CN115466613A - Mesoporous silica hydrogen peroxide fluorescent nano probe with aggregation-induced emission effect and preparation method thereof - Google Patents
Mesoporous silica hydrogen peroxide fluorescent nano probe with aggregation-induced emission effect and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Mesoporous Silica (MSNs) hydrogen peroxide fluorescent nano probe with aggregation induced emission effect (AIE) and a preparation method thereof, belonging to the technical field of organic-inorganic hybrid nano materials. The probe comprises a mesoporous silica material and a hydrogen peroxide responsive fluorescent molecule with AIE. H 2 O 2 The responsive CN functional molecule is prepared by two-step synthesis, and CN is further reacted with 3-iodopropyl trimethoxy silane to obtain a silane precursor (CN-Si) capable of being condensed. The surfactant micelle is used as a template agent, and CN-Si and tetraethyl orthosilicate are prepared into H by a one-step copolycondensation method 2 O 2 A fluorescent nanoprobe. The MSNs-based fluorescent probe can ensure the luminous efficiency through the immobilization of the silicon dioxide nano material, and the protection of the material framework can well improve the photostability of the CN fluorescent organic molecule and ensure the effective sensing of the probe.
Description
Technical Field
The invention relates to the technical field of organic-inorganic hybrid nano materials, in particular to a mesoporous silica hydrogen peroxide fluorescent nano probe with aggregation-induced emission effect and a preparation method thereof.
Background
The fluorescent silica organic-inorganic hybrid nano material can effectively combine the luminous performance of organic fluorescent dye and the structural advantages of the silica nano material, so that the field attracts more and more research attention. The silica material has good biocompatibility, photochemical stability and water dispersibility, and is easy to modify functions, so that the silica material provides an excellent carrier for assembling various luminescent materials. However, the conventional organic fluorescent molecules form aggregation after entering into a silica framework, thereby causing aggregation-induced fluorescence quenching (ACQ), which seriously affects the application performance of the fluorescent material in the fields of sensing and biomedicine. The discovery of aggregation-induced emission luminescent molecules (AIEgens) opens a new path for designing and synthesizing high-performance fluorescent nano materials. The intramolecular rotation caused by the aggregation and immobilization of AIEgenes in the silica nano material is limited, and the fluorescence enhancement and quantum yield increase of the luminophor can be caused, so that the MSN fluorescent nano probe with high-efficiency fluorescence can be obtained. In addition, due to the protective effect of the silica framework, the light stability of the AIEgens can be significantly improved, and a good foundation is provided for practical application.
Hydrogen peroxide (H) 2 O 2 ) Has important functions in the aspects of drug synthesis, environmental monitoring, clinical application, food production and the like and is a product of a plurality of enzymatic reactions in organisms. Thus H 2 O 2 The detection of (2) has important practical significance. At present, detection of H 2 O 2 The main methods include spectrophotometry, chemiluminescence, electrochemical methods, and fluorescence photometry. Some of the methods described above require long analysis times, some require expensive reagents, are costly, and some require the use of toxic reagents. Therefore, there is a need to develop a simple, sensitive, non-toxic hydrogen peroxide sensor.
Disclosure of Invention
One of the purposes of the invention is to design a fluorescent nano probe capable of realizing high-sensitivity and high-selectivity detection of hydrogen peroxide, and simultaneously overcome the defects of poor light stability, aggregation-induced quenching and the like of a fluorescent dye probe. The invention provides an organic fluorescent probe which has aggregation induced emission effect (AIE) property and responds to hydrogen peroxide, and a fluorescent nano probe introduced into an MSN material by a copolycondensation method. The original phase structure of MSN is kept, the fluorescence efficiency is effectively improved, the detection sensitivity is improved, the framework can protect the fluorescent group, and the photobleaching phenomenon is avoided.
