CN113770346B - Palladium nanosheets with peroxidase activity and preparation method thereof - Google Patents
Palladium nanosheets with peroxidase activity and preparation method thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 99
- 239000002135 nanosheet Substances 0.000 title claims abstract description 77
- 230000000694 effects Effects 0.000 title claims abstract description 34
- 102000003992 Peroxidases Human genes 0.000 title claims abstract description 28
- 108040007629 peroxidase activity proteins Proteins 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002064 nanoplatelet Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 238000001126 phototherapy Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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Abstract
The invention discloses a palladium nano-sheet with peroxidase activity and a preparation method thereof. The invention prepares the ultrathin palladium nanosheets by taking palladium acetylacetonate as a precursor and carbon monoxide as a reducing agent and a structure directing agent; alcohol is used as a solvent, and the palladium nano-sheet is subjected to surface reconstruction by stirring under mild conditions, so that the palladium nano-sheet with the wrinkled surface is generated, and the surface high-activity site is increased, so that the palladium nano-sheet has peroxidase activity. The method has simple process, low cost and easy industrial scale-up.
Description
Technical Field
The invention belongs to the field of nano enzymes, and particularly relates to a palladium nano sheet with peroxidase activity and a preparation method thereof.
Background
The palladium nano-sheet has the advantages of high specific surface area, large surface atomic ratio, high atomic utilization rate and good thermal stability, and the application in the aspect of tumor treatment is greatly focused by scientific researchers. The palladium nano-sheet has excellent tumor phototherapy and photodynamic therapy performances due to the strong surface plasmon resonance effect in the near infrared light range. The peroxidase activity can further enhance the tumor treatment effect of the nanomaterial. However, palladium nanoplates having peroxidase activity have not been reported yet. This is because carbon monoxide has a strong bonding force with the Pd (111) crystal plane as a structure directing agent in the synthesis process of the palladium nanoplatelets, and the growth of the crystal plane is restricted, so that the produced material is an ultrathin nanoplatelet, and the surface of the material is the Pd (111) crystal plane. The Pd (111) crystal plane is an inert crystal plane, and has low catalytic activity compared with other crystal planes such as Pd (100) and Pd (110), which inhibits peroxidase activity of the palladium nano-sheet.
At present, the content of high-activity sites on the surface of the palladium nano-sheet can be improved through crystalline phase engineering, pore-forming, size reduction and the like. For example, chem.commun.2017,53,1642 prepared palladium nanoplatelets with Pd (110) crystal faces on the surface. The method uses a compound containing pyridine groups as a structure directing agent. The preparation process of the compound is complex and has high cost. The literature angel.chem.int.ed.2018, 57,3435 introduces a pore structure in the palladium nano-sheet by etching, so that the content of an active crystal face is improved. Etching, however, causes a significant amount of noble metal palladium to be lost and may reduce the stability of the palladium nanoplatelets. Reducing the size of the palladium nanoplatelets can increase the content of the edge non-Pd (111) crystal planes to some extent (small 2014,10, no.15, 3139). However, the content of high active sites on the surface of the small-sized palladium nanoplatelets is still low. Therefore, there is a need to develop a palladium nanoplatelet having a large number of surface high active sites, high peroxidase activity, and a simple and easy-to-handle preparation method.
The present invention has been made in view of the above-mentioned circumstances.
Disclosure of Invention
It is an object of the present invention to provide palladium nanoplatelets having peroxidase activity.
The second object of the present invention is to provide a method for preparing palladium nanosheets having peroxidase activity.
The particle size of the palladium nano-sheet with peroxidase activity is 15-200 nm, and the thickness is 0.8-3.0 nm.
The surface of the palladium nano-sheet with peroxidase activity is wrinkled.
The preparation method of the palladium nano-sheet with peroxidase activity comprises the following steps:
(1) 50mg of palladium acetylacetonate, 10-100 mg of sodium bromide, 160mg of polyvinylpyrrolidone, 10mL of N, N-dimethylformamide and 0.5-10 mL of deionized water are added into a 100mL autoclave, and stirred at 25 ℃ for 2h. Carbon monoxide of 0.5MPa is filled, the temperature is raised to 80 ℃ and the reaction is carried out for 3h. And adding 12mL of acetone into the product, centrifugally separating, washing for 4 times by using ethanol/acetone (volume ratio is 1:6) mixed solution, and carrying out vacuum drying at 40 ℃ to obtain the palladium nano-sheet.
