CN114539544A - Copper phthalocyanine polymer nano particle and preparation method and application thereof - Google Patents
Copper phthalocyanine polymer nano particle and preparation method and application thereof Download PDFInfo
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- CN114539544A CN114539544A CN202210032991.6A CN202210032991A CN114539544A CN 114539544 A CN114539544 A CN 114539544A CN 202210032991 A CN202210032991 A CN 202210032991A CN 114539544 A CN114539544 A CN 114539544A
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- copper
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- phthalocyanine
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 124
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000001514 detection method Methods 0.000 claims abstract description 44
- 102000003992 Peroxidases Human genes 0.000 claims abstract description 32
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 14
- 108040007629 peroxidase activity proteins Proteins 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 150000001879 copper Chemical class 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FAAXSAZENACQBT-UHFFFAOYSA-N benzene-1,2,4,5-tetracarbonitrile Chemical compound N#CC1=CC(C#N)=C(C#N)C=C1C#N FAAXSAZENACQBT-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- -1 1,2,4, 5-benzenetetracarboxylic nitrile Chemical class 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims 1
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- 230000003197 catalytic effect Effects 0.000 abstract description 29
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- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
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Abstract
The invention provides copper phthalocyanine polymer nano-particles Cu-PcCP NPs, which are coordination complexes of a copper phthalocyanine polymer and copper ions; the phthalocyanine polymer is formed by connecting at least two phthalocyanine units sharing at least one benzene ring, and the molar ratio of the phthalocyanine units to copper ions of the phthalocyanine polymer is (1-2): 1; the structure of the phthalocyanine unit is shown below. As a new peroxidase mimic, the Cu-PcCP NPs have excellent enzyme-like catalytic activity, stronger substrate selectivity and good stability, can resist various severe conditions including high temperature and low pH, and can isolate a corresponding analysis system from oxygen when applied to a biomolecule detection sensor to ensure that the system can be used for detecting the target productThe polymer-based enzyme mimics can be used for specific, sensitive and stable biosensors. Based on Cu-PcCP NPs to H2O2And the L-cysteine and the glucose are detected, the linear range is wide, the detection limit is low, the good applicability of the detection of the biomolecules is shown, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of biomolecule detection, and particularly relates to copper phthalocyanine polymer nanoparticles and a preparation method and application thereof.
Background
Biosensor-mediated detection of biomolecules has become an increasingly important application in many fields, especially in disease diagnosis and treatment. Natural enzymes catalyzing various reactions in organisms have high substrate selectivity and catalytic efficiency, and are proved to be excellent biosensors for detecting biomolecules such as nucleic acid, protein, cells, glucose, dopamine, L-cysteine, glutathione and the like in the fields of disease diagnosis and bioanalysis. But the factors of high cost, instability in non-physiological environment, difficult storage and the like limit the further application of the compound. In this case, the nanomaterial having enzymatic activity is a substitute for natural enzymes due to its high stability, low cost, and adjustable catalytic activity.
To date, more than 50 nanomaterials have been found to have catalytic activity similar to natural enzymes such as Peroxidase (POD), Oxidase (OXD), Catalase (CAT), superoxide dismutase (SOD), glucose oxidase (GOx), etc. Among them, particularly, noble metal Nanoparticles (NPs), metal oxides, Metal Organic Frameworks (MOFs), and metal/heteroatom-doped carbon nanostructures have POD-like enzyme activities that catalyze the decomposition of hydrogen peroxide into more active radicals, and have been widely used in the field of bioassays. However, poor stability of use of metal oxides and MOFs, high adsorption rate of carbon-based materials interfering with their accuracy, and high cost of noble metal NPs have hindered the application of POD enzyme mimics as biosensors.