The invention provides a MSN-based H with AIE effect 2 O 2 The preparation method of the fluorescent nano probe utilizes a cyanobenzene borate fluorescent siloxane organic molecule (CN-Si) with AIE effect and tetraethyl silicate to synthesize the MSN material with AIE effect in one step through a co-assembly mode. The method can improve the light stability of CN fluorescent organic molecules, improve the luminous efficiency of the CN fluorescent organic molecules through the fixation of the silicon dioxide nano materials, and realize efficient and stable H 2 O 2 Sensing performance.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a mesoporous silica hydrogen peroxide fluorescent nano probe with aggregation-induced emission effect, which comprises a mesoporous silica Material (MSN) and hydrogen peroxide responsive fluorescent molecules with aggregation-induced emission effect (AIE);
the mesoporous silica material is used as a framework for fixing hydrogen peroxide responsive fluorescent molecules with aggregation-induced emission effect;
the hydrogen peroxide-responsive fluorescent molecule with aggregation-induced emission effect is immobilized on the pore walls of the MSN through covalent bonds.
Further, the hydrogen peroxide-responsive fluorescent molecule having an aggregation-induced emission effect is a cyanobenzene-based borate (CN) fluorescent organic molecule.
The borate fluorescent organic molecule based on the cyanostyrene has an AIE effect, and the optical stability of the borate fluorescent organic molecule modified on the porous material interface can be obviously improved.
The invention provides a preparation method of a mesoporous silica hydrogen peroxide fluorescent nano probe with aggregation-induced emission effect, which comprises the following steps:
(1) Preparing an intermediate organic compound 1 by reacting N, N-dimethylbenzaldehyde and p-bromophenylacetonitrile, wherein the intermediate organic compound 1 has a structural formula as follows:
(2) The intermediate organic compound 1 reacts with bis (pinacolato) diboron to obtain the hydrogen peroxide responsive fluorescent molecule (CN) with aggregation-induced emission effect, and the structural formula is as follows:
(3) 3-chloropropyl trimethoxyl silane and NaI are subjected to halogen exchange reaction to prepare 3-iodopropyl trimethoxyl silane;
(4) Carrying out quaternary ammonification reaction on the hydrogen peroxide responsive fluorescent molecule with the aggregation-induced emission effect in the step (2) and 3-iodopropyl trimethoxy silane to prepare a siloxane (CN-Si) fluorescent organic molecule based on the cyanobenzene borate;
(5) And (3) carrying out copolycondensation on tetraethyl orthosilicate (TEOS) and CN-Si to obtain the final hydrogen peroxide fluorescence nanoprobe (CN-MSN) based on the mesoporous silica and having the aggregation-induced emission effect.
The invention utilizes the cyanogen styrene borate siloxane fluorescence organic molecule (CN-Si) with AIE effect and tetraethyl orthosilicate to synthesize the MSNs material with AIE effect in one step by a co-assembly mode. Firstly, preparing the compound I by two-step synthesis 2 O 2 Responsive cyanostyrene-based borate fluorescent organic molecules (CN). 3-chloropropyltrimethoxysilane reacts with sodium iodide to prepare 3-iodopropyltrimethoxysilane; CN reacts with 3-iodopropyl trimethoxy silane to prepare a silane precursor (CN-Si) capable of being condensed; the precursor reacts with tetraethyl orthosilicate, a surfactant is used as a template agent, and H with AIE effect based on MSNs is prepared by a copolycondensation method 2 O 2 Fluorescent nanoprobes (CN-MSN). The method can improve the light stability of the CN fluorescent organic molecule, improve the luminous efficiency of the CN fluorescent organic molecule through the fixation of the silicon dioxide nano material, and improve the H pair 2 O 2 The sensing performance of (1).
