CN110967395B - Gold-loaded functionalized porous TiO2Thin film and application in SALDI-MS analysis - Google Patents
Gold-loaded functionalized porous TiO2Thin film and application in SALDI-MS analysis Download PDFInfo
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Abstract
The invention discloses a gold-loaded functionalized porous TiO2The film and the application in SALDI-MS analysis, the preparation method of the film is as follows: adding tetrabutyl titanate and absolute ethyl alcohol, stirring to obtain a precursor solution, and placing the carrier in a reactor; adding cetyl trimethyl ammonium bromide ethanol solution and ultrapure water into the precursor solution, carrying out ice bath, washing, heating and aging to obtain TiO2A film; immersing the carrier in acidic alcohol solution, stirring, washing, heating for ageing, and loading porous TiO2Immersing the carrier of the film into an acetone solution containing N-trimethoxysilylpropyl-N, N, N-trimethyl ammonium chloride, stirring, washing, heating and aging; immersing the carrier in HAuCl4Aqueous solution, stirred, rinsed and dipped in NaBH4Heating and aging in water solution in ice bath. The film has good reproducibility and salt tolerance, eliminates the background interference of the traditional organic matrix, and can realize the rapid analysis of low molecular weight compounds under a positive and negative ion dual mode.
Description
Technical Field
The invention belongs to the field of analytical chemistry, relates to a SALDI-MS substrate material, and particularly relates to a gold-loaded functionalized porous TiO2Thin films and their use in SALDI-MS analysis.
Background
Matrix-assisted laser desorption/ionization (MALDI) Mass Spectrometry (MS) relies on a matrix that absorbs laser energy to co-crystallize with the analyte to achieve high ionization and desorption efficiencies. MALDI has many advantages and is an indispensable tool for polymer analysis. However, the presence of a matrix can lead to a high chemical background in the region below the mass spectrum m/z 700, which presents challenges in analyzing small molecules. Surface-assisted laser desorption/ionization (SALDI) MS is a soft laser-based ionization technique. SALDI employs various nanostructured or microstructured substrates to transfer laser energy to an analyte to facilitate desorption/ionization of the analyte from the surface. The SALDI MS and the substitution of active surfaces for MALDI chemistry matrix further eliminates high background interference and gains widespread interest. In recent years, the SALDI MS has been developed as a technology with great potential due to the advantages of high throughput, no matrix interference in low-mass regions of mass spectra, capability of performing global analysis and tissue imaging on complex biological matrices, and the like, and can be used for understanding many challenges faced in modern research.
Three main types of substrates are currently used in SALDI, including semiconductor-based (e.g., porous silicon and silicon nanowire arrays), carbon-based (e.g., graphene and carbon nanotubes), and metal-based (e.g., gold and silver nanoparticles) materials. The structures have stronger ultraviolet absorption capacity, but the repeatability of detection signals of the materials is poor; the salt tolerance is poor; the hydrophobicity is poor, and the detection sensitivity is weakened; the action with the target surface is weak, and the ion source is easy to be polluted.
Therefore, the development of a substrate which has reproducibility, salt tolerance, low background interference and can detect and analyze a plurality of low molecular weight compounds is of great significance for the research of SALDI MS analysis.
Disclosure of Invention
The invention aims to overcome the defects of the existing MALDI technology and provide a gold-loaded functionalized porous TiO2Thin films and their use in SALDI-MS analysis.