In designing new generation biosensors, polymer materials have gradually become candidate materials to meet the above requirements. However, since the electron transfer capability of the polymer material is low, the enzyme-like activity is not ideal, and the sensing stability is poor, it is still a challenge to construct a polymer material biosensor with high sensitivity compared to the most advanced enzyme-like nanomaterial biosensor. Recent researches show that compared with traditional polymers, phthalocyanine-based high polymer materials have unique advantages, such as a strong pi conjugated system, a high pi-d delocalization effect, good conductivity, excellent metal chelating performance and high chemical stability. This may ultimately lead to high enzyme-like perception activities. Bai et al synthesized Manganese Phthalocyanine spherical and linear nanocrystals by supramolecular Self-assembly as POD enzyme mimics for catalytic Tumor therapy showing good in vitro and in vivo antitumor effect (Wang, j.; Gao, s.; Wang, x.; Zhang, h.; Ren, x.; Liu, j.; Bai, f. seif-isolated mangase Nanoparticles with Enhanced Peroxidase-Activity for Anti-Tumor therapy. nano. res 2021.). However, size and morphology are very important for enzyme mimetics as this affects their affinity to the substrate and the distribution of catalytically active sites. The manganese phthalocyanine reported in the above documents is a micromolecular substance formed by coordination of phthalocyanine and manganese ions, and most of commercial metal phthalocyanines or derivatives thereof exist in a micromolecular form at present, are easy to aggregate to form micron-sized particles due to strong hydrophobic effect, have small specific surface area, are less exposed in catalytic active centers, are difficult to contact with a substrate for catalytic reaction, greatly reduce catalytic efficiency, and are not beneficial to being subsequently applied as an enzyme mimic.
In order to meet the increasing requirements on detection sensitivity and selectivity, a novel POD enzyme mimic with high catalytic performance is further explored, so that the method has important significance in better biomolecule detection.
Disclosure of Invention
The invention aims to provide copper phthalocyanine polymer nanoparticles with good stability and high catalytic efficiency as a novel POD enzyme mimic.
The invention provides a copper phthalocyanine polymer nano particle which is characterized in that the copper phthalocyanine polymer nano particle is a coordination complex of a phthalocyanine polymer and copper ions; the phthalocyanine polymer is formed by connecting at least two phthalocyanine units sharing at least one benzene ring, and the molar ratio of the phthalocyanine units to copper ions of the phthalocyanine polymer is (1-2): 1, preferably (1.25-2): 1, more preferably 1.25: 1;
the structure of the phthalocyanine unit is as follows:
further, the particle diameter of the nanoparticles is 222.7 + -58.4 nm.
Furthermore, the nano-particle is prepared by dispersing 1,2,4, 5-benzene tetracarbonitrile and copper salt in alcohol and carrying out microwave reaction under the action of a catalyst.
Further, the molar ratio of the 1,2,4, 5-benzenetetracarboxylic nitrile to the copper salt is (4-5): (1-3), preferably 5: 2.
Further, the microwave reaction power is 300-350W, and the time is 5-15 min;
preferably, the microwave reaction power is 320W, and the time is 10 min.
The invention also provides a preparation method of the nano-particles, which comprises the following steps:
(1) dispersing 1,2,4, 5-benzene tetracarbonitrile and copper salt in alcohol, adding catalyst and dispersing uniformly;
(2) reacting the mixed system obtained in the step (1) under the action of microwaves;
further, the copper salt is cupric chloride, cupric bromide, cupric sulfate, cupric acetate, copper acetylacetonate; preferably copper chloride;
and/or the alcohol is ethylene glycol, n-amyl alcohol, n-octyl alcohol;
and/or, the catalyst is DBU.
More importantly, the molar ratio of the 1,2,4, 5-benzene tetracarboxylic nitrile to the copper salt is (4-5) to (1-3), preferably 5: 2.
Furthermore, the microwave is at a power of 300-350W for 5-15 min; preferably with a power of 320W for 10 min.
The invention also provides the application of the nano-particles in a biomolecule detection reagent; preferably, the nanoparticles act as peroxidase mimics in a biomolecule detection reagent.
