CN202339901U - High voltage assisted laser desorption ionization mass spectrometric analysis ion source - Google Patents

High voltage assisted laser desorption ionization mass spectrometric analysis ion source Download PDF

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Publication number
CN202339901U
CN202339901U CN2011204989217U CN201120498921U CN202339901U CN 202339901 U CN202339901 U CN 202339901U CN 2011204989217 U CN2011204989217 U CN 2011204989217U CN 201120498921 U CN201120498921 U CN 201120498921U CN 202339901 U CN202339901 U CN 202339901U
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China
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temperature control
ion source
laser desorption
desorption ionization
control plate
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Expired - Fee Related
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CN2011204989217U
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Chinese (zh)
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张成森
罗海
任昕昕
刘佳
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Peking University
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Peking University
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Abstract

The utility model discloses a high voltage assisted laser desorption ionization mass spectrometric analysis ion source, which comprises a laser, a support, a temperature control plate, a high-voltage power supply and sample surfaces with at least one surface conducting, wherein the temperature control plate is horizontally fixed on the support, the sample surfaces are flatwise placed on the temperature control plate and insulated from the temperature control plate, the high-voltage power supply is electrically connected with the sample surfaces, and the laser is located above the sample surfaces. The high voltage assisted laser desorption ionization mass spectrometric analysis ion source is easy, fast and convenient to operate, can obtain good sample signals in positive ion analysis mode and negative ion analysis mode, and can continuously analyze a plurality of samples; and can further inspect signal responses of the samples at different temperatures, obtain thermodynamic data and dynamic data of reactions and the like through temperature control on the sample surfaces.