(2) And ultrasonically dispersing the obtained palladium nano-sheets in alcohol with the mass of 500-10000 times of that of the palladium nano-sheets to obtain an alcohol solution of the palladium nano-sheets.
(3) Stirring the obtained alcoholic solution of the palladium nano-sheets for 0.5-20 days at 15-50 ℃ to obtain the alcoholic solution of the palladium nano-sheets on the surfaces of the folds.
(4) And (3) centrifugally separating the obtained alcohol solution of the palladium nano-sheets on the surfaces of the folds, washing the palladium nano-sheets with mixed liquid of ethanol/acetone (volume ratio is 1:3-1:12) for 3 times, and vacuum drying the palladium nano-sheets at the temperature of 30 ℃ for 6 hours to obtain the palladium nano-sheets on the surfaces of the folds with peroxidase activity.
Preferably, the alcohol in the step (2) is one or more of methanol, ethanol, n-propanol, isopropanol or ethylene glycol.
The invention has the beneficial effects that: according to the invention, by utilizing the characteristics of poor stability and easiness in spontaneous structure reconstruction of the ultrathin palladium nanosheets, the surface reconstruction of the palladium nanosheets is realized through simple stirring, and the palladium nanosheets with high-activity folded surfaces are generated, so that the palladium nanosheets without peroxidase activity are converted into the palladium nanosheets with high peroxidase activity; the method has simple process and mild condition, and is easy for industrial amplification; in addition to palladium nanoplatelets, inexpensive and environmentally friendly alcohols are the only reagents.
Drawings
Fig. 1: TEM image of palladium nanoplatelets according to example 1 of the present invention.
Fig. 2: TEM image of a corrugated surface palladium nanoplatelet according to example 1 of the present invention.
Fig. 3: the palladium nanoplatelets described in example 1 of the present invention were compared to the activity of the palladium nanoplatelet peroxidase on the corrugated surface.
Fig. 4: TEM image of a corrugated surface palladium nanoplatelet according to example 5 of the present invention.
Detailed Description
Example 1
(1) 50mg of palladium acetylacetonate, 50mg of sodium bromide, 160mg of polyvinylpyrrolidone, 10mL of N, N-dimethylformamide and 2mL of deionized water were added to a 100mL autoclave, and stirred at 25℃for 2 hours. Carbon monoxide of 0.5MPa is filled, the temperature is raised to 80 ℃ and the reaction is carried out for 3h. Adding 12mL of acetone into the product, centrifugally separating, washing for 4 times by using ethanol/acetone (volume ratio is 1:6) mixed solution, and vacuum drying at 40 ℃ to obtain the palladium nano-sheets with the particle size of 135nm and the thickness of 1.2 nm. The TEM image is shown in FIG. 1. As can be seen from fig. 1, the surface of the palladium nanoplatelets is smooth.
(2) And (3) dispersing 50mg of the palladium nano-sheets obtained in the step (1) in 500g of ethanol by ultrasonic waves to obtain an ethanol solution of the palladium nano-sheets.
(3) Stirring the ethanol solution of the palladium nano-sheets obtained in the step (2) for 10 days at 25 ℃ to obtain the ethanol solution of the palladium nano-sheets on the surfaces of the folds.
(4) And (3) centrifugally separating the ethanol solution of the palladium nano-sheets on the folded surfaces obtained in the step (3), washing 3 times by using mixed liquid of ethanol and acetone (volume ratio is 1:3), and vacuum drying for 6 hours at the temperature of 30 ℃ to obtain the palladium nano-sheets on the folded surfaces with peroxidase activity, wherein the particle size is 115nm, and the thickness is 1.2nm, and a TEM image of the palladium nano-sheets is shown in figure 2. As can be seen from fig. 2, the surface of the resulting material is corrugated.