The above purpose of the invention is realized by the following technical scheme:
gold-loaded functionalized porous TiO2A film prepared by the steps of:
step S1, preparing a precursor solution: adding a proper amount of tetrabutyl titanate and absolute ethyl alcohol into a reactor, magnetically stirring and fully mixing to form a precursor solution, and placing a carrier into the reactor;
step S2, preparing TiO2Film formation: adding proper amount of ethanol solution of hexadecyl trimethyl ammonium bromide into the precursor solution which is vigorously stirredAnd ultrapure water and ice bath are carried out, the modified carrier is thoroughly washed by absolute ethyl alcohol and water in sequence, and then the carrier is heated and aged to form TiO on the carrier2A film;
step S3, preparing functionalized porous TiO2Film formation: will support TiO2Soaking the carrier of the film into acidic ethanol solution and stirring to prepare porous TiO2Film, washing the porous TiO completely with absolute alcohol2Heating and aging the film carrier to remove cetyl trimethyl ammonium bromide and obtain porous TiO2A carrier for the thin film coating; immersing the carrier into an acetone solution containing N-trimethoxysilylpropyl-N, N, N-trimethyl ammonium chloride, magnetically stirring at normal temperature, washing with acetone, ethanol and water in sequence, and heating for aging;
step S4, loading gold: loading functionalized porous TiO2Immersion of the support of the film in HAuCl4Stirring in water solution at normal temperature, washing with ultrapure water, and immersing in NaBH4Ice-bath is carried out in the water solution, and finally heating and aging are carried out to obtain the product.
Further, the carrier in steps S1 and S2 is ITO glass.
Further, the ITO glass is used after being cleaned, and the cleaning process is as follows: firstly, soaking ITO glass in 1M NaOH aqueous solution overnight, then carrying out ultrasonic treatment on the ITO glass in acetone, ethanol and ultrapure water for 15min, finally thoroughly washing the ITO glass with ultrapure water and using N2And (5) drying.
Furthermore, the stirring speed in each step is 1500 r/min.
Further, the concentration of the ethanol solution of cetyltrimethylammonium bromide in step S2 was 50 mg/mL.
Further, 5mL of tetrabutyl titanate and 20mL of anhydrous ethanol were added to the reactor in step S1.
Further, the volume of the ethanol solution of cetyltrimethylammonium bromide in step S2 was 10 mL.
Any of the above gold-loaded functionalized porous TiO2The film is used as a substrate in the surface-assisted laser desorption ionization time-of-flight mass spectrometry detection of small molecular weight compounds.
Further, the small molecular weight compound refers to a compound having a molecular weight of less than 1000 daltons, and includes amino acids, fatty acids, alkaloids, flavones, saccharides, dopamine, urine metabolites, and serum metabolites.
Any of the above gold-loaded functionalized porous TiO2Use of a film for mass spectrometric imaging analysis of secondary metabolites indirectly by imprinted petals.
Has the advantages that:
the invention provides a gold-loaded functionalized porous TiO2The film is a high-efficiency Laser Desorption Ionization (LDI) material, the preparation method is simple and controllable, and the film substrate material has a regular porous structure, strong ultraviolet absorption capacity, high sensitivity, low background noise, good reproducibility, salt tolerance and quantitative capacity, and is a preferable substrate for analyzing low molecular weight compounds by surface-assisted laser desorption ionization mass spectrometry. The substrate material eliminates background interference of a traditional organic matrix, can quickly and efficiently realize accurate analysis of compounds with molecular weight less than 1000Dalton, such as amino acid, fatty acid, alkaloid, flavone, glucose, dopamine and a plurality of small molecule metabolites in a biological sample in a positive and negative ion mode, and can be used for analyzing distribution of various secondary metabolites in petal tissues by virtue of imprinting petal indirect imaging.
Drawings
FIG. 1 shows a gold-loaded functionalized porous TiO2Scanning electron microscope images of the film surface;
FIG. 2 shows a gold-loaded functionalized porous TiO2Contact angle analysis chart of film surface;
FIG. 3 shows gold-loaded functionalized porous TiO2Analyzing the mass spectrogram of the amino acid mixture by using the film as a substrate, wherein the mass spectrogram is a background interference peak;
FIG. 4 shows gold-loaded functionalized porous TiO2Analyzing the mass spectrogram of the fatty acid mixture by using the film as a substrate, wherein the mass spectrogram is a background interference peak;
FIG. 5 shows gold-loaded functionalized porous TiO2Analyzing the mass spectrum of the alkaloid mixture by using the film (b picture) and the conventional matrix CHCA (a picture); wherein, is background interference peak;
FIG. 6 is a graph of gold-loaded functionalized porous TiO2Detecting a mass spectrogram of glucose in serum by using a film, wherein an interpolation graph is a calibration curve of the glucose;
FIG. 7 is a photograph of the mass spectrum of vinblastine (m/z 337.20) and rutin (m/z 609.10) in Catharanthus roseus.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying drawings and examples, but not intended to limit the scope of the invention.