The invention has the beneficial effects that:
the invention provides copper phthalocyanine polymer nano-particle Cu-PcCP NPs with simple preparation method, which is used as a novel POD enzyme simulant, not only has excellent enzyme-like catalytic activity, but also has stronger substrate selectivity and good stability, can resist various severe conditions including high temperature and low pH, can isolate a corresponding analysis system from oxygen when being applied to a biomolecule detection sensor, and can ensure that the macromolecule-based enzyme simulant can be used for a specific, sensitive and stable biosensor. Based on Cu-PcCP NPs to H2O2And the L-cysteine and the glucose are detected, the linear range is wide, the detection limit is low, the good applicability of the detection of the biomolecules is shown, and the application prospect is wide.
Interpretation of terms of the invention:
"DBU" means 1, 8-diazabicyclo [5.4.0] undec-7-ene, CAS number 6674-22-2.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
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 shows the preparation of Cu-PcCP NPs and morphological characterization thereof. (a) The synthetic route of Cu-PcCP NPs is shown schematically; (b) SEM images of Cu-PcCP NPs; (c) TEM images of Cu-PcCP NPs; (d) dark field TEM images of Cu-PcCP NPs; (e) SAED mode for Cu-PcCP NPs; (f) EDS element surface scanning charts corresponding to C (blue), N (green) and Cu (pink); (g) element merged STEM images; (h) typical PXRD patterns for Cu-PcCP NPs; (i) EDS spectra corresponding to Cu-PcCP NPs. (j) line scan of Cu-PcCP NPs (g).
FIG. 2 is an SEM image of PcCP NPs showing both blocky and packed morphology.
FIG. 3 is a structural representation of Cu-PcCP NPs. (ii) Raman spectra of Cu-PcCP NPs and commercial CuPc; (b) FT-IR spectroscopy; (c) ultraviolet and visible spectrum. High resolution XPS spectra of Cu 2p (d), N1 s (e), and C1s (f) for Cu-PcCP NPs.
FIG. 4 is an XPS measurement spectrum of Cu-PcCP NPs.
FIG. 5 shows POD enzyme activity of Cu-PcCP NPs. (a) A schematic diagram of POD-like enzyme catalysis mechanism of Cu-PcCP NPs; (b) h2O2The ultraviolet-visible absorption spectrum of the reaction system in the presence; (c) ultraviolet-visible absorption spectra of Cu-PcCP NPs reaction systems with different concentrations; (d) time-dependent changes in oxTMB absorption intensity with changes in Cu-PcCP NPs concentration; (e) and (f) describe the relative POD-like enzyme activities of Cu-PcCP NPs under different pH conditions and at different temperatures, respectively. The highest is defined as 100% relative activity. Error bars were obtained by three measurements.
FIG. 6 is the relative POD enzyme activity of Cu-PcCP NPs at room temperature.
FIG. 7 is a steady state kinetic analysis of Cu-PcCP NPs. (a) H2O2And (b) the Michaelis-Menten curve for TMB; error bars were obtained by three measurements. Cu-PcCP NPs to (c) H2O2And (d) a Lineweaver-Burk plot of the kinetic constants of TMB. (e) The reported performance of non-noble metal POD enzyme mimics was compared to this work.
FIG. 8 is a colorimetric detection of H2O2. (a) Different concentrations of H2O2Ultraviolet-visible absorption spectrum of the reaction system; (b) h2O2The concentration-response curve detected. Illustration of the drawing H2O2Linear calibration graph of (a). Error bars represent the standard deviation of the three measurements.
FIG. 9 is a colorimetric detection of L-cysteine. (a) Schematic diagram of L-cysteine colorimetric method based on Cu-PcCP NPs inhibition. (b) Ultraviolet-visible absorption spectra of different concentrations of L-cysteine reaction systems. (c) L-cysteine assay concentration-absorbance curve. Inset is a linear calibration plot for L-cysteine. (d) influence of pH on the activity of Cu-PcCP NPs. (e) Selective assays for L-cysteine detection were performed by monitoring changes in absorbance in the presence of L-cysteine and its analogs. Error bars represent the standard deviation of the three measurements.
