CN107247087A - One kind enhancing laser desorption is attached with ionizing substrate and preparation method thereof - Google Patents
One kind enhancing laser desorption is attached with ionizing substrate and preparation method thereof Download PDFInfo
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- CN107247087A CN107247087A CN201710348529.6A CN201710348529A CN107247087A CN 107247087 A CN107247087 A CN 107247087A CN 201710348529 A CN201710348529 A CN 201710348529A CN 107247087 A CN107247087 A CN 107247087A
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- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
- G01N27/628—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas and a beam of energy, e.g. laser enhanced ionisation
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Abstract
The present invention is that a kind of enhancing laser desorption is attached with ionizing substrate, the substrate is using the colloidal crystal with opal structural as template, tungsten titanium oxide is preceding aggressiveness, and it is attached with ionizing substrate that the tungsten titanium oxide photonic crystal prepared by template duplicating is used as laser desorption；The photonic crystal has counter opal structure, and the absorption of its forbidden band and tungsten titanium oxide, optical maser wavelength are coupled；By adjusting the lattice size of the section photonic crystal, the forbidden band edge of tungsten titanium oxide photonic crystal is set to be in the position of parsing optical maser wavelength, the interaction of increase laser and substrate, so as to strengthen, laser desorption is attached and Ionization Efficiency.Size of the invention by adjusting tungsten titanium oxide photonic crystal lattice, makes its forbidden photon band agree with laser wave appearance, adds the action time of laser and detected sample, so as to enhance laser desorption effect.Applied to the preparation process that sample is simplified in Mass Spectrometer Method, the interference of background signal is reduced, detection sensitivity is improved.
Description
Technical field
The present invention relates to biomedical research, analysis detection field, a kind of slower rays effect of utilization photonic crystal is specifically designed
The base material of laser desorption ionization should be strengthened with the band gap properties of metal oxide.
Background technology
Mass spectrometry is a strong technical method in material analysis, is that the development of molecular biology is made
Tremendous contribution.Such as it is used to determine element periodic table, biological tissue's constituent analysis, histotomy imaging etc..Mass spectrum
Analytic approach is mainly made up of three parts：Ion gun, mass analyzer, ion detector.Thus it will be seen that sample from
Sonization is a very important step.It has now been found that many sample ionizations obtain method, wherein matrix enhancement laser desorption
The attached focus that discussion is still with ionization.We are special by the band gap of the slow light effect of photonic crystal and metal oxide semiconductor
Property be combined, prepared it is a kind of strengthen laser desorption it is attached with ionization base material.
The inverse opal photonic crystal being made based on metal oxide semiconductor, material inherently have good extinction,
Optical-electronic and light thermal property, along with the slow light effect of photonic crystal increases light absorbs and energy conversion time, are further highlighted latent
Good desorption ionization performance.Thus, we, which design to prepare, a kind of can strengthen the base of laser desorption effect
Bottom --- tungsten titanium oxide photonic crystal, the optical property that it has by exploratory development, strengthens what it was applied in terms of mass spectrum
Potentiality.
The content of the invention
Technical problem:The present invention solves the technical problem of providing, a kind of enhancing laser desorption is attached with ionizing substrate
Preparation method, the efficiency for improving mass spectrum laser desorption ion gun.
Technical scheme:In order to solve the above technical problems, a kind of enhancing laser desorption that the present invention is used is attached with ionizing base
Bottom is：Using the colloidal crystal with opal structural as template, tungsten titanium oxide is preceding aggressiveness, the tungsten prepared by template duplicating
Titanium oxide photonic crystal is attached with ionizing substrate as laser desorption；The photonic crystal has counter opal structure, its forbidden band
Absorption, optical maser wavelength with tungsten titanium oxide are coupled；By adjusting the lattice size of the section photonic crystal, make tungsten titanium oxide
The forbidden band edge of photonic crystal is in the position of parsing optical maser wavelength, the interaction of increase laser and substrate, so as to strengthen sharp
Photodissociation absorption and Ionization Efficiency.