Example 1:
gold-loaded functionalized porous TiO2A film prepared by the steps of:
step S1, preparing a precursor solution: adding 5mL of tetrabutyl titanate and 20mL of absolute ethyl alcohol into a reactor, stirring by magnetic force for 5min, fully mixing to form a precursor solution, and placing ITO glass in the reactor;
step S2, preparing TiO2Film formation: adding 10mL of cetyl trimethyl ammonium bromide ethanol solution with the concentration of 50mg/mL and 1% (V/V) of ultrapure water into the vigorously stirred precursor solution in sequence, carrying out ice bath for 2h, then flushing the modified ITO glass completely with absolute ethanol and water in sequence, aging for 2h at 80 ℃, and forming TiO on the ITO2Thin film (TDF/ITO);
step S3, preparing functionalized porous TiO2Film formation: TDF/ITO was immersed in 0.1M HCl ethanol solution and stirred for 15min to prepare porous TiO2The preparation method comprises the following steps of (1) thoroughly washing a film (PTDF/ITO) by absolute ethyl alcohol, ageing the film at 80 ℃ for 2 hours, immersing the PTDF/ITO into an acetone solution containing 1% (V/V) N-trimethoxysilylpropyl-N, N, N-trimethyl ammonium chloride, magnetically stirring the film at normal temperature for 2 hours, then washing the film by acetone, ethyl alcohol and water in sequence, and ageing the film at 80 ℃ for 2 hours;
step S4, loading gold: dipping the functionalized PTDF/ITO in 5mM HAuCl4In the aqueous solution, stirred at room temperature for 8 hours, rinsed with ultrapure water, and immersed in 0.1M NaBH4Ice-bath is carried out in the water solution for 2h, and finally aging is carried out for 2h at 80 ℃. FIG. 1 shows a gold-loaded functionalized porous TiO2Scanning electron microscope images of the film surface. FIG. 2 shows the loading of Au-CuFunctionalized porous TiO2The contact angle analysis chart of the film surface can show that the film surface is hydrophobic.
The ITO glass is used after being cleaned, and the cleaning process is as follows: firstly, soaking ITO glass in 1M NaOH aqueous solution overnight, then carrying out ultrasonic treatment on the ITO glass in acetone, ethanol and ultrapure water for 15min, finally thoroughly washing the ITO glass with ultrapure water and using N2And (5) drying.
The stirring speed in the steps is 1500 r/min.
Example 2:
gold-supporting functionalized porous TiO prepared in example 12The method for analyzing the amino acid by the thin film surface assisted laser desorption ionization mass spectrum in the positive ion mode comprises the following specific operations:
mixing 17 amino acids (glycine, alanine, gamma-aminobutyric acid, serine, proline, valine, threonine, leucine, asparagine, aspartic acid, lysine, methionine, histidine, phenylalanine, arginine, tyrosine and tryptophan) to prepare a 1mM solution, and dropwise adding 0.2 mu L of the amino acid mixed solution to the gold-loaded functionalized porous TiO2And (3) carrying out surface-assisted laser desorption ionization mass spectrometry (mass spectrogram shown in figure 3) on the surface of the film in a positive ion mode after drying. It can be seen from FIG. 3 that 17 amino acids were detected, with low background interference and exhibiting a higher signal-to-noise ratio (S/N). The results show that the substrate material can be used as a SALDI substrate for analyzing amino acid small molecules.
Example 3:
gold-supporting functionalized porous TiO prepared in example 12The method for analyzing fatty acid by using the film surface assisted laser desorption ionization mass spectrum in the negative ion mode comprises the following specific operations: mixing 14 fatty acids (undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, docosanoic acid, and tetracosanoic acid) to obtain 1mM solution, and adding 0.2 μ L of fatty acid mixed solution dropwise into the loaded gold-functionalized porous TiO2Drying the film surface, and performing surface-assisted laser desorption ionization mass spectrometry (mass spectrogram is shown in figure)Shown at 4). From fig. 4, it can be seen that 14 fatty acids were detected, with low background interference and exhibiting a higher signal-to-noise ratio. The results show that the substrate material can be used as a SALDI substrate for analyzing fatty acid small molecules.
