high-efficiency multifunctional enzyme-like catalysts.
It will be apparent that various other modifications, substitutions and alterations can be made in the present invention without departing from the basic technical concept of the invention as described above, according to the common technical knowledge and common practice in the field.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 structural characterization of Fe-PorBC and Fe-PcBC at the atomic scale. (a) schematic structural diagram of Fe-PorBC; (b, c) AC-HAADF-STEM images of Fe-PorBC; (d) schematic structural diagram of Fe-PcBC; (e, f) AC-HAADF-STEM images of Fe-PcBC.
FIG. 2 of (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) the relative POD activity of different iron-based biocatalysts; (b) With H 2 O 2 And V of Fe-PorBC and Fe-PcBC with TMB as substrate max And TON values.
FIG. 4 reactive oxygen species generated by Fe-PorBC and Fe-PcBC. Recording (a) OH signal and (c) O 2 · - An EPR spectrum of the signal; record (b). OH signal and (d) O 2 · - Fluorescence spectrum of the signal.
FIG. 5 (a) MB degradation assay for Fe-PorBC and Fe-PcBC; (b) TBA quenching OH and BQ quenching O in MB catalytic degradation process 2 · - (ii) a POD activity of Fe-PorBC and Fe-PcBC under different (c) pH conditions and (d) temperatures, absorbance at pH 4.5 defined as 100%; * P<0.001. FIG. 6 various mimetic enzyme activities of Fe-PorBC and Fe-PcBC. (a) Catalytic generation of O by Fe-PorBC and Fe-PcBC 2 A time-dependent process of; (b) UV-visible absorption spectra of Fe-PorBC and Fe-PcBC catalyzed by oxidation of TMB (oxTMB) in HAc-NaAc buffer (0.1M, pH 4.5); (c) For recording O 2 · - An EPR spectrum of the signal; (d) UV-visible absorption spectra of Fe-PorBC and Fe-PcBC catalyzed oxidation of CB in PBS buffer (pH5.8); (e) Recording OCl - Fluorescence spectrum of the signal; (f) Fe-PorBC and Fe-PcBC inUltraviolet-visible absorption spectrum of DTNB catalyzed and oxidized in PBS buffer (pH 7.4); (g) Time-dependent curves for the catalytic degradation of DTNB by Fe-PorBC and Fe-PcBC; * P is<0.001。
FIG. 7 is a schematic diagram of a synthetic route of Fe-PorBC.
FIG. 8 is a schematic diagram of the synthetic route of Fe-PcBC.
FIG. 9 SEM photographs and size distributions of Fe-PorBC (a, b) and Fe-PcBC (c, d). Scale bar: 1 μm.
FIG. 10 (a) TEM and (b) high resolution TEM images of Fe-PorBC.
FIG. 11 (a) TEM, (b) high resolution TEM, (c, d) HAADF-STEM images of Fe-PcBC.
FIG. 12 shows (a) FT-IR spectrum and (b) UV-vis spectrum of Fe-PcBC, pcFe and Pc.
Typical XRD spectra of Fe-PorBC and Fe-PcBC.
Detailed Description
The raw materials and equipment used in the invention are known products, and are obtained by purchasing products sold in the market.
Example 1: preparation of iron porphyrin-based biocatalyst Fe-PorBC
The Fe-PorBC is synthesized by a one-pot method, and a schematic diagram of a synthetic route is shown in figure 7.