FIG. 10 is a colorimetric detection of glucose. (a) Schematic diagram of cascade catalytic detection of glucose by Cu-PcCP NPs; (b) ultraviolet-visible absorption spectra of glucose reaction systems of different concentrations; (c) concentration-absorbance curve for glucose assay. Inset linear calibration plot for glucose; (d) influence of pH on the activity of Cu-PcCP NPs; (e) the selective analysis of glucose detection is performed by monitoring the change in absorbance in the presence of glucose and its analogs. Insert photograph of reaction solution of glucose and the like. Error bars represent the standard deviation of the three measurements.
Detailed Description
The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.
Example 1 preparation of copper phthalocyanine Polymer nanoparticles (Cu-PcCP NPs)
1,2,4, 5-Benzenetetracarbonitrile (89mg,0.5mmol) and CuCl were first introduced2(26.8mg,0.2mmol) was well dispersed in 10ml of ethylene glycol. Then, 1, 8-diazabicyclo (5,4,0) undec-7-ene (DBU) was added to the mixture as a catalyst. And (3) ultrasonically dispersing the mixed solution for 10min, putting the whole system into a microwave oven, and reacting for 10min at 180 ℃ (320W). After the experiment was completed, the product was transferred while hot and washed sequentially with ethylene glycol, 3% hydrochloric acid, deionized water and ethanol. And drying the precipitate at 60 ℃ in vacuum overnight to obtain the Cu-PcCP NPs.
For comparison, metal-free phthalocyanine conjugated polymer nanoparticles (PcCP NPs) were also synthesized for subsequent characterization, in a manner consistent with that of Cu-PcCP NPs, but the product precipitated in excess deionized water.
Example 2 preparation of copper phthalocyanine Polymer nanoparticles (Cu-PcCP NPs)
The dosage of the raw materials is as follows: 1,2,4, 5-Benzenetetracarbonitrile (0.4mmol) and CuCl2(0.1mmol) and the remainder as in example 1, according to the procedure of example 1.
Example 3 preparation of copper phthalocyanine Polymer nanoparticles (Cu-PcCP NPs)
The dosage of the raw materials is as follows: 1,2,4, 5-Benzenetetracarbonitrile (0.4mmol) and CuCl2(0.3mmol) and the remainder as in example 1, according to the procedure of example 1.
The beneficial effects of the Cu-PcCP NPs of the invention are demonstrated by the following experimental examples.
Experimental example 1 characterization of copper phthalocyanine Polymer nanoparticles (Cu-PcCP NPs)
The invention uses 1,2,4, 5-benzene tetracarbonitrile and CuCl2The microwave-assisted polymerization of (1) produces Cu-PcCP NPs in which 1, 8-diazabicyclo (5,4,0) undec-7-ene (DBU) ensures the formation of a conjugated network by cyclization (FIG. 1 a). Characterization of the Cu-PcCP NPs from example 1 clearly revealed by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) that the prepared products were about 222.7 + -58.4 nm in diameter and spherical in morphology (FIGS. 1b, c). However, metal-free phthalocyanine conjugated polymer nanoparticles (PcCP NPs) exhibit bulk and stacked morphology (fig. 2), mainly due to strong pi-pi interactions between molecular layers. Thus, CThe u ion plays an important role in the regulation of the spherical morphology. High angle annular dark field scanning transmission electron microscopy (HAADF-STEM) (FIG. 1d) also shows the spherical size and approximate surface structure of Cu-PcCP NPs. Furthermore, no significant crystal structure was observed for both high resolution TEM and HAADF-STEM, confirming that the predominant structure of Cu-PcCP NPs is an amorphous structure as illustrated by the SAED image (FIG. 1 e). Furthermore, powder X-ray diffraction (PXRD) (fig. h) showed only one typical conjugated polymer peak at 26 ° of Cu-PcCP NPs, no Cu or CuO crystallization peak, consistent with STEM and SAED data. To explain the composition of Cu-PcCP NPs, HAADF-STEM images were further taken, the corresponding element mapping images and energy spectra (EDS) (fig. 1f, i) clearly show C, N and the presence of Cu elements, with Cu uniformly dispersed in N-doped carbon. In addition, EDS line scan elemental analysis was further performed at the area of overlap of the area distribution (fig. 1g), as indicated by the green arrow along the direction of the individual nanoparticles, consistent with the elemental area distribution results (fig. 1 j).