Example 4:
gold-supporting functionalized porous TiO prepared in example 12The membrane and the conventional matrix CHCA were analyzed for alkaloids in positive ion mode, as follows: weighing 10mg CHCA dissolved in 1ml acetonitrile water solution (V/V, 6:4), mixing 7 alkaloids (trigonelline, ephedrine, laburnine, aloperine, oxymatrine, scopolamine, and racanisodamine) to obtain 1mM solution, and adding 0.2 μ L alkaloid mixed solution dropwise into the loaded gold-functionalized porous TiO2And (3) dripping 0.2 mu L of alkaloid mixed solution and 0.2 mu L of CHCA matrix solution on the surface of the film in sequence on the surface of the common ITO glass, and performing laser desorption ionization mass spectrometry in a positive ion mode after drying (the mass spectrogram is shown in figure 5). From FIG. 5, it can be found that the supported gold-functionalized porous TiO was compared with CHCA2The thin film substrate detected 7 alkaloids, low background interference and showed higher signal to noise ratio, while the traditional CHCA matrix detected not only no target alkaloids but also strong interfering signals. The results show that the substrate material can be used as a SALDI substrate for analyzing alkaloid small molecules.
Example 5:
gold-supporting functionalized porous TiO prepared in example 12The film reproducibility is examined, and the specific operation is as follows: respectively preparing dopamine (Dop), glucose (Glu), histidine (His) and Stearic Acid (SA) with the concentration of 1.0 mM, and sequentially dropwise adding 0.2 mu L of four standard substance solutions to the gold-loaded functionalized porous TiO2And (3) carrying out surface-assisted laser desorption ionization mass spectrometry on the surface of the film. 10 data were collected for each sample and the Relative Standard Deviation (RSD) of the signal-to-noise ratio of detection for each substance was calculated (as shown in Table 1). As can be seen from Table 1, it can be seen that the gold-supported-functionalized porous TiO was2The film has good reproducibility.
TABLE 1 gold-loaded functionalized porous TiO2Film reproducibility test chart
Example 6:
supported gold-functionalized porous TiO prepared using example 12The membrane quantitative detection of glucose in mouse serum specifically comprises the following steps: glucose calibration curves were obtained in glucose standard solutions of different concentrations (0.5, 1, 3, 5, 7, 9mM) and 5mM isotopic solutions of glucose. Collecting a blood sample of the SD rat, standing for 2 hours at room temperature, centrifuging for 10min at 4 ℃, and collecting supernatant, namely serum at 4000 r/min. Isotope D-glucose-1-13C is added into serum, the final concentration is 5mM, acetonitrile (acetonitrile: serum: 1:3, V/V) is added for simple pretreatment, most of high-abundance protein in the serum sample is removed, then vortex is carried out for 5min, centrifugation is carried out for 10min at 4 ℃, 13000r/min, and the serum is collected for SALDI-MS analysis. FIG. 6 is a graph of gold-loaded functionalized porous TiO2And detecting a mass spectrogram and a glucose calibration curve of glucose in serum by using the film. And calculating the glucose content in the rat serum according to the glucose calibration curve, comparing by using a glucose detection kit, and further verifying the reliability of the method. Table 1 shows the glucose measurements in the serum of three rats by different methods. The results show that the glucose content in the mouse serum measured by the method is basically consistent with the result measured by the glucose kit.
TABLE 2 determination of glucose in the serum of three rats by different methods
Example 7:
supported gold-functionalized porous TiO prepared using example 12And (3) indirectly imaging and analyzing secondary metabolites by using the thin film imprinted petals. The specific operation is as follows: dissecting fresh flower, pressing the upper surface of petal on the gold-loaded functionalized porous TiO2Sequentially placing dust-free paper and common glass on the back of petal on film, and fixing with adhesive tapeThen, the flowers were manually embossed by applying pressure on a 45 x 100mm area for 5 minutes using a manual vice press. Immediately after stamping, tissue residue was removed from the substrate with forceps and, after drying in air, the petal blots were analyzed for imaging. FIG. 7 is a mass spectrum imaging of vinblastine (m/z 337.20) and rutin (m/z 609.10) in Catharanthus roseus, and it can be seen that vinblastine is distributed in the whole petal, but is mainly distributed in the central part of the petal, rutin is mainly distributed in the central part of the petal, and the content of other parts is extremely low, so that the substrate can be used for detecting some secondary metabolites in the petal imprinting.