1. Synthesis of porphyrin-based biocatalysts (PorBC)
1) Synthesis of monodisperse Polystyrene (PS) microspheres
Monodisperse PS microspheres were prepared according to the method described in the literature (Shen, K.; zhang, L.; chen, X.; liu, L.; zhang, D.; han, Y.; chen, J.; long, J.; luque, R.; li, Y.; et al, ordered Macro-Microporous Metal-Organic Framework Single crystals, 2018,359, 206-210.). The preparation method comprises the following steps: styrene (39 mL) was first washed with 12mL of aqueous NaOH (10 wt.% concentration) and deionized water, respectively, to remove stabilizers, and then the washed styrene was poured into a three-necked flask containing 300mL of deionized water. 1.5g of polyvinylpyrrolidone (PVP) was added to a three-necked flask, and the mixed solution was bubbled with nitrogen for 15min and refluxed for 30min with magnetic stirring at 95 ℃. Finally, 0.5g K was added to a three-necked flask 2 S 2 O 8 And 50mL of deionized Water-initiated benzeneAnd (3) polymerizing ethylene. 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) Synthesis of PS @ Por by using monodisperse PS microspheres as template
First, 5mL of a suspension of monodisperse PS microspheres with a solid content of 5wt.% was ultrasonically mixed with 250mL of glacial acetic acid for 30min to form a homogeneous suspension. Then, 52.5mg of terephthalaldehyde (BDA) and 54 μ L of pyrrole were added to the suspension and subjected to ultrasonic treatment for 30min, 1mL of trifluoroacetic acid (TFA) and 5mL of Nitrobenzene (NBZ) were added as a catalyst and an oxidizing agent, respectively, and ultrasonic treatment 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 a black polystyrene microsphere-loaded porphyrin polymer named PS @ Por.
3) Synthetic PorBC
Adding PS @ Por into 50mL toluene, ultrasonically dispersing 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, which is named as PorBC.
2. Synthesis of Fe-PorBC
10mg of PorBC was added to a vial containing 2mL of Dimethylformamide (DMF). Subsequently, feCl is added 3 (8.1mg, 0.05mM) was added to the solution and sonicated for 10min with continuous stirring at 120 ℃ for 12h. And then filtering the product, washing a filter cake with DMF (dimethyl formamide), deionized water and ethanol for three times respectively, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the hollow spherical Fe-PorBC.
Example 2: preparation of iron phthalocyanine based biocatalyst Fe-PcBC
The Fe-PcBC is prepared by a rapid microwave heating process, and a schematic synthetic route is shown in figure 8. First 1,2,4, 5-pyromellitic nitrile (89mg, 0.5 mM) and FeCl 3 (32.4 mg,0.2 mM) were mixed 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, and respectively using ethylene glycol and 3% hydrochloric acid as filter cakesWashing with deionized water and ethanol in sequence, and drying at 60 ℃ in vacuum overnight to obtain Fe-PcBC.
The beneficial effects of the present invention are demonstrated by the following experimental examples.
The following experimental examples used Fe-PorBC prepared from example 1 and Fe-PcBC prepared from example 2; the control samples are shown in Table 1 and are all commercially available.
TABLE 1 control sample information
| Name (R) | Specification of | Manufacturer(s) of |
| 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 methods
Solid NMR spectra were measured on a Bruker AV400 spectrometer operating at 75.5MHz 13 C. Fe-PcBC and Fe-PorBC have been subjected to 13 C cross polarization and magic angle spin spectroscopy studies. Performing Fourier transform infrared spectroscopy (FT-IR) analysis on the sample with Nicolet-560 spectrophotometer (Nicol, US) in the range of 4000-500cm -1 Resolution of 2cm -1 . Raman spectra were recorded on a Horiba Jobin Yvon LabRam HR800 with an excitation wavelength of 633nm. The ultraviolet-visible (UV-vis) absorption spectrum was performed on an 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 Microscopy (TEM) images and EDS mapping images were obtained by operating a Talos F200x TEM microscope (feiltd., USA) at 200 kV. The crystalline phase state of the sample was observed with a Bruker D8 focused x-ray diffractometer under copper radiation at a voltage of 40 kV. The sample was scanned over a2 theta range of 5 to 80. The ESR experiments were performed on a JEOL-FA200ESR spectrophotometer. Fluorescence measurements were performed on a Hitachi F-4600 fluorescence spectrophotometer.