Description

A kind of high pressure assisted laser desorption ionization massspectrum is analyzed ion source
Technical field
The utility model relates to chemical analysis field, relates in particular to a kind of high pressure assisted laser desorption ionization massspectrum and analyzes ion source.
Background technology
Ion source is one of mass spectrometric core component, and its effect is the ion that sample is transformed into gas phase.At present, common mass ion source mainly contains: electron impact ionization source (EI), chemical ionization source (CI), fast atom bombardment source (FAB), electron spray ionisation source (ESI), APCI source (APCI), substance assistant laser desorpted ionized source (MALDI) etc.These ionogenic ionization mechanisms are different, are applicable to the compound that ionization is dissimilar respectively, obtain the molecular ion and the fragment ion thereof of respective compound.These ion sources need use under vacuum condition mostly or before mensuration, need loaded down with trivial details preprocessing process, can not be under the original state of sample to its carry out continuously, real-time, high throughput analysis.In recent years; Having occurred with desorption electrospray ionization (DESI) and real time direct analysis (DART) technology is the multiple novel normal pressure open type ion source of representative; They combine the normal pressure desorption technology of sample with its ioning method; Thereby do not need the sample pretreatment of any (or seldom), just can carry out direct rapid analysis sample.
In various novel normal pressure open type ion sources, attach the ion source of technology based on laser desorption and pay close attention to because of its unique advantage has received widely.Laser can instantaneously provide higher energy to sample surfaces on the one hand, helps the desorption of macromolecular substances such as protein, DNA; Laser has higher spatial resolution on the other hand, is suitable for the imaging analysis of material or biological tissue.
These comprise based on the normal pressure open type ion source that laser desorption attaches technology: the electron spray assisted laser desorption attaches ionization (ELDI); Laser lift-off electro-spray ionization (LAESI), substance assistant laser desorpted attach electro-spray ionization (MALDESI) and laser desorption and attach spraying back ionization (LDSPI) etc.Their common feature is the lagging ionization technology that can electron spray (ESI) ioning method be attached the gas phase sample of generation as laser desorption, therefore has similar working principle.With LDSPI is example: laser radiation places the solid-state or liquid sample on sample target surface; Make the sample molecule desorption come out to get into gas phase; And merge mutually with charged spray droplet in electron spray zone, after obtain gaseous ion with one or more electric charges with the similar desolvation process of ESI.LDSPI can obtain ionization effect preferably under the cation analytical model; But under the anion analytical model, be difficult to obtain good sample ions signal; This is because the normally used spraying solvent of LDSPI (methanol or acetonitrile/water) is difficult to the stable spraying of formation under the anion analytical model, causes that Ionization Efficiency is lower thereafter.
People such as Muddiman once carried out improvement to their MALDESI ion source; They are Ionized electron spray afterwards; But voltage directly is added on the metal surface of carrying sample; Promptly on the substance assistant laser desorpted sample surfaces that attaches ioning method, increase high voltage, made the Ionization Efficiency of sample make moderate progress.But this method needs in sample, to sneak into matrix, has not only increased the complexity of analytic process, has also destroyed original state of sample simultaneously, and the existence of matrix has limited this The Application of Technology easily to the analysis generation interference of micromolecular compound.
In addition, the serviceability temperature control system not only can cause reaction, the conditioned reaction speed of sample through heating in novel normal pressure open type ion source, and can be to optionally ionization of sample.For example, people such as Nilles through the temperature of Control work gas, have realized containing the separation and the detection of mixture of three kinds of molecules of identical nominal molecular weight in the real time direct analytical technology.Yet, in the ionogenic report of various normal pressure open types that attaches based on laser desorption, also do not see with the utility model in the application of similar temperature control equipment.
The utility model content
The technical problem that the utility model solves is to provide a kind of and need add matrix, analyzes easy, ion source fast.
In order to overcome the above problems; The utility model provides a kind of high pressure assisted laser desorption ionization massspectrum to analyze ion source; Comprise the sample surfaces of laser, support, temperature control plate, high voltage source and at least one surface conductance, the temperature control plate level is fixed on the support, and sample surfaces lies on the temperature control plate and with the temperature control plate and insulate; High voltage source is electrically connected with sample surfaces, and laser is positioned at the sample surfaces top.
Since when being employed in laser desorption and attaching on the metal sample surface on-load voltage, guaranteed under the positive and negative ion analytical model, all can obtain sample signal intensity and signal to noise ratio preferably; Owing to matrix need in determinand, do not added or carry out other sample pretreatments, simplified operation again, the possibility of having avoided matrix to disturb simultaneously for sample.
Description of drawings
When combining accompanying drawing to consider; Through with reference to following detailed, can more completely understand the utility model better and learn wherein many attendant advantages easily, accompanying drawing described herein is used to provide the further understanding to the utility model; Constitute the part of the utility model; Illustrative examples of the utility model and explanation thereof are used to explain the utility model, do not constitute the improper qualification to the utility model, wherein:
Fig. 1 is that the utility model high pressure assisted laser desorption ionization massspectrum is analyzed ionogenic structural representation Fig. 1;
Fig. 2 is that the utility model high pressure assisted laser desorption ionization massspectrum is analyzed ionogenic structural representation Fig. 2;
Fig. 3 is that the utility model high pressure assisted laser desorption ionization massspectrum is analyzed ionogenic structural representation Fig. 3;
Fig. 4 is the structural representation of the utility model support;
Fig. 5 is the structural representation of the utility model conductive metal sheet;
Fig. 6 is the structural representation of the utility model fixed part.
Embodiment
Following embodiment with reference to Fig. 1-6 pair the utility model describes.
For make above-mentioned purpose, feature and advantage can be more obviously understandable, below in conjunction with accompanying drawing and embodiment the utility model done further detailed explanation.
The utility model provides a kind of high pressure assisted laser desorption ionization (HALDI, High Voltage Assisted Laser Desorption Ionization) mass spectral analysis ion source.In the HALDI mass spectral analysis; Fluid sample directly is added on the metal sample surface; Dependence loads on the external voltage of sample surfaces and is charged; Under laser radiation, go out tiny charged drop, obtain sample ions, and under effect of electric field, get into the mass spectrum injection port with one or more electric charges through the desolvation process from the sample surfaces desorption.Though; The sample ions process of HALDI and the ionization process of LDSPI have similarity; Under the cation analytical model, all can produce sample ions signal preferably, still visibly different with LDSPI is that HALDI also can obtain stable ion signal under the anion analytical model; And need not add matrix with improved MALDESI compared with techniques, analyze easy, quick.In addition,, can also investigate the signal response of sample under different temperatures through the sample surfaces temperature control, and the thermodynamics and kinetics data of acquisition reaction etc.On the temperature control plate, place sample surfaces a plurality of and the external voltage conducting, can realize the continuous analysis of a plurality of samples through the control motorized precision translation stage.
Embodiment
High pressure assisted laser desorption ionization massspectrum that the utility model provides is analyzed ion source structure shown in Fig. 1-3, comprises 1, support, and 2, conductive metal sheet, 3, the temperature control plate, 4, fixed part, 5, sample surfaces, laser.Its medium-height trestle 1 can be fixedly connected with the D translation platform, with the package unit support fixation.Conductive metal sheet 2 is fixed through the metal screw with support 1, and external voltage can be transmitted on the conductive metal sheet 2 through the metal screw.Temperature control plate 3 can be buy or homemade electric hot plate, electric heating piece or cooling piece etc.Sample surfaces 5 is coated with the other materials thin slice of metal level for sheet metal or surface.Fixed part 4 can be installed in support 1 lower end and vertically be slidingly connected with support 1.The laser emitted laser is a pulse laser, is radiated on the sample of sample surfaces 5 carryings.
Support 1 is processed into like phenolic plastics etc. by the insulation heat proof material, and its left surface has screwed hole, can be fixedly connected with the D translation platform and all member supporting are fixed, maintenance sample surfaces 5 horizontal positioned in the time of fixedly.There is the horizontal groove that can embed conductive metal sheet 2 upper end of support 1, and there is screwed hole the top of horizontal groove, can conductive metal sheet 2 be fixed on the support 1 through screw.The lower end of support 1 is useful on the rectangle groove that installs and fixes parts 4, and mounted fixed part 4 is up-down adjustment vertically.Screwed hole is arranged in the middle of the lower end of support 1, can regulate the position of fixed part 4 through screw at vertical direction.
Conductive metal sheet 2 can be processed by gold, silver or other conducting metals or alloy, also can be processed by the other materials that the surface is coated with one deck conducting metal or alloy.The left end of conductive metal sheet 2 can embed in the groove of support 1 and through the metal screw and be fixed.External voltage is generally ± and 3.5kV is to ± 5.5kV, can be transmitted on the conductive metal sheet 2 through the metal screw.The right-hand member of conductive metal sheet 2 can further pass to one or more sample surfaces 5 with voltage through conductive tape, electric wire, metal spring leaf or other electric conducting materials.
Temperature control plate 3 can be heater or a refrigerating plant that buy or homemade plate (sheet) shape, like electric heating piece, ceramic far-infrared heating film or semiconductor chilling plate etc.One end of temperature control plate 3 is clipped between support 1 and the fixed part 4, and the gap between adjusting fixed part 4 and the support 1 is the temperature control plate 3 of different-thickness fixedly.Size according to temperature control plate 3 is different, and its upper surface can be placed one or more sample surfaces 5.Can accurately control the surface temperature of temperature control plate 3 through thermostat,, need the external temperature element of surface overlap joint above that if the temperature control plate of selecting for use 3 does not have built-in temperature element.If temperature control plate 3 outer surfaces of selecting for use are metal, need at its surperficial applying insulating heat-conduction material, like the thermal conductive silicon rubber cushion, to avoid the external voltage influence possible to temperature control plate 3.Type according to the temperature control plate of selecting for use 3 is different, and temperature controlling range is different, should be taken into account the influence that selected temperature possibly brought during use, should carry out corresponding safe precaution measure when serviceability temperature is higher.
Fixed part 4 is by the insulation heat proof material; Like phenolic plastics etc.; Be processed into; The lower end is passed the groove of support 1 and vertically is slidingly connected with support 1, can regulate the position of fixed part 4 through regulating the middle screw in support 1 lower end, and fix the temperature control plate 3 between fixed part 4 and the support 1.