Further, the molar ratio of the N, N-dimethylbenzaldehyde to the p-bromophenylacetonitrile in the step (1) is 1:1.
further, in the step (2), the molar ratio of the intermediate organic compound 1 to the bis (pinacolato) diboron is 3:4.
further, in the step (3), the molar ratio of the 3-chloropropyltrimethoxysilane to the NaI is 2:3.
further, the preparation of the siloxane fluorescent organic molecule based on the cyanobenzene borate in the step (4) comprises the following specific steps: heating CN and 3-iodopropyl trimethoxy silane in ethyl acetate according to a molar ratio of 5:
further, the hydrogen peroxide fluorescent nanoprobe with aggregation-induced emission effect in the step (5) is prepared by the following specific steps: cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, the pH value of the aqueous solution is adjusted by using a sodium hydroxide solution to prepare a CTAB aqueous solution, tetraethyl orthosilicate (TEOS) is used as an inorganic silane precursor, the synthesized CN-Si is used as an organic silicon precursor, the organic silicon precursor is dripped into the CTAB aqueous solution under the stirring condition, after the dripping is finished, the mixed solution is stirred for 1 hour at the temperature of 80 ℃, then cooled to the room temperature, a CN-MSN material is obtained by filtering, the obtained CN-MSN is refluxed for 24 hours in a methanol/hydrochloric acid solution, the CTAB surfactant template is removed, and the obtained product is subjected to suction filtration and vacuum drying.
Further, the molar ratio of hexadecyl trimethyl ammonium bromide to sodium hydroxide is 1:1.
the invention also provides application of the hydrogen peroxide fluorescent nano probe with aggregation-induced emission effect based on the mesoporous silica in detecting hydrogen peroxide.
The invention discloses the following technical effects:
(1) The invention utilizes quaternization reaction to synthesize precursor molecules of the CN-Si organosilane coupling agent, and the molecules can be connected into a silicon dioxide framework by stable covalent bonds through hydrolytic polycondensation of trimethoxy silane while keeping the AIE effect and the hydrogen peroxide sensing performance of the CN molecules.
(2) According to the invention, the prepared CN-Si is fixed in the MSN material by a one-step copolycondensation method, the material not only can effectively avoid ACQ, but also can effectively improve the light stability of CN by the protection of the MSN matrix.
(3) The CN-MSN fluorescent nanoprobe prepared by the invention can effectively realize the sensing of hydrogen peroxide, and the synthesis method is simple, easy to operate, low in use cost of raw materials and instruments and equipment, and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a diagram of intermediate organic Compound 1 prepared in example 1 1 H NMR spectrum;
FIG. 2 shows CN molecules prepared in example 2 1 An H NMR spectrum;
FIG. 3 is a schematic representation of the CN-Si molecule prepared in example 4 1 An H NMR spectrum;
FIG. 4 is a Mass Spectrometry (MS) spectrum of a CN-Si molecule prepared in example 4;
FIG. 5 shows the change of fluorescence emission of CN-Si prepared in example 4 in different water/ethanol mixed solvents;
FIG. 6 is a comparison of infrared spectra of CN-MSN material and CN, CN-Si and pure MSN;
FIG. 7 is a TEM image of the CN-MSN material of example 6;
FIG. 8 is a nitrogen adsorption-desorption curve of the CN-MSN material of example 6;
FIG. 9 is the fluorescence spectrum of CN-MSN sensor hydrogen peroxide in example 7;
FIG. 10 is a graph showing the optical stability of CN-MSN and CN-Si under UV light in example 8.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated or intervening value in a stated range, and every other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
Example 1
N, N-dimethylbenzaldehyde (4.0g, 26.80mmol)) and p-bromophenylacetonitrile (5.24g, 26.72mmol) were added to 60mL of anhydrous methanol, and a potassium hydroxide methanol solution (4 mL, 0.5M) was added under stirring, and the solution became cloudy. The turbid solution was reacted for 3 hours under stirring at room temperature, left to stand for 1 hour, and after filtering off the solid precipitate under reduced pressure, it was recrystallized from ethanol to give a pure yellow intermediate organic compound 1 as a solid, which was dried under vacuum for 1 day (yield 75%). 1 H NMR(400MHz,CDCl 3 ) 3.07 (s, 6H, -CH 3), 6.75 (d, 2H, arH), 7.37 (s, 1H, CH), 7.49-7.58 (m, 4H, arH) and 7.86 (d, J =10Hz,2H, arH) of intermediate organic Compound 1 prepared in example 1 1 The H NMR spectrum is shown in detail in FIG. 1).