2. Results of the experiment
XPS atomic ratio and Fe atomic weight ratio of the materials
TABLE 3 fitting results of C1s spectra in different materials
TABLE 4 fitting results of N1s spectra in different materials with relative N content
TABLE 5 Fe K-edge EXAFS Curve fitting parameters for each sample (S02 = 0.90)
a N: a coordination number; b r: the distance between the absorber and the backscattered atoms; c σ 2 : a Debye-Waller factor; d ΔE 0 : and correcting the internal potential. R factor: degree of fitting. e Fitting range:
and
f fitting range:
and
g fitting range:
and
according to SEM observation (figure 9), the Fe-PorBC and the Fe-PcBC prepared by the invention are both spherical in shape, and the particle sizes are respectively about 220nm and 141.7nm. TEM shows (fig. 10 and 11) that Fe-PorBC and Fe-PcBC have disordered carbon structures, without Fe clusters or nanoparticles, indicating that the polymer is amorphous and free of metal atom aggregation. AC-HAADF-STEM further observed a large number of small bright spots in the carbon substrate, demonstrating that the Fe in Fe-PorBC and Fe-PcBC is monoatomic and consistent with the theoretical structure (FIGS. 1 a-f).
By means of solids 13 C NMR and raman spectroscopy investigated the chemical structure of conjugated polymers. As shown in figure 2a of the drawings, 13 the peak at 136.5ppm in the C NMR spectrum was assigned to C 2 、C meso 、C β 119.1ppm of the peak ascribed to C α And C 2 Successful construction of iron porphyrin based conjugated polymers was confirmed. 13 The three peaks in the C NMR spectrum at 164.5, 132.4, 114.9ppm are due to the phthalocyanine macrocycle in the iron phthalocyanine based conjugated polymer network (fig. 2 b). In addition, fe-PorBC was at 1332cm -1 The Raman spectrum of (A) shows typical B 1g Mode, this is caused by the symmetric pyrrole ring oscillation of the porphyrin molecule (fig. 2 c). Similarly, raman spectrum of Fe-PcBC obtained A with phthalocyanine molecule vibrating in-plane 1g 、B 1g And B 2g The mode is verified to be 677 cm, 744 cm and 1456cm respectively -1 (FIG. 2 d), indicating the successful synthesis of two conjugated polymers.
FT-IR and UV-vis further investigated the Fe-PcBC extended conjugated structure. FT-IR spectroscopy showed (FIG. 12 a) that the C-H of Fe-PcBC was 1118cm compared to PcFe small molecules -1 The signal at (A) is significantly reduced, indicating that the in-plane bending vibration of C-H at the periphery of the benzene ring is reduced, confirming that the phthalocyanine monomer is polymerized. UV-vis further found that the B and Q bands of Fe-PcBC were significantly red-shifted compared to PcFe, indicating that Fe-PcBC generates an extended conjugated structure through the attachment of benzene rings (FIG. 12B). In addition, XRD showed that both Fe-PcBC and Fe-PorBC showed a typical conjugated polymer peak around 26 deg. (FIG. 13), and no crystalline peak of Fe or iron oxide, which proved that both were amorphous structures without metal element, which is also consistent with STEM data.
The experiments show 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 peroxidase-like enzyme
1. Experimental methods
(1) Peroxidase-mimetic activity assay
Monitoring of H with TMB as substrate 2 O 2 The peroxidase activity of the biocatalyst was determined. To 1.926mL of acetic acid-sodium acetate buffer (HAc-NaAc) (0.1M, pH 4.5) was added biocatalyst (4 mg/mL, 25. Mu.L), H 2 O 2 (100mM, 25. Mu.L) and TMB (41.6 mM, 24. Mu.L in DMF) were mixed well. After incubation at 25 ℃ for 10min, the absorbance of the reaction solution at 652nm was recorded using a microplate reader. In addition, the pH stability and thermal stability of the biocatalyst were determined by measuring the absorbance at 652nm of the biocatalyst 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 a mixture containing biocatalyst (4 mg/mL, 25. Mu.L), H 2 O 2 (100mM, 25. Mu.L) and HAc-NaAc buffer solutions (0.1M, pH 4.5) at different concentrations of TMB were mixed, and the absorbance of the reaction solution at 652nm was recorded with a microplate reader for different times. To study the biocatalyst on H 2 O 2 Using a constant concentration of TMB and varying concentrations of H 2 O 2 As a substrate. Likewise, the reaction kinetics of the biocatalyst on TMB was also determined by using a constant concentration of H 2 O 2 And various concentrations of TMB as substrate. The reaction rate and substrate concentration were fitted in the Michaelis-Menten equation and kinetic constants (V) were calculated max And K m ) The Michaelis-Menten equation is as follows:
in the formula, V 0 As initial reaction rate, V max Is the maximum reaction rate. Wherein, V max Is obtained under the condition of saturated substrate. [ S ]]Substrate concentration is used. K m And the mie constant, which represents the substrate concentration at which the initial reaction rate reached half of its maximum reaction rate.
