CN107247087B - Enhanced laser desorption and ionization substrate and preparation method thereof - Google Patents
Enhanced laser desorption and ionization substrate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an enhanced laser desorption and ionization substrate, which takes a colloid crystal with an opal structure as a template, takes tungsten titanium oxide as a prepolymer, and takes a tungsten titanium oxide photonic crystal prepared by template replication as a laser desorption and ionization substrate; the photonic crystal has an inverse opal structure, and the forbidden band of the photonic crystal is coupled with the absorption of tungsten titanium oxide and the laser wavelength; by adjusting the size of the crystal lattice of the section of photonic crystal, the forbidden band edge of the tungsten titanium oxide photonic crystal is positioned at the position of analyzing laser wavelength, and the interaction between laser and a substrate is increased, so that the laser desorption and ionization efficiency is enhanced. According to the invention, the size of the tungsten-titanium oxide photonic crystal lattice is adjusted, so that the photon forbidden band is matched with the wavelength of the laser, the action time of the laser and the sample to be detected is prolonged, and the laser desorption effect is enhanced. The method is applied to mass spectrometry, simplifies the preparation process of samples, reduces the interference of background signals and improves the detection sensitivity.
Description
Technical Field
The invention relates to the field of biomedical research, analysis and detection, in particular to a substrate material for enhancing laser desorption ionization by utilizing the slow light effect of a photonic crystal and the band gap characteristic of a metal oxide.
Background
Mass spectrometry is a powerful technical method in the analysis of material, and makes a great contribution to the development of molecular biology. Such as for determining elements of the periodic table, analysis of biological tissue components, imaging of tissue sections, and the like. The mass spectrometry consists of three main components: ion source, mass analyzer, ion detector. From this we can see that ionization of the sample is a very important step. Many methods of sample ionization have been discovered, and matrix-enhanced laser desorption and ionization remain the hot spots in question. The slow light effect of photonic crystals and the band gap characteristic of semiconductor metal oxides are combined to prepare the substrate material for enhancing laser desorption and ionization.
The inverse opal photonic crystal prepared based on the semiconductor metal oxide has good light absorption, photo-electricity and photo-thermal properties, and the slow light effect of the photonic crystal increases the light absorption and energy conversion time, so that the potential good desorption ionization performance is further highlighted. Therefore, the tungsten-titanium oxide photonic crystal which is a substrate capable of enhancing the laser desorption effect is designed and prepared, and the potential of the tungsten-titanium oxide photonic crystal in the application aspect of mass spectrum is enhanced by exploring and researching the optical performance of the tungsten-titanium oxide photonic crystal.
Disclosure of Invention
The invention mainly solves the technical problem of providing a preparation method of an enhanced laser desorption and ionization substrate, which is used for improving the efficiency of a mass spectrum laser desorption ion source.
In order to solve the technical problems, the invention adopts a substrate for enhancing laser desorption and ionization, which comprises the following components: taking a colloid crystal with an opal structure as a template, taking tungsten titanium oxide as a prepolymer, and taking a tungsten titanium oxide photonic crystal prepared by template replication as a laser desorption and ionization substrate; the photonic crystal has an inverse opal structure, and the forbidden band of the photonic crystal is coupled with the absorption of tungsten titanium oxide and the laser wavelength; by adjusting the size of the crystal lattice of the section of photonic crystal, the forbidden band edge of the tungsten titanium oxide photonic crystal is positioned at the position of analyzing laser wavelength, and the interaction between laser and a substrate is increased, so that the laser desorption and ionization efficiency is enhanced.
The preparation method of the enhanced laser desorption and ionization substrate comprises the following steps:
1) preparing a colloid crystal template with an opal structure:
preparing a polymer colloidal nanoparticle solution, immersing a conductive substrate into the solution, preparing a colloidal crystal template through self-assembly of the colloidal nanoparticles, and heating to a temperature close to the glass transition temperature of the polymer to connect and reinforce the colloidal nanoparticles;
2) preparing a tungsten titanium oxide photonic crystal:
filling a tungsten-titanium oxide prepolymer solution into the gaps of the colloidal crystal template prepared in the step 1), then heating the sample, and filling the tungsten-titanium oxide into the gaps of the colloidal crystal template after oxidizing and drying; and finally, calcining the sample, removing the colloidal crystal template, and preparing the tungsten titanium oxide photonic crystal with the inverse opal structure as the enhanced laser desorption and ionization substrate.
Wherein the content of the first and second substances,
the polymer colloid nano particles in the step 1) are monodisperse nano particles of polystyrene PS, polymethyl methacrylate PMMA, polyacrylonitrile PAN or copolymers thereof.