Example 2
Yellow intermediate organic compound 1 (1g, 3.04mmol) was dissolved in 30mL of anhydrous toluene, bis-triphenylphosphine palladium dichloride ((0.04g, 0.082mmol)), triphenylphosphine (0.04g, 0.152mmol), potassium acetate (0.40g, 4.17mmol) were added as catalyst under nitrogen protection, and excess bis (pinacolato) diboron (1.03g, 4.05mmol) was added, wherein the molar ratio of 1 to bis (pinacolato) diboron was 3:4. the mixed solution is heated to 110 ℃ and reacted for 8h. After the reaction, toluene was removed under reduced pressure, and dichloromethane was added for extraction. The dichloromethane extract was further washed with water, the organic layer was separated, dried for 4 hours by adding anhydrous sodium sulfate, the anhydrous sodium sulfate was filtered, the resulting solution was distilled under reduced pressure to remove the solvent, and the crude product was subjected to column purification to obtain a CN molecule having AIE effect (yield 60%). 1 H NMR(400MHz,CDCl 3 ) 1.29 (s, 12H, CH3), 3.05 (s, 6H, CH3), 6.68 (d, 2H, arH), 7.48 (s, 1H, CH), 7.68 (d, 2H, arH) and 7.75-7.85 (m, 4H, arH) of CN molecule prepared in example 2 1 The H NMR spectrum is shown in FIG. 2).
Example 3
3-chloropropyltrimethoxysilane (30.0 g,151.0 mmol) and excess NaI (34.0 g,226.6 mmol) were heated under reflux in 200mL of acetone for 72h to effect a halogen exchange reaction, excess solvent was distilled off under reduced pressure, pentane was added, the sodium salt was removed by filtration, and the solvent was distilled off under reduced pressure to obtain 3-iodopropyltrimethoxysilane as a colorless oil (yield 73%).
Example 4
Adding CN (1.00g, 2.67mmol) and excessive 3-iodopropyltrimethoxysilane (0.93g, 3.21mmol) into ethyl acetate, adding potassium carbonate catalyst, performing quaternary ammoniation reaction, refluxing for 3 days, cooling to room temperature, filtering to remove catalyst, distilling under reduced pressure to remove excessive solvent, adding n-hexane, precipitating solid CN-Si, standing for half an hour, precipitating supernatant, adding n-hexane, treating with ultrasound, standing for half an hour, repeatedly washing for three times, filtering to obtain solid,drying gave pure CN-Si solid (50% yield). 1 H NMR(400MHz,CDCl 3 )1.36(s,12H,CH 3 ),2.925-3.118(s,6H,CH 3 ),3.238(s,1H,OCH 3 ) 6.575 to 6.667 (m, 1H, arH), 6.777 to 6.860 (m, 1H, arH), 7.083 (d, 1H, arH), 7.398 to 7.506 (m, 2H, CH and ArH), 7.607 to 7.674 (m, 1H, arH) and 7.765 to 7.928 (m, 3H, arH), (of CN-Si molecules prepared in example 4) 1 The H NMR spectrum is shown in FIG. 3). ESI + HR-MS calcd for CNSB-Si [ M + H ]] + 537.56, found. Note: in the process of nuclear magnetism characterization, methoxyl (-OCH) 3 ) Hydrolysis resulted in only one of the H groups at 3.238ppm of methoxy groups.
Example 5
The aggregation-induced emission enhancement effect of CN-Si is demonstrated by fluorescence emission spectra and luminescence photographs of CN-Si molecules in water/ethanol mixed solutions of different ratios. The CN-Si molecules can be well dissolved in the absolute ethanol solution, but the CN-Si solution gradually becomes turbid with the addition of poor solvent water to generate aggregation, and the fluorescence intensity of the aggregated CN-Si also shows a trend of increasing with the turbidity increase of the solution, which further proves that the CN-Si molecules have the AIE effect (the fluorescence emission change of the CN-Si prepared in example 4 in different water/ethanol mixed solvents is shown in detail in figure 5).