The catalytic activity of the biocatalyst is defined as follows:
K cat ＝V max /[E 0 ] (2-2)
in the formula, K cat The reaction constant is expressed as the maximum amount of substrate converted per active catalytic center (TON). E 0 Is the molar concentration of the metal active center.
(3) Detection of reactive oxygen radicals
3.1 Fluorescent probe test
TA as fluorescent Probe (. Lamda.) ex ＝315nm，λ em =440 nm) detection of biocatalyst catalysis H 2 O 2 OH produced by decomposition. To 1.5mL HAc-NaAc buffer solution (0.1M, pH 4.5) was added biocatalyst (4 mg/mL, 30. Mu.L), 4mM NaTA (a reaction of NaOH and TA) and 60mM H 2 O 2 Then, the mixed solution was incubated at 37 ℃ for 12 hours, and the fluorescence spectrum of the reaction solution was measured by a fluorescence spectrometer. Using HE as fluorescent probe (. Lamda.) ex ＝470nm，λ em =624 nm) detection of biocatalyst catalyzed H 2 O 2 O produced by decomposition 2 To prepare. First, a buffered HAc-NaAc solution of biocatalyst (pH 4.5, 100. Mu.g/mL, 1.5 mL) was mixed with H 2 O 2 (100mM, 1.5. Mu.L) were mixed and incubated at 37 ℃ for 30min. Then, HE-ethanol solution (1 mg/mL,1.5 mL) was added, and after further incubation for 30min, the fluorescence spectrum of the reaction solution was measured by a fluorescence spectrometer.
3.2 EPR test
Detection of biocatalyst catalyzed H with DMPO as spin capture agent 2 O 2 OH produced by decomposition. To 0.5mL HAc-NaAc buffer (0.1M, pH 4.5) was added biocatalyst (4 mg/mL, 50. Mu.L) and H 2 O 2 (10. Mu.L, 10M) was added, and after mixing, 10. Mu.L of DMPO was added. After incubation at 25 ℃ for 10min, the reaction solution was aspirated by a capillary for EPR test. DMSO is used to replace HAc-NaAc buffer solution, DMPO is used as capture agent to generate O 2 · - The detection is performed in the same procedure.
2. Results of the experiment
TABLE 6 relative POD Activity of different iron-based biocatalysts
Note: fe content (wt%) represents the mass fraction of iron, intensity of ox TMB represents the Intensity of oxidized TMB, normalized Intensity of ox TMB represents the Intensity of oxidized TMB after normalization (i.e., the Intensity at the same Fe content), and Relative Intensity ratio (%).
TABLE 7 with H 2 O 2 Kinetic comparison of simulated POD catalytic activity for substrates
Note: k is m Is the Michaelis constant, V max To maximum reaction velocity, V 0 Is the initial reaction rate. [ E ] 0 ]Michaelis-Menten plots were fitted by varying substrate concentrations for molar concentrations of metal active sites. The conversion number (TON) is the maximum amount of substrate converted per active catalytic center, K cat Is the catalytic constant. K cat /K m Values represent catalytic efficiency.