The attached preparation method with ionizing substrate of enhancing laser desorption of the present invention comprises the following steps：
1) preparation of the colloidal crystal template of opal structural：
Configure polymeric colloid nano-particle solution, conductive substrate immersed in solution, by colloidal nanoparticles from
Assembling prepares colloidal crystal template, and the glass transition temperature being then heated to close to polymer adds colloidal nanoparticles connection
Gu；
2) preparation of tungsten titanium oxide photonic crystal：
Oligomer solution before tungsten titanium oxide is filled into step 1) made from colloidal crystal template gap in, then to sample
Product are heated, after oxidation drying, and tungsten titanium oxide is filled in the gap of colloidal crystal template；Finally sample is carried out
Calcining, removes colloidal crystal template, prepares the tungsten titanium oxide photonic crystal with counter opal structure and swashs as enhancing
Photodissociation is adsorbed and ionization substrate.
Wherein,
Step 1) described in polymeric colloid nano-particle be polystyrene PS, it is polymetylmethacrylate, poly-
Acrylonitrile PAN or its copolymer monodisperse nanoparticle.
Step 2) described in tungsten titanium oxide before oligomer solution be with tetra-n-butyl titanate TBOT, titanium tetrachloride TiCl4、
Titanium sulfate TiSO4, tungsten chloride WCl6, the mixed solution that tungstates or tungsten phosphate are solute.
Beneficial effect：The enhancing laser desorption prepared by the present invention is attached and ionization substrate has advantages below：
(1) the enhancing laser desorption prepared in the present invention is attached with ionizing substrate for counter opal structure, with very high
Specific surface area, it is easy to carry sample.
(2) band gap properties of tungsten titanium oxide and the slow light effect of photonic crystal are combined by the present invention, are prepared
Substrate can greatly enhance the effect of laser desorption ionization.
Brief description of the drawings
Fig. 1 tungsten titanium oxide photonic crystals prepare schematic diagram.
Embodiment
A kind of enhancing laser desorption of the present invention is attached with ionizing substrate using the colloidal crystal with opal structural as mould
Plate, tungsten titanium oxide be preceding aggressiveness, the tungsten titanium oxide photonic crystal prepared by template duplicating be used as laser desorption it is attached with from
Sonization substrate.The photonic crystal has counter opal structure, and the absorption of its forbidden band and tungsten titanium oxide, optical maser wavelength are coupled；It is logical
The lattice size of photonic crystal is saved described in toning, the forbidden band edge of tungsten titanium oxide photonic crystal is in parsing optical maser wavelength
Position, the interaction of increase laser and substrate, so as to strengthen, laser desorption is attached and Ionization Efficiency.
The attached preparation method with ionizing substrate of enhancing laser desorption of the present invention comprises the following steps：
1) preparation of the colloidal crystal template of opal structural：
Configure polymeric colloid nano-particle solution, conductive substrate immersed in solution, by colloidal nanoparticles from
Assembling prepares colloidal crystal template, and the glass transition temperature being then heated to close to polymer adds colloidal nanoparticles connection
Gu.
2) preparation of tungsten titanium oxide photonic crystal：
Oligomer solution before tungsten titanium oxide is filled into step 1) made from colloidal crystal template gap in, then to sample
Product are heated, after oxidation drying, and tungsten titanium oxide is filled in the gap of colloidal crystal template；Finally sample is carried out
Calcining, removes colloidal crystal template, prepares the tungsten titanium oxide photonic crystal with counter opal structure and swashs as enhancing
Photodissociation is adsorbed and ionization substrate.
Step 1) described in polymer nano-particle be polystyrene (PS), it is polymethyl methacrylate (PMMA), poly-
The monodisperse nanoparticle of acrylonitrile (PAN) or its copolymer.
Step 2) described in tungsten titanium oxide before oligomer solution be with tetra-n-butyl titanate (TBOT) or titanium tetrachloride
(TiCl4) or titanium sulfate (TiSO4) and tungsten chloride (WCl6) or mixed solution that tungstates or tungsten phosphate are solute.