In order to gain insight into the carbon structure, FIG. 3a shows the Raman spectra of Cu-PcCP NPs. At 677, 744, 1456cm-1Respectively show A at the root1g,B1gAnd B2gMode, which is the result of the planar vibration of the phthalocyanine molecule. From Fourier Infrared Spectroscopy (FT-IR) analysis (FIG. 3b), it can be seen that Cu-PcCP NPs are integrated via a quasi-phthalocyanine macrocyclic topology and are connected via a closed conjugated structure. Notably, 1118cm representing the peripheral C-H in-plane bending vibration on the benzene ring of Cu-PcCP NPs-1The peaks at (a) show significantly lower signals than commercial copper phthalocyanine (CuPc), demonstrating that the phthalocyanine unit structure has been integrated into the Cu-PcCP NPs. In the visible-ultraviolet spectrum (fig. 3c), Cu-PcCP NPs have a distinct blue shift in the B-band and a red shift in the Q-band, compared to CuPc molecules, indicating extended conjugation through benzene ring linkages. The surface chemical structure was further analyzed by X-ray photoelectron spectroscopy (XPS). As shown in FIG. 3, XPS measurements confirmed the presence of C, N, Cu in the Cu-PcCP NPs and given the relative amounts of the elements, C, N, Cu in an atomic ratio of 69.2%, 11%, 1.1%, that is, the relative molar ratio of N atoms to Cu atoms was N: Cu 10:1, while each of the phthalocyanines in the phthalocyanine polymer was phthaleinThe cyanine unit (or each repeating unit) contains 8N atoms, and each phthalocyanine unit can be coordinately bound to 1 copper ion. Thus, the molar ratio relationship of the repeating units of the phthalocyanine polymer to the copper ions is 1.25:1 (fig. 4); the Cu-PcCP NPs of example 2 and example 3 were subjected to XPS test at the same time, and the ratio of the repeating unit of the phthalocyanine polymer to copper calculated as described above was 2:1 and 1.5:1, respectively. High resolution XPS spectra of Cu 2p orbitals clearly demonstrated the simultaneous presence of Cu (i) and Cu (ii) (fig. 3d), where Cu (i) predominates in Cu-PcCP NPs without zero valent metal component (relative atomic ratio 63.75%), i.e. the molar ratio of monovalent copper ions to divalent copper ions was 3.5: 1. Furthermore, the spectrum of N1 s Cu-PcCP NPs (FIG. 3e) shows the presence of isoindole rings (-N)β-399.8 eV), the peaks at 400.3eV and 401.2eV of the binding energy are associated with the central Cu atom (-N-M) and the nitrogen atom near the protonated N (-NH), respectively. As shown in fig. 3f, at C1s XPS, the corresponding high resolution spectra can be deconvoluted into C/C-C, C-N and pi-pi satellite peaks. The high deconvolution strength of pi-pi relative to the corresponding peak of Cu-PcCP NPs is likely due to extended conjugation and strong bonding between the central metal ion and the phthalocyanine macrocycle.
The results prove that the copper phthalocyanine polymer nanoparticles prepared by the invention form a crosslinking network by the copper phthalocyanine polymer to form a spherical structure with the particle size of 222.7 +/-58.4 nm, and the molar ratio of phthalocyanine to copper ions in the polymer is (1-2): 1, preferably 1.25: 1; the copper ions comprise monovalent copper ions and divalent copper ions, the molar ratio is 3.5:1, and a large number of limited-domain metal active centers exist in a polymer network, so that the catalyst has application potential as a novel catalyst.