TABLE 8 kinetic comparison of POD-simulated catalytic activity with TMB as substrate
First, POD performance of Fe-PorBC and Fe-PcBC was evaluated by TMB color reaction. As shown in FIG. 3a and Table 6, under the condition of the same Fe content, the absorbance of the oxTMB generated by the catalysis of Fe-PorBC and Fe-PcBC is the highest, which shows that the catalytic activity of the two catalysts is better than that of other small-molecular iron-based catalysts. In addition, fe-PcBC has higher absorbance than Fe-PorBC, indicating that Fe-PcBC has better POD performance. Results of steady state kinetic testing (FIG. 3b, tables 7 and 8) 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 substrate TMB, fe-PcBC max (130.0) is about 13.5 times that of Fe-PorBC (9.06). TON value (H) of Fe-PcBC 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, fe-PcBC catalyzes more rapidly, turnover of substrate is faster, and affinity to substrate is better, ultimately leading to its catalytic efficiency (K) cat /K m ) Extremely high and far higher than Fe-PorBC (H) 2 O 2 146 times, TMB 90 times).
In order to elucidate the catalytic mechanism of Fe-PorBC and Fe-PcBC, the ROS generated in the catalytic process were explored by using EPR spectroscopy and a fluorescent probe. As shown in FIG. 4a, the characteristic peak signal intensity of the DMPO/. OH adduct is clearly 1:2:2:1, illustrating that Fe-PorBC and Fe-PcBC catalyze H 2 O 2 OH is produced in the decomposition process. TA as OH specific fluorescent probe detection found that both generated OH, and Fe-PorBC was slightly higher in fluorescence intensity than Fe-PcBC, indicating that Fe-PorBC produced more OH (FIG. 4 b). Furthermore, EPR analysis showed that when the reaction solution was replaced with DMSO, the signal intensity of Fe-PcBC was 1:1:1:1:1 (FIG. 4 c), which is a typical DMPO/O 2 · - Characteristic peak of adduct, indicating that Fe-PcBC catalyzes H 2 O 2 O is also generated during the decomposition process 2 · - . Further captures O by specific probe HE 2 · - Intermediate (FIG. 4 e), the results show that the absorbance at 623nm is higher for the Fe-PcBC group, indicating that Fe-PcBC is able to produce more O 2 · - This is consistent with the EPR results.
The invention further explores the catalytic oxidation capacity of Fe-PorBC and Fe-PcBC by utilizing MB degradation experiments. As shown in FIG. 5a, compared with Fe-PorBC (13.5%), the catalytic degradation rate of the Fe-PcBC on MB after 30min reaches 74.8%, which is much higher than that of the Fe-PorBC, and the excellent catalytic oxidation performance of the Fe-PcBC is shown. To investigate the production of OH and O by Fe-PcBC 2 · - t-Butanol (TBA) and p-Benzoquinone (BQ) as OH and O, respectively 2 · - The scavenger of (1). As shown in FIG. 5b, the absorbance of oxTMB decreased rapidly with either TBA or BQ addition, indicating OH and O 2 · - Intermediate product in ROS generation process of Fe-PcBCPlay an important role. Wherein BQ has a large influence on absorbance, and indicates that ROS generated by Fe-PcBC is mainly O 2 · - 。
In addition, the present inventors also studied the effect of pH and temperature on POD activity, as shown in fig. 5c, d, fe-PorBC and Fe-PcBC showed the best POD activity at pH =4 and maintained high catalytic activity over a wide temperature range, showing the catalytic stability of Fe-PorBC and Fe-PcBC under severe environment.
The above results show that Fe is the same as the existing Fe-based biocatalyst under the condition of the same Fe content 3 O 4 Compared with TPPFe, hemin and PcFe, the conjugated polymers Fe-PorBC and Fe-PcBC provided by the invention have more excellent POD activity. In addition, compared with Fe-PorBC, fe-PcBC has better POD activity, better catalytic kinetics and stronger catalytic oxidation capacity.