Example 6
CTAB (200 mg) and sodium hydroxide (350. Mu.L, 4M) were dissolved in 100mL of deionized water and heated to 80 ℃ with stirring for 1h. 1g TEOS and 0.1g CN-Si were added simultaneously to the above CTAB aqueous solution under stirring, the mixture was stirred at 80 ℃ for 2 hours and then cooled to room temperature, and filtered to give CN-MSN material, which was confirmed by IR spectroscopy to be successfully attached to MSN (see FIG. 6 for comparison of IR spectra of CN-MSN material with CN, CN-Si and pure MSN). The obtained CN-MSN material is refluxed in a methanol/hydrochloric acid (16. And comparing the obtained infrared spectrogram of the CN-MSN material with CN, CN-Si and MSN spectrograms, and displaying that the infrared spectrogram of the CN-MSN material has an intramolecular chemical bond stretching and bending vibration peak of CN and simultaneously has a stretching and bending vibration peak of Si-O-Si of the MSN material.
The Transmission Electron Microscope (TEM) image of the CN-MSN material prepared in example 6 of the present invention is shown in fig. 7, which shows that the hybrid mesoporous material exhibits a good pore structure.
The nitrogen adsorption-desorption curve of the CN-MSN material prepared in the embodiment 6 of the invention is shown in figure 8, and the hybrid mesoporous material has good specific surface area and pore structure.
Example 7
CN-MSN was dispersed in PBS aqueous solution (PBS/ethanol = 99/1), and different amounts of hydrogen peroxide (1-2 × 10) were added -4 M). After standing at room temperature for 1 hour, the nanoprobe was found to exhibit good hydrogen peroxide fluorescence response properties compared to the CN-MSN solution before and after addition of hydrogen peroxide (the fluorescence spectrum of CN-MSN sensing hydrogen peroxide in example 7 is detailed in fig. 9).
Example 8
By comparing the light stability of CN-MSN and CN-Si, the PBS aqueous solution (PBS/ethanol =99/1, volume ratio) of the materials and molecules is illuminated under an ultraviolet lamp and the change of the fluorescence along with the time is observed, and 90-minute tracking experiments are carried out to find that CN-MSN can still retain the fluorescence intensity higher than 80% after the ultraviolet lamp is continuously illuminated for 90 minutes, and CN-Si lacks the protection effect of a silica framework and the fluorescence is reduced to 60% (the optical stability diagram of CN-MSN and CN-Si under the illumination of the ultraviolet lamp in example 8 is shown in figure 10 in detail). The results prove that the stability of the probe is effectively improved by the protection effect of the CN-MSN material framework.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. A mesoporous silica hydrogen peroxide fluorescence nanoprobe with aggregation-induced emission effect is characterized by comprising a mesoporous silica material and hydrogen peroxide responsive fluorescent molecules with aggregation-induced emission effect;
the mesoporous silica material is used as a framework and is used for fixing hydrogen peroxide responsive fluorescent molecules with aggregation-induced emission effect;
the hydrogen peroxide responsive fluorescent molecule with the aggregation-induced emission effect is fixed on the pore wall of the mesoporous silica material by a chemical bond through a copolycondensation method.
2. The mesoporous silica hydrogen peroxide fluorescent nanoprobe with aggregation-induced emission effect according to claim 1, wherein the hydrogen peroxide-responsive fluorescent molecule with aggregation-induced emission effect is a cyanobenzene-based borate fluorescent organic molecule.