Experimental example 2 peroxidase-like Activity and Steady-State kinetics of copper phthalocyanine Polymer nanoparticles (Cu-PcCP NPs)
TMB is commonly used for detection of POD enzyme mimics as a chromogenic substrate (figure 5 a). As shown in FIG. 5b, Cu-PcCP NPs pass through H2O2The fast catalytic oxidation of TMB to oxTMB (blue) with characteristic absorbance at 652nm and negligible activity of PcCP NPs, mainly due to the conjugated structure of Cu-PcCP NPs, with one hydrogen atomThe transfer from the amino group of TMB to the hydroxyl adsorbate is faster. Furthermore, when the concentration of Cu-PcCP NPs is from 10mg L-1Increased to 50mg L-1In time, the absorption peak gradually increased (fig. 5 c). As can be seen from FIG. 5d, the absorbance at 652nm of the Cu-PcCP NPs at different concentrations varied with time, exhibiting a concentration dependence, i.e., the higher the concentration, the better the catalytic activity. The effect of working pH and temperature on Cu-PcCP NPs class POD enzyme catalysis was investigated. Cu-PcCP NPs show higher catalytic Activity under different pH conditions and temperatures (FIG. 5e, f), and are superior to natural enzymes (e.g., HRP (Gao, L.; Zhuang, J.; Nie, L.; Zhang, J.; Zhang, Y.; Gu, N.; Wang, T.; Feng, J.; Yang, D.; Perrett, S.; et al. Intrasic Peroxidase-Like Activity of Ferromagnetic nanoparticiles. Nat. Nanotechnol.2007,2, 577-583)). In addition, the relative catalytic activity of Cu-PcCP NPs remained above 95% after 1 month at room temperature (fig. 6), indicating good stability and availability.
A steady state kinetic method was used to characterize the POD-like enzyme activity of the enzyme mimics. With H2O2And TMB as substrates, and the enzyme kinetic parameters (K) of Cu-PcCP NPs were measured separatelym、Vmax、KcatAnd Kcat/Km). Typical Michaelis-Menten kinetic profiles for two catalytic reactions initiated by Cu-PcCP NPs were obtained (FIGS. 7a, c), whose Lineweaver-Burk reciprocal plots reflect a good linear relationship (FIGS. 7b, d). In contrast, K of Cu-PcCP NPsmLower value, VmaxHigher, indicating that it has stronger affinity and faster reaction speed than the reported Cu-based POD enzyme mimetics (table 1).
TABLE 1 Steady-State kinetic parameters of copper-based POD enzyme mimetics
(Note: K)mIs the Michaelis constant, VmaxThe maximum reaction rate. The concentration was chosen to give a good fit of the Michaelis-Menten plot as the substrate concentration varied. KcatIs the catalytic constant, and KcatHigher values represent more substrate converted per active catalytic center. Kcat/KmIndicating the catalytic efficiency. )
Important index (V) in catalytic reactionmaxAnd Kcat) In one aspect, Cu-PcCP NPs have very good advantages over other non-noble metal-based POD enzyme mimics in the past (FIG. 7e, Table 2 (in H)2O2As substrate)).
TABLE 2 Cu-PcCP NPs and other reported peroxidase mimetics at POD enzyme kinetic parameters (substrate: H)2O2) Comparison of aspects
(Note: K)mIs the Michaelis constant, VmaxThe maximum reaction rate. [ E ]0]The molar concentration of the metal active site is chosen to give a good fit of the Michaelis-Menten plot as the substrate concentration is varied. KcatIs the catalytic constant, and KcatHigher values represent more substrate converted per active catalytic center. )
Furthermore, the catalytic index of Cu-PcCP NPs has significant advantages even compared to other metal phthalocyanine compounds reported in the prior art (table 3).
TABLE 3 Steady-State kinetic parameters of copper-based POD enzyme mimetics
(Note: K)mIs the Michaelis constant, VmaxIs at mostThe reaction rate. [ E ]0]The molar concentration of the metal active site is chosen to give a good fit of the Michaelis-Menten plot as the substrate concentration is varied. KcatIs the catalytic constant, and KcatHigher values represent more substrate converted per active catalytic center. Kcat/KmIndicating the catalytic efficiency. )
The above results demonstrate that the unusual peroxidase catalytic performance of the Cu-PcCP NPs of the invention is a POD enzyme mimic which is resistant to temperature and pH changes and has good stability.