The tungsten-titanium oxide prepolymer solution in the step 2) is prepared from tetrabutyl titanate TBOT and titanium tetrachloride TiCl4Titanium sulfate TiSO4Tungsten chloride WCl6Tungstate or tungstophosphate is used as a mixed solution of solutes.
Has the advantages that: the enhanced laser desorption and ionization substrate prepared by the invention has the following advantages:
(1) the enhanced laser desorption and ionization substrate prepared by the method is of an inverse opal structure, has a very high specific surface area, and is easy to bear a sample.
(2) The invention combines the band gap characteristic of tungsten titanium oxide and the slow light effect of photonic crystal, and the prepared substrate can greatly enhance the effect of laser desorption ionization.
Drawings
FIG. 1 is a schematic diagram of the preparation of a tungsten titanium oxide photonic crystal.
Detailed Description
The enhanced laser desorption and ionization substrate takes a colloidal crystal with an opal structure as a template, takes tungsten titanium oxide as a prepolymer, and takes a tungsten titanium oxide photonic crystal prepared by template replication as a laser desorption and ionization substrate. The photonic crystal has an inverse opal structure, and the forbidden band of the photonic crystal is coupled with the absorption of tungsten titanium oxide and the laser wavelength; by adjusting the size of the crystal lattice of the photonic crystal, the forbidden band edge of the tungsten titanium oxide photonic crystal is positioned at the position of analyzing the laser wavelength, and the interaction between the laser and the substrate is increased, so that the laser desorption and ionization efficiency is enhanced.
The preparation method of the enhanced laser desorption and ionization substrate comprises the following steps:
1) preparing a colloid crystal template with an opal structure:
preparing a polymer colloid nano particle solution, immersing the conductive substrate into the solution, preparing a colloid crystal template through self-assembly of the colloid nano particles, and then heating to a temperature close to the glass transition temperature of the polymer to connect and reinforce the colloid nano particles.
2) Preparing a tungsten titanium oxide photonic crystal:
filling a tungsten-titanium oxide prepolymer solution into the gaps of the colloidal crystal template prepared in the step 1), then heating the sample, and filling the tungsten-titanium oxide into the gaps of the colloidal crystal template after oxidizing and drying; and finally, calcining the sample, removing the colloidal crystal template, and preparing the tungsten titanium oxide photonic crystal with the inverse opal structure as the enhanced laser desorption and ionization substrate.
The polymer nanoparticles in the step 1) are monodisperse nanoparticles of Polystyrene (PS), polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN) or copolymers thereof.
The tungsten-titanium oxide prepolymer solution in the step 2) is prepared from tetra-n-butyl titanate (TBOT) or titanium tetrachloride (TiCl)4) Or titanium sulfate (TiSO)4) With tungsten chloride (WCl)6) Or mixed solution with tungstate or tungstophosphate as solute.
The first embodiment is as follows: preparation of tungsten titanium oxide photonic crystal substrate with photon forbidden band at 293nm
(1) Preparation of polystyrene colloid crystal template with opal structure by vertical pulling method
And (3) carrying out centrifugal purification on the monodisperse polystyrene nanoparticles with the particle size of 176nm to prepare a colloidal nanoparticle solution with the mass percent of the colloidal nanoparticles being 5%. And (3) treating the washed and dried glass slide by plasma for 5min, fixing the glass slide on a pulling instrument, and vertically immersing the glass slide in the colloidal nanoparticle solution. The pulling speed of the pulling instrument is set to be 3mm/h, the pulling instrument is placed in the environment to avoid vibration, and the pulling instrument is started after the pulling instrument is static for 1-2 h. And after the pulling is finished, placing the polystyrene colloid crystal template in a 90 ℃ oven for 2h to connect and reinforce the particles.
(2) Preparing tungsten-titanium oxide prepolymer solution
With tetra-n-butyl titanate (TBOT) and tungsten chloride (WCl)6) As the source of tungsten titanium oxide metal element. Ethanol is used as a solvent, and the molar ratio is WCl6TBOT, ethanol is 1:2:100, then the solution is sealed in dark place and stirred for 2h at normal temperature to be mixed evenly.
(3) Preparation of tungsten titanium oxide photonic crystals
Spin coating or pouring tungsten-titanium oxide prepolymer solution into gaps of the prepared polystyrene colloidal crystal template; then horizontally standing for 12h on a hot bench at 45 ℃ to ensure that the prepolymer solution fully reacts to generate tungsten-titanium oxide; and finally, calcining the mixture in a tube furnace at 450 ℃ for 2.5 hours to remove the polystyrene colloid crystal template, thereby preparing the tungsten titanium oxide inverse opal photonic crystal with the photon forbidden band at 293 nm.