The invention provides a gold-loaded functionalized porous TiO2High temperature is not needed in the preparation process of the film substrate material, and the experimental operation is simple and convenient. The surface of the film is hydrophobic, so that the film is beneficial to concentrating a low-abundance sample with high sample amount, improves the sensitivity, has good salt tolerance and reproducibility, and can quantitatively detect some small molecule metabolites in a biological sample, such as glucose in serum.
The substrate material does not need a matrix, eliminates background interference existing in the matrix and can realize rapid analysis of low molecular weight compounds.
The substrate material can be applied to detecting low molecular weight compounds under a positive and negative ion dual mode.
The base material can realize petal imprinting and indirect imaging of distribution of various secondary metabolites in petal tissues. The petals of the catharanthus roseus are blotted, and alkaloids, flavonoids, sugars and related metabolites are detected.
The above-described embodiments are intended to be illustrative of the nature of the invention, but those skilled in the art will recognize that the scope of the invention is not limited to the specific embodiments.
Claims (9)
1. Gold-loaded functionalized porous TiO2A film, characterized by being prepared by the steps of:
step S1, preparing a precursor solution: adding a proper amount of tetrabutyl titanate and absolute ethyl alcohol into a reactor, magnetically stirring and fully mixing to form a precursor solution, and placing a carrier into the reactor;
step S2, preparing TiO2Film formation: adding proper amount of ethanol solution of hexadecyl trimethyl ammonium bromide and ultrapure water into the precursor solution which is vigorously stirred, carrying out ice bath, completely flushing the modified carrier with absolute ethanol and water in sequence, heating and aging to form TiO on the carrier2A film;
step S3, preparing functionalized porous TiO2Film formation: will support TiO2Soaking the carrier of the film into acidic ethanol solution and stirring to prepare porous TiO2Film, washing the porous TiO completely with absolute alcohol2Heating and aging the film carrier to remove cetyl trimethyl ammonium bromide and obtain porous TiO2A carrier for the thin film coating; immersing the carrier into an acetone solution containing N-trimethoxysilylpropyl-N, N, N-trimethyl ammonium chloride, magnetically stirring at normal temperature, washing with acetone, ethanol and water in sequence, and heating for aging;
step S4, loading gold: loading functionalized porous TiO2Immersion of the support of the film in HAuCl4Stirring in water solution at normal temperature, washing with ultrapure water, and immersing in NaBH4Ice-bath is carried out in the water solution, and finally heating and aging are carried out to obtain the product.
2. The gold-loaded functionalized porous TiO of claim 12A film characterized by: the carrier in steps S1 and S2 is ITO glass.
3. The gold-loaded functionalized porous TiO of claim 22The film is characterized in that the ITO glass is used after being cleaned, and the cleaning process is as follows: firstly, soaking ITO glass in 1M NaOH aqueous solution overnight, then carrying out ultrasonic treatment on the ITO glass in acetone, ethanol and ultrapure water for 15min, finally thoroughly washing the ITO glass with ultrapure water and using N2And (5) drying.
4. The gold-loaded functionalized porous TiO of claim 12A film characterized by: the stirring speed in each step is 1500 r/min.
5. The gold-loaded functionalized porous TiO of claim 12A film characterized by: the concentration of the ethanol solution of cetyltrimethylammonium bromide in step S2 was 50 mg/mL.
6. The supported gold-functionalized porous TiO of claim 52A film characterized by: in step S1, 5mL of tetrabutyl titanate and 20mL of absolute ethanol were added to the reactor.
7. The gold-supporting-functionalized porous TiO of claim 62A film characterized by: the volume of the ethanol solution of cetyltrimethylammonium bromide in step S2 was 10 mL.