Sample surfaces 5 is generally the gold-plated silicon chip of upper surface for sheet metal or the surperficial other materials thin slice that is coated with metal level.Sample surfaces 5 lies on the temperature control plate 3, the sample that can the heat transferred of temperature control plate 3 be carried.The upper surface of sample surfaces 5 can pass through conductive tape, electric wire, metal spring leaf or other electric conducting materials and conducting metal oblique cut grafting, thereby external voltage is passed to the sample that carries on the sample surfaces 5.Sample to be analyzed directly is added on the sample surfaces 5 of ultrasonic cleaning.A plurality of sample surfaces 5 are placed on the temperature control plate 3 in certain sequence, and conduct with conductive metal sheet 2 respectively, set the motorized precision translation stage program and can realize various article automatic continuous analysis.
Laser for buy or the pulse laser built of design voluntarily.The wavelength of the pulse laser that laser is launched is 1064nm.The frequency adjustable of pulse laser is generally 20Hz.The energy of pulse laser is adjustable, is generally 1.1mJ/pulse.When fluid sample and external voltage conducting, the pulsed laser irradiation that laser is launched is on the fluid sample that sample surfaces 5 carries, and desorption goes out tiny charged drop, perhaps directly goes out sample ions from the sample surfaces desorption.
The rapidoprint of support 1 and fixed part 4 is guaranteeing under the firm prerequisite it can is phenolic plastics, pottery, also can make other insulation heat proof materials.
Conductive metal sheet 2 can be designed to difformity, and its material can be different types of conducting metal, also can not use conductive metal sheet 2 directly external voltage to be carried on the sample surfaces 5.
Screw through regulating support 1 lower end can be fixed on temperature control plate 3 between support 1 and the fixed part 4, also can adopt fixedly temperature control plate 3 of other modes.
Temperature control plate 3 can be tabular, sheet, strip or other shapes.
Sample surfaces 5 can be square, rectangle, circle or other shapes, and its size is decided according to the sample size that loads.
Sample surfaces 5 is through conductive tape, electric wire, metal spring leaf or other electric conducting materials and conducting metal oblique cut grafting, thus with the external voltage conducting.Also can adopt other modes that voltage is loaded on the sample surfaces 5.
Between support 1 and the fixed part 4 certain adjustable range is arranged, when the size of temperature control plate 3 exceeds existing adjustable range, but support 1 and fixed part 4 that processing dimension matches.
Fixed part 4 lower ends embed the groove of support 1 and are slidingly connected with support 1, and the position of regulating fixed part 4 through support 1 lower end screw is temperature control plate 3 fixedly, also can adopt fixedly temperature control plate 3 of other modes.
High pressure assisted laser desorption ionization massspectrum is analyzed ion source, direct analyzing liquid sample, and the solvent of liquid sample can be methanol, acetonitrile/water etc.During laser radiation, should be taken into account sample solvent contingent reaction even burning under laser radiation, and carry out corresponding safety prevention measure.When heat on the surface, should be taken into account the at high temperature contingent variation of sample and solvent thereof and carry out corresponding safety prevention measure.
When temperature control plate 3 outer surfaces are electric conducting material, should coat one deck heat-conducting insulation material, avoid applied voltage to damage the electric elements in the temperature control plate 3., ion source should avoid directly contacting the parts of on-load voltage when working.
Should wear lasering protective eyeglass when opening laser.
The optical maser wavelength that laser is selected for use can be at infrared, visible or ultraviolet band.
All screw threads, screw and nut in the present embodiment also can be English system guaranteeing both can be metric system under the prerequisite that matches each other.
The ionogenic package unit of the above mass spectrum high pressure assisted laser desorption can place on the adjustable translation stage of three-dimensional.
Ion source analytic sample method is following:
Mounting bracket 1, conductive metal sheet 2, temperature control plate 3, fixed part 4 and sample surfaces 5.Sample is directly placed on the sample surfaces 5; Through the temperature of external thermostat adjusting temperature control plate 3, thereby control is placed on the temperature of the sample on the sample surfaces 5; External voltage is transmitted on the conductive metal sheet 2 through the metal screw, and further is delivered to sample surfaces 5 through conductive tape (or a metal spring leaf), and external voltage is loaded into and makes sample charged on the sample the most at last; Sample goes out tiny charged drop from the sample surfaces desorption under laser radiation, obtains the sample ions with one or more electric charges through the desolvation process, and under effect of electric field, gets into the mass spectrum injection port.Though; The sample ions process of HALDI and the process of LDSPI have similarity; Under the cation analytical model, all can produce sample ions signal preferably, still visibly different with LDSPI is that HALDI also can obtain stable ion signal under the anion analytical model; And need not add matrix with improved MALDESI compared with techniques, analyze easy, quick.In addition,, can also investigate the signal response of sample under different temperatures through the sample surfaces temperature control, and the thermodynamics and kinetics data of acquisition reaction etc.On the temperature control plate, place sample surfaces a plurality of and the external voltage conducting, can realize the continuous analysis of a plurality of samples through the control motorized precision translation stage.
As stated, the embodiment of the utility model has been carried out explanation at length, but as long as break away from the inventive point and the effect of the utility model in fact a lot of distortion can not arranged, this will be readily apparent to persons skilled in the art.Therefore, such variation also all is included within the protection range of the utility model.