Experimental example 3: performance testing of biocatalyst multienzyme Activity
1. Experimental methods
(1) Mimic Oxidase (OXD) Activity assay
The OXD activity of the material was studied using TMB as substrate. To 1.951mL of HAc-NaAc buffer (0.1M, pH 4.5) were added the material (4 mg/mL, 25. Mu.L) and TMB (41.6 mM, 24. Mu.L in DMF) and mixed well. After incubation at 25 ℃ for 10min, the absorbance of the reaction solution at 652nm was recorded using a microplate reader. The oxygen, air and nitrogen are introduced to compare the activity of the simulated OXD.
(2) Catalase (CAT) Activity test
For investigating material decomposition H 2 O 2 In 20mL of HAc-NaAc buffer solution (0.1M, pH 4.5), the material (10 mg/mL, 20. Mu.L) and H were added 2 O 2 (10M, 200. Mu.L), oxygen production was measured at various time points using a dissolved oxygen meter.
(3) Activity test for Haloperoxidase (HPO)
Hypochlorite ion (ClO) - ) Specifically binds to CB, thereby oxidizing the blue CB to pink, such that the uv absorbance of the CB decreases from 640nm and increases at 520nm, with an equivalent point at about 540 nm. In 1.84mL of CBTo a PBS solution (0.1M, pH5.8, final concentration of CB of 200. Mu.M) were added a material (4 mg/mL, 150. Mu.L) and H 2 O 2 (100mM, 10. Mu.L). After incubation at 25 ℃ for 30min, the absorbance of the reaction solution at 640nm and 520nm was recorded using a microplate reader.
APF as fluorescent probe (lambda) ex ＝485nm，λ em =514 nm) of OCl produced in a catalytic reaction of a detection 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 (100mM, 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 fluorescent microplate reader.
(4) Glutathione peroxidase mimetic (GPx) Activity assay
5,5' -dithiobis (2-nitrobenzoic acid) (DTNB) is a thiol indicator. Its disulfide bond is cleaved to yield 2-nitro-5-thiobenzoic acid, whose characteristic absorbance at 408nm decreases with the passage of time. Changes in UV absorption spectra at different time points were monitored by adding material (4 mg/mL, 25. Mu.L) and 5mM GSH in 2mL PBS (0.1M, pH 7.4) followed by DTNB (3 mg/mL, 30. Mu.L).
2. Results of the experiment
Enzymes exhibit a wide variety of catalytic activities on different substrates under different catalytic conditions, which is called multienzyme activity. After verifying that Fe-PorBC and Fe-PcBC have the POD activity imitation, the invention also researches the CAT, OXD, HPO and GPx imitation performances of the Fe-PorBC and the Fe-PcBC. As shown in FIG. 6a, when used in CAT enzyme catalyzed reaction, fe-PcBC reached 22.07mg/L of oxygen yield 5.9 times that of Fe-PorBC (3.72 mg/L), showing good H yield 2 O 2 The decomposition capability. In addition, in O 2 As the substrate, the oxMB of Fe-PcBC has higher absorbance at 652nm, which shows that the OXD activity is far better than that of Fe-PorBC (FIG. 6 b), and O generated in the reaction 2 · - Was also detected by EPR (fig. 6 c). HPO enzymes catalyze H 2 O 2 Oxidation of halides to ClO - And thus specifically recognized by CB and APF. As can be seen from FIG. 6d, the CB UV absorption spectrum of Fe-PcBC drops rapidly at 640nm, indicating that more ClO is produced, compared to Fe-PorBC - . In addition, APF also detected ClO produced by Fe-PorBC and Fe-PcBC - The higher fluorescence intensity also demonstrates that Fe-PcBC has better HPO-like activity (FIG. 6 e). GPx enzyme can convert the radical scavenger reduced Glutathione (GSH) to oxidized glutathione (GSSG) by redox reactions, and therefore the GPx-mimicking activity of Fe-PorBC and Fe-PcBC was studied using DTNB as a thiol indicator. As shown in FIG. 6f,g, fe-PcBC showed a high GSH consumption rate of 77.34% over 30min reaction time, while Fe-PorBC showed 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 activities of simulating CAT, OXD, HPO and GPx besides excellent activity of simulating POD, and can be used as high-efficiency multifunctional enzyme simulating catalysts. In addition, fe-PcBC has better activity of imitating POD, CAT, OXD, HPO and GPx compared with Fe-PorBC.