(5) 3 mu L of the palladium nano sheet aqueous dispersion liquid obtained in the step (1) is added into 3mL of commercial 3,3', 5' -tetramethyl benzidine color development liquid, after reaction for 10min, optical absorption of 3,3', 5' -tetramethyl benzidine oxidation products is measured by an ultraviolet-visible spectrophotometer, and a spectrum chart is shown in figure 3. As can be seen from fig. 3, there is no apparent 3,3', 5' -tetramethylbenzidine oxidation product, indicating that the palladium nanoplatelets have no peroxidase activity.
(6) 3 mu L of the palladium nano sheet aqueous dispersion liquid obtained in the step (4) with the concentration of 1mg/mL is added into 3mL of commercial 3,3', 5' -tetramethyl benzidine color development liquid, after reaction for 10min, optical absorption of 3,3', 5' -tetramethyl benzidine oxidation products is measured by an ultraviolet-visible spectrophotometer, and a spectrum chart is shown in figure 4. As can be seen from fig. 4, a large amount of 3,3', 5' -tetramethylbenzidine was oxidized, indicating that the palladium nanoplatelets on the corrugated surface have high peroxidase activity.
Example 2
(1) 50mg of palladium acetylacetonate, 10mg of sodium bromide, 160mg of polyvinylpyrrolidone, 10mL of N, N-dimethylformamide and 0.5mL of deionized water were added to a 100mL autoclave, and stirred at 25℃for 2 hours. Carbon monoxide of 0.5MPa is filled, the temperature is raised to 80 ℃ and the reaction is carried out for 3h. Adding 12mL of acetone into the product, centrifugally separating, washing for 4 times by using ethanol/acetone (volume ratio is 1:6) mixed solution, and vacuum drying at 40 ℃ to obtain the palladium nano-sheets with the particle size of 220nm and the thickness of 0.8 nm.
(2) 50mg of the palladium nano-sheet obtained in the step (1) is ultrasonically dispersed in 100g of methanol to obtain a methanol solution of the palladium nano-sheet.
(3) And (3) stirring the methanol solution of the palladium nano-sheets obtained in the step (2) for 5 days at 35 ℃ to obtain the methanol solution of the palladium nano-sheets on the surfaces of the folds.
(3) And (3) centrifugally separating the methanol solution of the obtained palladium nano-sheets on the folded surfaces, washing 3 times by using mixed liquid of ethanol/acetone (volume ratio is 1:6), and vacuum drying for 6 hours at the temperature of 30 ℃ to obtain the palladium nano-sheets on the folded surfaces with peroxidase activity, wherein the particle size is 200nm and the thickness is 0.8 nm.
Example 3
(1) 50mg of palladium acetylacetonate, 100mg of sodium bromide, 160mg of polyvinylpyrrolidone, 10mL of N, N-dimethylformamide and 10mL of deionized water were added to a 100mL autoclave and stirred at 25℃for 2 hours. Carbon monoxide of 0.5MPa is filled, the temperature is raised to 80 ℃ and the reaction is carried out for 3h. Adding 12mL of acetone into the product, centrifugally separating, washing for 4 times by using ethanol/acetone (volume ratio is 1:6) mixed solution, and vacuum drying at 40 ℃ to obtain the palladium nano-sheet with the particle size of 18nm and the thickness of 3 nm.
(2) 50mg of the palladium nano-sheet obtained in the step (1) is ultrasonically dispersed in 100g of n-propanol to obtain an n-propanol solution of the palladium nano-sheet.
(3) Stirring the n-propanol solution of the palladium nano-sheets obtained in the step (1) at 15 ℃ for 20 days to obtain the n-propanol solution of the palladium nano-sheets on the wrinkled surfaces.
(4) And (3) centrifugally separating the obtained normal-propanol solution of the palladium nano-sheets on the folded surfaces, washing 3 times by using mixed liquid of ethanol/acetone (volume ratio is 1:12), and vacuum drying for 6 hours at the temperature of 30 ℃ to obtain the palladium nano-sheets on the folded surfaces with peroxidase activity, wherein the particle size is 15nm and the thickness is 3 nm.
Example 4
(1) 50mg of the palladium nanoplatelets obtained in example 1 were ultrasonically dispersed in 100g of ethylene glycol to obtain an ethylene glycol solution of palladium nanoplatelets.