3. The preparation method of the mesoporous silica hydrogen peroxide fluorescent nanoprobe with the aggregation-induced emission effect as claimed in any one of claims 1-2, characterized by comprising the following steps:
(1) Preparing an intermediate organic compound 1 by reacting N, N-dimethylbenzaldehyde and p-bromophenylacetonitrile, wherein the intermediate organic compound 1 has a structural formula as follows:
(2) The intermediate organic compound 1 reacts with bis (pinacolato) diboron to obtain the hydrogen peroxide responsive fluorescent molecule with aggregation-induced emission effect, and the structural formula is as follows:
(3) 3-chloropropyl trimethoxyl silane and NaI are subjected to halogen exchange reaction to prepare 3-iodopropyl trimethoxyl silane;
(4) Carrying out quaternary ammonification reaction on the hydrogen peroxide responsive fluorescent molecule with aggregation-induced emission effect in the step (2) and 3-iodopropyl trimethoxy silane to prepare a siloxane fluorescent organic molecule based on the cyanobenzene borate;
(5) And (3) copolycondensating tetraethyl orthosilicate and siloxane fluorescent organic molecules based on the cyanobenzene borate to obtain the final mesoporous silica hydrogen peroxide fluorescent nano probe with the aggregation-induced emission effect.
4. The method according to claim 3, wherein the molar ratio of the N, N-dimethylbenzaldehyde to the p-bromophenylacetonitrile in the step (1) is 1:1.
5. the production method according to claim 3, characterized in that the molar ratio of the intermediate organic compound 1 to the bis (pinacolato) diboron in step (2) is 3:4.
6. the preparation method according to claim 3, wherein the molar ratio of the 3-chloropropyltrimethoxysilane to the NaI in step (3) is 2:3.
7. the preparation method according to claim 3, wherein the step (4) of preparing the siloxane fluorescent organic molecule based on the cyanostyrene borate comprises the following specific steps: heating hydrogen peroxide responsive fluorescent molecules with aggregation-induced emission effect and 3-iodopropyl trimethoxy silane in ethyl acetate according to a molar ratio of 5 to 6 for reaction, adding excessive potassium carbonate as a catalyst, performing reflux reaction on the mixture for 72 hours, filtering to remove the catalyst, performing reduced pressure distillation to remove excessive solvent, cooling the residual reaction mixed solution to room temperature, adding n-hexane, precipitating solid siloxane fluorescent organic molecules based on the cyanostyrene borate, standing for half an hour, precipitating supernatant, adding n-hexane, performing ultrasonic treatment, standing for half an hour, repeatedly washing for three times, performing suction filtration to obtain the solid, and drying to obtain the siloxane fluorescent organic molecules based on the cyanostyrene borate.
8. The preparation method according to claim 3, wherein the hydrogen peroxide fluorescent nanoprobe with aggregation-induced emission effect in the step (5) is prepared by the following specific steps: cetyl trimethyl ammonium bromide and sodium hydroxide are dissolved in deionized water to obtain a cetyl trimethyl ammonium bromide aqueous solution, then tetraethyl orthosilicate and siloxane fluorescent organic molecules based on the cyanobenzene borate are added into the cetyl trimethyl ammonium bromide aqueous solution under stirring, and the mixed solution is stirred for 1 hour at 80 ℃ and then cooled to room temperature.
9. The method according to claim 8, wherein the molar ratio of hexadecyl trimethyl ammonium bromide to sodium hydroxide is 1; the mass ratio of the tetraethyl orthosilicate to the siloxane fluorescent organic molecules based on the cyanobenzene borate is 10-0.2.
10. Use of the mesoporous silica-based hydrogen peroxide fluorescent nanoprobe with aggregation-induced emission effect property according to any one of claims 1 to 2 in the detection of hydrogen peroxide.
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CN117569014A (en) * | 2023-11-16 | 2024-02-20 | 齐鲁工业大学(山东省科学院) | H (H) 2 O 2 Preparation method of gas film sensing material and antibacterial property research thereof |
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CN117569014A (en) * | 2023-11-16 | 2024-02-20 | 齐鲁工业大学(山东省科学院) | H (H) 2 O 2 Preparation method of gas film sensing material and antibacterial property research thereof |
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