Embodiment one：Forbidden photon band is located at the preparation of 293nm tungsten titanium oxide photonic crystal base
(1) vertical czochralski method prepares the polystyrene colloid crystal template with opal structural
Particle diameter is subjected to centrifugal purification for 176nm monodisperse polystyrene nano-particle, colloidal nanoparticles matter is prepared
Measure the colloidal nanoparticle solution that percentage is 5%.Will be by washing dried slide corona treatment 5min, Ran Hougu
It is scheduled on lifting instrument, is dipped vertically into colloidal nanoparticle solution.Lifting instrument sets pull rate to be 3mm/h, places environment and keeps away
Start lifting instrument after exempting from vibrations, static 1-2h.Polystyrene colloid crystal template is placed in 2h in 90 DEG C of baking ovens by lifting after finishing
Make particle reinforcement by connection.
(2) oligomer solution before configuration tungsten titanium oxide
Using tetra-n-butyl titanate (TBOT) and tungsten chloride (WCl6) originated as tungsten titanium oxide metallic element.With ethanol
It is WCl according to mol ratio for solvent6:TBOT:Ethanol=1:2:100 prepare solution, then seal solution lucifuge, under normal temperature
Stirring 2h is allowed to well mixed.
(3) tungsten titanium oxide photonic crystal is prepared
By oligomer solution spin coating before tungsten titanium oxide or it is poured into the polystyrene colloid crystal template gap of preparation；So
The horizontal rest 12h in 45 DEG C of thermal station, makes preceding oligomer solution fully react generation tungsten titanium oxide afterwards；It is finally putting into tube furnace
In 450 DEG C calcining 2.5h to remove polystyrene colloid crystal template so that prepare forbidden photon band be located at 293nm tungsten titanium
Oxide inverse opal photonic crystal.
Embodiment two：Forbidden photon band is located at the preparation of 316nm tungsten titanium oxide photonic crystal base
(1) vertical deposition method prepares the polystyrene colloid crystal template with opal structural
Particle diameter is subjected to centrifugal purification for 183nm monodisperse polystyrene nano-particle, colloidal nanoparticles matter is prepared
Measure the colloidal nanoparticle solution that percentage is 0.2%.Will be by washing dried slide corona treatment 5min, vertically
Immerse in colloidal nanoparticle solution, remains stationary is motionless, be placed in the insulating box that temperature is 50 DEG C.4 days are stood, its solution is treated
Polystyrene colloid crystal template prepared by deposition is can be taken off after volatilization, then polystyrene colloid crystal template is placed in
2h makes particle reinforcement by connection in 90 DEG C of baking ovens.
(2) oligomer solution before configuration tungsten titanium oxide
Using titanium tetrachloride (TiCl4) and tungstates (Na2WO4·2H2O) originated as tungsten titanium oxide metallic element.With
Ethanol is solvent, is Na according to mol ratio2WO4·2H2O:TiCl4:Ethanol=1:2:100 prepare solution, then by solution lucifuge
Stirring 2h is allowed to well mixed under sealing, normal temperature.
(3) tungsten titanium oxide photonic crystal is prepared
By oligomer solution spin coating before tungsten titanium oxide or it is poured into the polystyrene colloid crystal template gap of preparation；So
The horizontal rest 12h in 45 DEG C of thermal station, makes preceding oligomer solution fully react generation tungsten titanium oxide afterwards；It is finally putting into tube furnace
In 450 DEG C calcining 2.5h to remove polystyrene colloid crystal template so that prepare forbidden photon band be located at 316nm tungsten titanium
Oxide inverse opal photonic crystal.
Claims (5)
1. one kind enhancing laser desorption is attached with ionizing substrate, it is characterised in that：The substrate is with opal structural
Colloidal crystal is template, and tungsten titanium oxide is preceding aggressiveness, and the tungsten titanium oxide photonic crystal prepared by template duplicating, which is used as, to swash
Photodissociation is adsorbed and ionization substrate.
2. enhancing laser desorption according to claim 1 is attached with ionizing substrate, it is characterised in that：The photonic crystal tool
There is counter opal structure, the absorption of its forbidden band and tungsten titanium oxide, optical maser wavelength are coupled；By adjusting the section photonic crystal
Lattice size, makes the forbidden band edge of tungsten titanium oxide photonic crystal be in the position of parsing optical maser wavelength, increase laser and substrate
Interaction, so as to strengthen, laser desorption is attached and Ionization Efficiency.