8. The gold-loaded functionalized porous TiO of any one of claims 1 to 72The film is used as a substrate in the surface-assisted laser desorption ionization time-of-flight mass spectrometry detection of small molecular weight compounds; wherein the small molecular weight compound refers to a compound with a molecular weight of less than 1000Dalton, and comprises amino acids, fatty acids, alkaloids, flavones, saccharides, dopamine, urine metabolites and serum metabolites.
9. The gold-loaded functionalized porous TiO of any one of claims 1 to 72Use of a film for mass spectrometric imaging analysis of secondary metabolites indirectly by imprinted petals.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120819A (en) * | 1993-12-10 | 1996-04-17 | 东陶机器株式会社 | Multi-functional material having photo-catalytic function and production method therefor |
| CN101329301A (en) * | 2007-06-19 | 2008-12-24 | 佳能株式会社 | Substrate for mass spectrometry, mass spectrometry, and mass spectrometer |
| CN101574650A (en) * | 2009-05-26 | 2009-11-11 | 上海应用技术学院 | Mesoporous photocatalytic film and preparation method thereof |
| CN103272634A (en) * | 2013-05-28 | 2013-09-04 | 常州大学 | Preparation method of nano metal loaded molecular sieve based catalyst |
| CN103721705A (en) * | 2014-01-14 | 2014-04-16 | 武汉理工大学 | Porous TiO2 fiber loaded noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN105567260A (en) * | 2005-09-20 | 2016-05-11 | 罗利克有限公司 | Print Functionalized photoreactive compounds |
| CN106835077A (en) * | 2017-01-20 | 2017-06-13 | 陕西科技大学 | A kind of preparation method of the porous Au coatings for suppressing Multipactor |
| CN107537479A (en) * | 2017-08-15 | 2018-01-05 | 武汉理工大学 | A kind of degrading volatile organic pollutant catalyst and preparation method thereof |
-
2019
- 2019-12-20 CN CN201911329979.6A patent/CN110967395B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120819A (en) * | 1993-12-10 | 1996-04-17 | 东陶机器株式会社 | Multi-functional material having photo-catalytic function and production method therefor |
| CN105567260A (en) * | 2005-09-20 | 2016-05-11 | 罗利克有限公司 | Print Functionalized photoreactive compounds |
| CN101329301A (en) * | 2007-06-19 | 2008-12-24 | 佳能株式会社 | Substrate for mass spectrometry, mass spectrometry, and mass spectrometer |
| CN101574650A (en) * | 2009-05-26 | 2009-11-11 | 上海应用技术学院 | Mesoporous photocatalytic film and preparation method thereof |
| CN103272634A (en) * | 2013-05-28 | 2013-09-04 | 常州大学 | Preparation method of nano metal loaded molecular sieve based catalyst |
| CN103721705A (en) * | 2014-01-14 | 2014-04-16 | 武汉理工大学 | Porous TiO2 fiber loaded noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN106835077A (en) * | 2017-01-20 | 2017-06-13 | 陕西科技大学 | A kind of preparation method of the porous Au coatings for suppressing Multipactor |
| CN107537479A (en) * | 2017-08-15 | 2018-01-05 | 武汉理工大学 | A kind of degrading volatile organic pollutant catalyst and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Effect of the titania morphology on the Au/TiO2-catalyzed aerobic epoxidation of stilbene;Pascal Lignier 等;《Catalysis Today》;20080613;第355-360页 * |
| Quantitative MALDI Imaging of Spatial Distributions and Dynamic Changes of Tetrandrine in Multiple Organs of Rats;Weiwei Tang 等;《Theranostics》;20190125;第9卷(第4期);第932-944页 * |
| SBA-15 Anchored Metal Containing Catalysts in the Oxidative Desulfurization Process;Marcello Crucianelli 等;《Catalysts》;20191123;第1-30页 * |
| Ti02纳晶多孔薄膜的制备及性能研究;于大勇;《精细石油化工进展》;20051231;第6卷(第6期);第41-48页 * |
| 高热稳定性有序介孔TiO2/活性炭制备及其孔-孔协同光催化性能;刘晨 等;《中国科学：化学》;20141231;第44卷(第11期);第1788-1799页 * |
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