Experimental example 3 application of copper phthalocyanine polymer nanoparticles (Cu-PcCP NPs) as peroxidase mimics to biomolecule detection
1. Colorimetric detection of H2O2
Since hydrogen peroxide plays a crucial role in the oxidation of TMB in the peroxidase-catalyzed cycle, H2O2The quantitative detection of (A) is of great significance for the extension of the biosensing application of the Cu-PcCP NPs. As shown in FIG. 8a, the Cu-PcCP NPs-TMB system has H at different concentrations2O2Different blue solutions (oxTMB) can be produced in the presence. By analyzing the linear calibration plot (FIG. 8b), H was determined in the range of 5-100. mu.M2O2Has a limit of detection (LOD) of 4.88. mu.M and a correlation coefficient of 0.99817. Further, the relative standard deviation (RSD%) of the detection Limit (LOD) was 1.1% (n ═ 3). Table 4 shows that the LOD of this sample is lower than that of other enzyme mimics, demonstrating that Cu-PcCP NPs have higher H2O2The detection potential and the detection sensitivity are high.
TABLE 4 Cu-PcCP NPs with other reported peroxidase mimetics assay H2O2Performance comparison of (2).
2. Colorimetric method for detecting L-cysteine
In recent years, the application of peroxidase mimics in the field of biosensing has been rapidly developed. L-halfCystine is a typical semi-essential amino acid in the human body and plays an important role in various processes of cellular functions such as protein synthesis, metabolism, detoxification and the like. In view of the important role of L-cysteine in various diseases, it is clear that there is a need for a qualitative and quantitative method to detect the amino acid in the shortest time. It is reported that the catalytic activity of peroxidase can be inhibited by the interaction of-SH with a metal atom in the presence of L-cysteine, thereby realizing the chromogenic detection of L-cysteine. Therefore, thanks to the unique peroxidase activity of Cu-PcCP NPs, we investigated the catalytic oxidation of TMB in the presence of different concentrations of L-cysteine (FIG. 9 a). As can be seen from FIG. 9b, as the concentration of L-cysteine was gradually increased, the absorption peak of oxTMB was also gradually decreased, showing a concentration-dependent reaction. The linear calibration curve range is 20-200 μ M (R)20.99338), the LOD is about 4.27 μ M (S/N — 3) (fig. 9 c). As shown in Table 5, the LOD of the Cu-PcCP NPs is equivalent to that of other nano-materials, and the detection range is remarkably increased, which indicates that the Cu-PcCP NPs can bear higher L-cysteine concentration in the solution.
Also, the detection performance of Cu-PcCP NPs in different environments was further explored, and it was found that Cu-PcCP NPs still exhibit good L-cysteine detection capability in a wider pH range (FIG. 9 d). The selectivity of the detection of L-cysteine is verified by using a plurality of amino acids and glutathione as interfering substances (figure 9e), and the result shows that the detection system can resist other interferences and has good selectivity on the L-cysteine. To verify the reliability of the method, L-cysteine assays were performed in biological samples. Human serum was assayed using standard sample addition methods. According to the results shown in Table 6, the recovery rate of L-cysteine is 98.1-103.4%, and the RSD limit is 1.2-2.7%, which is a strong empirical evidence, and the applicability of Cu-PcCP NPs in clinical diagnostic reagents is proved.
TABLE 5 comparison of the Performance of Cu-PcCP NPs for L-cysteine detection with other POD enzyme mimetics
TABLE 6 recovery of L-cysteine assay in human serum with Cu-PcCP NPs (n ═ 5)
3. Colorimetric method for detecting glucose
Glucose content in body fluids is a very important physiological parameter, and excess glucose in blood can lead to many endocrine metabolic diseases, such as diabetes. Catalytic glucose decomposition to H in combination with GOx2O2And Cu-PcCP NPs catalyze H2O2Decomposing into the properties of ROS, we integrated glucose oxidase (GOx) with Cu-PcCP NPs to form a natural enzyme-artificial enzyme cascade biosensor (fig. 10 a). As shown in FIG. 10b, the absorbance intensity at 652nm increased with increasing glucose concentration, and the concentration-absorbance curve (FIG. 10c) shows a linear calibration curve ranging from 0 to 600. mu.M. The LOD of the cascade biosensor can reach 21.1 mu M at the lowest. Notably, the glucose sensors constructed with Cu-PcCP NPs have comparable detection limits and a wider linear range than the other glucose sensors summarized in table 7. We then examined the detection performance of Cu-PcCP NPs under different environments, and found that it still maintains good detection ability for glucose under wide pH conditions (FIG. 10 d). The selectivity of glucose detection is verified by taking glucose analogues, ions and glutathione as interfering substances (FIG. 10e), and the result shows that the detection system can resist other interference and has good selectivity on glucose. To verify the feasibility of Cu-PcCP NPs in practical applications, the glucose concentration in serum was determined using standard addition methods, as shown in Table 8. The recovery rate of the glucose is 97.9-98.2%, and the RSD is 1.4-2.6%. Therefore, the strategy for constructing the cascade biosensor by taking Cu-PcCP NPs as POD enzyme mimics has wide application prospect in detection of glucose in diluted human serum samples in medical diagnosis and biological analysis.