3. a kind of attached preparation method with ionization substrate of enhancing laser desorption as claimed in claim 1 or 2, its feature exists
In：The preparation method comprises the following steps：
1) preparation of the colloidal crystal template of opal structural：
Polymeric colloid nano-particle solution is configured, conductive substrate is immersed in solution, passes through the self assembly of colloidal nanoparticles
Colloidal crystal template is prepared, the glass transition temperature being then heated to close to polymer makes colloidal nanoparticles reinforcement by connection；
2) preparation of tungsten titanium oxide photonic crystal：
Oligomer solution before tungsten titanium oxide is filled into step 1) made from colloidal crystal template gap in, then sample is entered
Row heating, after oxidation drying, tungsten titanium oxide is filled in the gap of colloidal crystal template；Finally sample is forged
Burn, remove colloidal crystal template, prepare the tungsten titanium oxide photonic crystal with counter opal structure as enhancing laser
Desorption and ionization substrate.
4. the attached preparation method with ionization substrate of enhancing laser desorption according to claim 3, it is characterised in that：Step
1) polymeric colloid nano-particle described in is polystyrene PS, polymetylmethacrylate, polyacrylonitrile (PAN) or its
The monodisperse nanoparticle of copolymer.
5. the attached preparation method with ionization substrate of enhancing laser desorption according to claim 3, it is characterised in that：Step
2) oligomer solution is with tetra-n-butyl titanate TBOT, titanium tetrachloride TiCl before the tungsten titanium oxide described in4, titanium sulfate TiSO4、
Tungsten chloride WCl6, the mixed solution that tungstates or tungsten phosphate are solute.
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Citations (7)
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|---|---|---|---|---|
| DE112004000253T5 (en) * | 2003-02-10 | 2006-02-02 | Waters Investments Ltd., New Castle | Adsorption, detection and identification of ambient air components with desorption / ionization on silicon and mass spectrometry (DIOS-MS) |
| US20060097143A1 (en) * | 2004-10-25 | 2006-05-11 | Bruker Daltonik Gmbh | Protein profiles with atmospheric pressure ionization |
| CN1872661A (en) * | 2006-04-29 | 2006-12-06 | 东南大学 | Ultra hydrophobic surface material with multilevel structure, and preparation method |
| CN101587038A (en) * | 2009-06-26 | 2009-11-25 | 中国科学院合肥物质科学研究院 | Liquid sample desorption ionization method under atmospheric pressure |
| CN102426187A (en) * | 2011-11-21 | 2012-04-25 | 程金生 | Graphene matrix and application of graphene matrix in matrix-assisted laser desorption/ionization-time of flight-mass spectrometry detection |
| 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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2017
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| DE112004000253T5 (en) * | 2003-02-10 | 2006-02-02 | Waters Investments Ltd., New Castle | Adsorption, detection and identification of ambient air components with desorption / ionization on silicon and mass spectrometry (DIOS-MS) |
| US20060097143A1 (en) * | 2004-10-25 | 2006-05-11 | Bruker Daltonik Gmbh | Protein profiles with atmospheric pressure ionization |
| CN1872661A (en) * | 2006-04-29 | 2006-12-06 | 东南大学 | Ultra hydrophobic surface material with multilevel structure, and preparation method |
| CN101587038A (en) * | 2009-06-26 | 2009-11-25 | 中国科学院合肥物质科学研究院 | Liquid sample desorption ionization method under atmospheric pressure |
| CN101587038B (en) * | 2009-06-26 | 2011-07-20 | 中国科学院合肥物质科学研究院 | Liquid sample desorption ionization method under atmospheric pressure |
| 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 |
| CN102435643A (en) * | 2011-09-15 | 2012-05-02 | 东南大学 | Inverse opal colloidal crystal gas sensor array and preparation method thereof |
| CN102426187A (en) * | 2011-11-21 | 2012-04-25 | 程金生 | Graphene matrix and application of graphene matrix in matrix-assisted laser desorption/ionization-time of flight-mass spectrometry detection |
Non-Patent Citations (1)
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| HONGYU ZHEN.ETAL: "A surfactant-free co-assembly route to fabricate 2D TiO2–WO3 composite inverse opal films for photochromic applications", 《NEW JOURNAL OF CHEMISTRY》 * |
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