Claims (10)

1. a high pressure assisted laser desorption ionization massspectrum is analyzed ion source; It is characterized in that; Comprise the sample surfaces of laser, support, temperature control plate, high voltage source and at least one surface conductance, the temperature control plate level is fixed on the support, and sample surfaces lies on the temperature control plate and with the temperature control plate and insulate; High voltage source is electrically connected with sample surfaces, and laser is positioned at the sample surfaces top.
2. a kind of according to claim 1 high pressure assisted laser desorption ionization massspectrum is analyzed ion source, and it is characterized in that: said laser is a pulse laser.
3. a kind of according to claim 1 high pressure assisted laser desorption ionization massspectrum is analyzed ion source, and it is characterized in that: said support is processed by the High-Voltage Insulation heat proof material.
4. analyze ion source like the said a kind of high pressure assisted laser desorption ionization massspectrum of claim 3, it is characterized in that: said High-Voltage Insulation heat proof material is phenolic plastics.
5. a kind of according to claim 1 high pressure assisted laser desorption ionization massspectrum is analyzed ion source, and it is characterized in that: said sample surfaces is the gold-plated silicon chip of upper surface.
6. a kind of according to claim 1 high pressure assisted laser desorption ionization massspectrum is analyzed ion source, and it is characterized in that: also comprise the electric three-dimensional translation stage, support is fixed on the electric three-dimensional translation stage.
7. analyze ion source like the said a kind of high pressure assisted laser desorption ionization massspectrum of one of claim 1 to 6; It is characterized in that: also comprise conductive metal sheet; Conductive metal sheet is fixed on the support, and high voltage source is electrically connected with conductive metal sheet earlier, and conductive metal sheet is electrically connected with sample surfaces again.
8. analyze ion source like the said a kind of high pressure assisted laser desorption ionization massspectrum of claim 7, it is characterized in that: said conductive metal sheet is processed by the other materials that gold, silver or alloy or surface are coated with metal level or alloy-layer.
9. analyze ion source like the said a kind of high pressure assisted laser desorption ionization massspectrum of one of claim 1 to 6; It is characterized in that: also comprise the fixed part that an insulation heat proof material is processed; The temperature control plate holder is fixed between support and fixed part and by fixed part, and fixed part is installed in the support lower end and vertically is slidingly connected with support.
10. analyze ion source like the said a kind of high pressure assisted laser desorption ionization massspectrum of one of claim 1 to 6, it is characterized in that: heater or refrigerating plant that said temperature control plate is plate or sheet.
CN2011204989217U 2011-12-02 2011-12-02 High voltage assisted laser desorption ionization mass spectrometric analysis ion source Expired - Fee Related CN202339901U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104616961A (en) * 2015-02-16 2015-05-13 江苏天瑞仪器股份有限公司 Ion source three-dimensional linkage mechanism
CN111684271A (en) * 2018-02-09 2020-09-18 浜松光子学株式会社 Sample support and method for producing sample support

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104616961A (en) * 2015-02-16 2015-05-13 江苏天瑞仪器股份有限公司 Ion source three-dimensional linkage mechanism
CN111684271A (en) * 2018-02-09 2020-09-18 浜松光子学株式会社 Sample support and method for producing sample support
US11948787B2 (en) 2018-02-09 2024-04-02 Hamamatsu Photonics K.K. Sample support, and manufacturing method of sample support

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Granted publication date: 20120718

Termination date: 20141202

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