TABLE 7 comparison of the Performance of Cu-PcCP NPs for detecting glucose with other POD enzyme mimics
Table 8 recovery test for human serum glucose analysis using the proposed assay method (n ═ 5)
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In conclusion, the copper phthalocyanine polymer nano particle Cu-PcCP NPs with a simple preparation method provided by the invention is used as a novel POD enzyme simulant, has excellent enzyme-like catalytic activity, stronger substrate selectivity and good stability, can resist various severe conditions including high temperature and low pH, can isolate a corresponding analysis system from oxygen when being applied to a biomolecule detection sensor, and can be used for a specific, sensitive and stable biosensor. Based on Cu-PcCP NPs to H2O2And the L-cysteine and the glucose are detected, the linear range is wide, the detection limit is low, the good applicability of the detection of the biomolecules is shown, and the application prospect is wide.
Claims (10)
1. A copper phthalocyanine polymer nanoparticle, which is a coordination complex of a copper phthalocyanine polymer and copper ions; the phthalocyanine polymer is formed by connecting at least two phthalocyanine units sharing at least one benzene ring, and the molar ratio of the phthalocyanine units to copper ions of the phthalocyanine polymer is (1-2): 1;
the structure of the phthalocyanine unit is as follows:
2. the nanoparticle according to claim 1, wherein the nanoparticle has a particle size of 222.7 ± 58.4 nm.
3. Nanoparticles according to claim 1 or 2, which are prepared by dispersing 1,2,4, 5-benzenetetracarboxylic nitrile and a copper salt in an alcohol and carrying out a microwave reaction under the action of a catalyst.
4. Nanoparticles according to claim 3, wherein the molar ratio of 1,2,4, 5-benzenetetracarboxylic nitrile to copper salt is (4-5) to (1-3), preferably 5: 2.
5. The nanoparticle according to claim 3, wherein the microwave reaction power is 300-350W and the time is 5-15 min;
preferably, the microwave reaction power is 320W, and the time is 10 min.
6. A method for preparing nanoparticles as claimed in any one of claims 1 to 5, comprising the steps of:
(1) dispersing 1,2,4, 5-benzene tetracarbonitrile and copper salt in alcohol, adding catalyst and dispersing uniformly;
(2) reacting the mixed system obtained in the step (1) under the action of microwaves.
7. The method according to claim 6, wherein the copper salt is copper chloride, copper bromide, copper sulfate, copper acetate, copper acetylacetonate; preferably copper chloride;
and/or, the alcohol is ethylene glycol, n-amyl alcohol, n-octyl alcohol;
and/or, the catalyst is DBU.
8. The method according to claim 6, wherein the molar ratio of 1,2,4, 5-benzenetetracarboxylic nitrile to copper salt is (4-5): (1-3), preferably 5: 2.
9. The preparation method according to claim 6, wherein the microwave is applied at a power of 300-350W for 5-15 min; preferably with a power of 320W for 10 min.
10. Use of the nanoparticle of any one of claims 1 to 5 in a reagent for the detection of biomolecules; preferably, the nanoparticles act as peroxidase mimics in a biomolecule detection reagent.
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