In conclusion, the invention provides a conjugated polymer biocatalytic material as well as a preparation method and application thereof, belonging to the field of biocatalysis. The invention discovers that the Fe-based biocatalyst is the same as the existing small-molecular iron-based biocatalyst for the first time 3 O 4 Compared with TPPFe, hemin and PcFe, the conjugated polymer provided by the invention has more excellent POD (peroxidase) activity. The present invention also found that, in addition to having excellent pseudo-POD activity, the conjugated polymer provided by the present invention also has excellent pseudo-POD, CAT, OXD, HPO and GPx activities. 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 preparation of high-efficiency multifunctional enzyme-like catalysts.
Claims (10)
1. A conjugated polymer material, characterized in that: the polymer is formed by connecting repeating structural units shown in formula I or formula II through covalent bonds:
wherein M is a metal atom.
2. The conjugated polymer material of claim 1, wherein: m is Fe.
3. The conjugated polymer material according to claim 1 or 2, characterized in that: the porphyrin-based conjugated polymer is a polymer formed by connecting repeating structural units shown in a formula I through covalent bonds, and is a product obtained by reacting porphyrin-based conjugated polymers and metal salts serving as raw materials, wherein the porphyrin-based conjugated polymers are polymers formed by connecting repeating structural units shown in a formula III through covalent bonds:
4. the conjugated polymer material of claim 3, wherein: the mass ratio of the porphyrin-based conjugated polymer to the metal salt is (1.0-2.0): 1, preferably 1.2; the metal salt is iron salt, preferably Fe 3+ 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.
5. The conjugated polymer material according to claim 3 or 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 porphyrin polymer loaded by the polystyrene microspheres; adding the porphyrin polymer loaded by the polystyrene microspheres into toluene, stirring for 10-14 hours, filtering, and retaining the solid to obtain a porphyrin-based conjugated polymer;
preferably, the proportion of the polystyrene microsphere suspension, the benzene dicarbaldehyde and the pyrrole is (4-6) mL: (50-55) mg: (50-60) μ L, preferably 5mL:52.5mg:54 mu L of the solution; in the polystyrene microsphere suspension, the solid content of the polystyrene microspheres is 4-6 wt.%, preferably 5wt.%; the reaction is carried out in the presence of trifluoroacetic acid and nitrobenzene; the reaction temperature is 60-100 ℃, preferably 80 ℃ and the reaction time is 10-14 hours, preferably 12 hours.
6. The conjugated polymer material according to claim 1 or 2, characterized in that: the polymer is formed by connecting repeating structural units shown in a formula II through covalent bonds, and is a product obtained by reacting 1,2,4, 5-benzene tetracyanonitrile and metal salt serving as raw materials.
7. The conjugated polymer material of claim 6, wherein: the molar ratio of the 1,2,4, 5-benzenetetracarboxylic nitrile to the metal salt is (1.5-3.5): 1, preferably 2.5; the metal salt is iron 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 is carried out in the presence of a catalyst, the catalyst is an organic base, and the organic base is preferably 1, 8-diazacyclo (5, 4, 0) undec-7-ene.
8. Use of a conjugated polymer material according to any one of claims 1 to 7 in the preparation of a biomimetic catalyst.
9. Use according to claim 8, characterized in that: the enzyme is POD enzyme, CAT enzyme, OXD enzyme, HPO enzyme and/or GPx enzyme.
10. Use according to claim 8 or 9, characterized in that: the enzyme-like catalyst is a medicament for preventing and/or treating bacterial infection and a medicament for accelerating wound healing.
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