(2) Stirring the ethylene glycol solution of the palladium nano-sheets obtained in the step (1) for 0.5 days at 50 ℃ to obtain the ethylene glycol solution of the palladium nano-sheets on the surfaces of the folds.
(3) And (3) centrifugally separating the glycol solution of the obtained palladium nanosheets on the corrugated surfaces, washing 3 times by using mixed liquid of ethanol/acetone (volume ratio is 1:6), and vacuum drying for 6 hours at the temperature of 30 ℃ to obtain the palladium nanosheets with the corrugated surfaces with peroxidase activity, wherein the diameter is 115nm and the thickness is 1.2 nm.
Example 5
(1) 5g of the palladium nanoplatelets obtained in example 1 were ultrasonically dispersed in 2.5kg of isopropanol to obtain an isopropanol solution of the palladium nanoplatelets.
(2) Stirring the isopropanol solution of the palladium nano-sheets obtained in the step (1) for 3 days at the temperature of 30 ℃ to obtain the isopropanol solution of the palladium nano-sheets on the wrinkled surfaces.
(3) The obtained isopropanol solution of the palladium nano-sheets on the folded surfaces is subjected to centrifugal separation, the palladium nano-sheets are washed 3 times by mixed liquid of ethanol/acetone (volume ratio is 1:6), and are dried in vacuum for 6 hours at the temperature of 30 ℃ to obtain the palladium nano-sheets on the folded surfaces with peroxidase activity, wherein the diameter is 110nm, the thickness is 1.2nm, and a TEM image of the palladium nano-sheets is shown in figure 4. As can be seen from fig. 4, the surface of the resulting material is wrinkled, which illustrates that the method does not affect the surface reconstruction effect after the amplifying operation.
Claims (3)
1. The preparation method of the palladium nano-sheet with peroxidase activity comprises the steps of enabling the particle size of the palladium nano-sheet with peroxidase activity to be 15-200 nm, enabling the thickness to be 0.8-3.0 nm, and enabling the surface to be in a corrugated shape;
the method is characterized by comprising the following steps of:
(1) Dispersing palladium nano-sheets in alcohol by ultrasonic to obtain an alcohol solution of the palladium nano-sheets; the mass ratio of the palladium nano-sheet to the alcohol is 1:500-10000;
(2) Stirring the obtained alcoholic solution of the palladium nano-sheets at 15-50 ℃ to obtain the alcoholic solution of the palladium nano-sheets on the surfaces of the folds;
(3) Centrifugally separating the obtained alcohol solution of the palladium nano-sheets on the surfaces of the folds, washing the alcohol solution by using mixed liquid of ethanol and acetone with the volume ratio of 1:3-1:12, and vacuum drying the alcohol solution at the temperature of 30 ℃ for 6h to obtain the palladium nano-sheets on the surfaces of the folds with peroxidase activity;
the palladium nano-sheet in the step (1) is prepared by the following steps: adding 50mg palladium acetylacetonate, 10-100 mg sodium bromide, 160mg polyvinylpyrrolidone, 10mL N, N-dimethylformamide and 0.5-3 mL deionized water into a 100mL high-pressure reaction kettle, and stirring at 25 ℃ for 2 h; filling carbon monoxide of 0.5MPa, heating to 80 ℃, and reacting for 3 h; adding 12mL acetone into the product, centrifugally separating, washing for 4 times by using ethanol/acetone mixed solution with the volume ratio of 1:6, and vacuum drying at 40 ℃ to obtain the palladium nano-sheet.
2. The method according to claim 1, wherein the alcohol in step (1) is one or more of methanol, ethanol, n-propanol, isopropanol or ethylene glycol.
3. The method of claim 1, wherein the stirring in step (2) is performed for a period of 0.5 to 20 days.
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| CN105537619A (en) * | 2015-12-29 | 2016-05-04 | 天津大学 | Palladium nano-particles with peroxidase activity and preparation method thereof |
| AU2020100704A4 (en) * | 2020-05-05 | 2020-06-11 | Chen, Shumeng Miss | A method of synthesis of ultrathin palladium nanosheet with peroxidase mimetic activity for the colorimetric detection of H2O2 |
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