Example two: preparation of tungsten titanium oxide photonic crystal substrate with photon forbidden band at 316nm
(1) Vertical deposition method for preparing polystyrene colloid crystal template with opal structure
And (3) carrying out centrifugal purification on the monodisperse polystyrene nanoparticles with the particle size of 183nm to prepare a colloidal nanoparticle solution with the mass percent of the colloidal nanoparticles being 0.2%. And (3) treating the washed and dried glass slide by plasma for 5min, vertically immersing the glass slide into the colloidal nanoparticle solution, keeping the glass slide still, and placing the glass slide in a thermostat at the temperature of 50 ℃. Standing for 4 days, taking out the polystyrene colloidal crystal template prepared by deposition after the solution is volatilized, and then placing the polystyrene colloidal crystal template in a drying oven at 90 ℃ for 2 hours to connect and reinforce the particles.
(2) Preparing tungsten-titanium oxide prepolymer solution
By using titanium tetrachloride (TiCl)4) Andtungstate (Na)2WO4·2H2O) is used as a tungsten titanium oxide metal element source. Ethanol is used as a solvent, and the molar ratio is Na2WO4·2H2O:TiCl4Preparing a solution from ethanol at a ratio of 1:2:100, sealing the solution in a dark place, and stirring for 2 hours at normal temperature to uniformly mix the solution.
(3) Preparation of tungsten titanium oxide photonic crystals
Spin coating or pouring tungsten-titanium oxide prepolymer solution into gaps of the prepared polystyrene colloidal crystal template; then horizontally standing for 12h on a hot bench at 45 ℃ to ensure that the prepolymer solution fully reacts to generate tungsten-titanium oxide; and finally, calcining the mixture in a tube furnace at 450 ℃ for 2.5 hours to remove the polystyrene colloid crystal template, thereby preparing the tungsten titanium oxide inverse opal photonic crystal with the photon forbidden band positioned at 316 nm.
Claims (3)
1. A preparation method for enhancing laser desorption and ionization substrates is characterized in that the substrates take colloidal crystals with opal structures as templates, tungsten titanium oxide as a precursor, and tungsten titanium oxide photonic crystals prepared by template replication as laser desorption and ionization substrates;
the photonic crystal has an inverse opal structure, and the forbidden band of the photonic crystal is coupled with the absorption of tungsten titanium oxide and the laser wavelength; by adjusting the size of the crystal lattice of the photonic crystal, the forbidden band edge of the tungsten titanium oxide photonic crystal is positioned at the position of analyzing the laser wavelength, and the interaction between the laser and the substrate is increased, so that the laser desorption and ionization efficiency is enhanced;
the preparation method comprises the following steps:
1) preparing a colloid crystal template with an opal structure:
preparing a polymer colloidal nanoparticle solution, immersing a conductive substrate into the solution, preparing a colloidal crystal template through self-assembly of the colloidal nanoparticles, and heating to a temperature close to the glass transition temperature of the polymer to connect and reinforce the colloidal nanoparticles;
2) preparing a tungsten titanium oxide photonic crystal:
filling a tungsten-titanium oxide prepolymer solution into the gaps of the colloidal crystal template prepared in the step 1), then heating the sample, and filling the tungsten-titanium oxide into the gaps of the colloidal crystal template after oxidizing and drying; finally, calcining the sample, removing the colloidal crystal template, and preparing the tungsten titanium oxide photonic crystal with the inverse opal structure as an enhanced laser desorption and ionization substrate;
the size range of the polymer colloid nano particles is 176-183 nm, so that the aperture of the obtained inverse opal structure is 176-183 nm.
2. The method of claim 1, wherein the laser desorption and ionization enhancement substrate is prepared by: the polymer colloid nano particles in the step 1) are monodisperse nano particles of polystyrene PS, polymethyl methacrylate PMMA, polyacrylonitrile PAN or copolymers thereof.
3. The method of claim 1, wherein the laser desorption and ionization enhancement substrate is prepared by: the tungsten-titanium oxide prepolymer solution in the step 2) is prepared from tetrabutyl titanate TBOT and titanium tetrachloride TiCl4Titanium sulfate TiSO4Tungsten chloride WCl6Tungstate or tungstophosphate is used as a mixed solution of solutes.
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| CN102435643A (en) * | 2011-09-15 | 2012-05-02 | 东南大学 | Inverse opal colloidal crystal gas sensor array and preparation method thereof |
| JP5990000B2 (en) * | 2011-01-31 | 2016-09-07 | 公益財団法人野口研究所 | Preparation of measurement sample for MALDI mass spectrometry |
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| DE102004051785B4 (en) * | 2004-10-25 | 2008-04-24 | Bruker Daltonik Gmbh | Protein profiles with air MALDI |
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| CN102435643A (en) * | 2011-09-15 | 2012-05-02 | 东南大学 | Inverse opal colloidal crystal gas sensor array and preparation method thereof |
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