CN101458226B - Neutral desorption apparatus and neutral desorption extractive electrospray lonization mass spectrometry method - Google Patents
Neutral desorption apparatus and neutral desorption extractive electrospray lonization mass spectrometry method Download PDFInfo
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- CN101458226B CN101458226B CN 200810224770 CN200810224770A CN101458226B CN 101458226 B CN101458226 B CN 101458226B CN 200810224770 CN200810224770 CN 200810224770 CN 200810224770 A CN200810224770 A CN 200810224770A CN 101458226 B CN101458226 B CN 101458226B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0459—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples
- H01J49/0463—Desorption by laser or particle beam, followed by ionisation as a separate step
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/145—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using chemical ionisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
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Abstract
The invention discloses a neutral desorption device and a neutral desorption extraction electrospray ionization mass spectrographic (ND-EESI-MS) analysis method. The neutral desorption device mainly comprises an air inlet tube and a sample tube which are diagonally arranged, and are fixed in a frame, an outlet of the air inlet tube is adjacent to an inlet of the sample tube and stretches out of the frame, wherein, an inlet of the air inlet tube is communicated with an air pump which conveys neutral gas to the air inlet tube, an outlet of the sample tube is communicated with a sample feed tube of an EESI, the outer layer of the air inlet tube is equipped with a heating jacket, and can be further equipped with a liquid charging tube, and an outlet of the liquid charging tube is adjacent to the outlet of the air inlet tube and the inlet of the sample tube. The ND-EESI-MS analysis method is that the neutral desorption device collects samples and introduces sample flow into an extraction electrospray ionization source through the outlet of the sample tube for mass spectrographic analysis. The device and the method are especially applicable to rapid and real-time analysis of complex biological samples, food, medicines, environmental samples and the like, and also can perform in situ in vivo analysis on organisms.
Description
Technical field
The present invention relates to the analytical chemistry field, be particularly related in the mass spectrometric analysis method and the matching used sample drawing-in system of mass spectrometer ion source, be specially the neutral desorption apparatus that high-voltage electric field or charged particle etc. and detected object are isolated from time and space, and the technology of using this neutrality desorption apparatus and electron spray extraction ionization source sample to be carried out the harmless mass spectrophotometry of original position.
Background technology
The development of modern social economy and science and technology has proposed new challenge to analytical chemistry.The exploitation of original position, real-time, online, non-destruction, high flux, high sensitivity, high selectivity, low-loss analysis test method is the focus of modern analysis science and the target of pursuit.In numerous analysis test methods, the mass-spectrometry method is considered to a kind of universality method that possesses simultaneously high specific and high sensitivity and be widely applied.Therefore, the mass-spectrometry method of original position, real-time, online, non-destruction, high flux, low-loss is one of target of pursuing of people always, is an important trend of mass-spectrometric technique development.
Mass spectrometer itself generally partly is comprised of sample drawing-in system, ion gun, ion-optic system, mass analyzer, detecting device, Data Acquisition and Conversion System (DACS), vacuum system etc.Mass-spectrometry and mass spectrometer developing history show, new ionogenic development and exploitation have the meaning of particular importance.The mass spectrum scholar generally believes no matter be to organic mass spectrometry or inorganic mass spectrum, the heart of mass spectrometer all is ionization sources.American scientist John Fen En (John B.Fenn) exactly because etc. obtained Nobel chemistry Prize in 2002 having made major contribution aspect development electron spray ionisation (ESI) this soft ionization source.Yet the mass spectral:mass spectrographic ionization source of development and exploitation can carry out ionization after all requiring sample is converted into specific conformation in last 100 years.Therefore, in these conventional ionization sources, before being measured, sample must carry out the pre-service of sample.In fact, from sample introduction to obtaining data, the needed time of mass spectroscopy measuring process itself is no more than the several seconds, but the time of sample pretreatment then may reach a few hours even a couple of days.In some important application scenarios, on-the-spot on-line determination such as the pharmaceuticals industry Chinese medicine tablet, the monitoring of trace explosive on the luggage, the Quality Identification of food, commodity inspection in the foreign trade, live body pharmacokinetics research etc., all wishing can be in the situation that need not sample pretreatment carry out nondestructive Fast Measurement to sample.
Enter 21 century, people have carried out bold exploration for the mass spectrum express-analysis of complicated substrate sample, have obtained important progress.2004, professor Cooks of Purdue university waits and has delivered first piece of article about electron spray desorption ionization (DESI) at Science, in the situation that need not carry out sample pretreatment, successfully obtained the mass spectrum of trace materials on the different surfaces, for realize need not sample pretreatment mass spectrometric analysis method opened a window.The DESI technology has caused ardent repercussion immediately in the world, and many groups have begun the research of this respect immediately in the world.After 1 year, what Japanese scholars was developed is published on the U.S. Anal.Chem. magazine with similar another novel ionization source (DART) technology of DESI, and has obtained Pittsburgh's gold medal in same year.Studies show that, DESI and DART are the important tool of surface analysis, in a lot of occasions or even preferred option.Autumn in 2005, DESI and DART technology are all successfully introduced to the market in the North America, and single ion gun is not less than 100,000 U.S. dollars in the market price of the U.S..Up to the present, these two technology still prohibit selling to China.
For the domestic situation that is difficult to buy relevant device, and consider some deficiency in DESI and DART source, the inventor has developed electron spray extraction ionization source (EESI) since 2005, the directly undiluted people's urine of mensuration of sample pretreatment can need not, the complex samples such as milk (H.W.Chen, A.Venter, and R.G.Cooks, Extractiveelectrospray ionization for direct analysis of undiluted urine, milk and other complexmixtures without sample preparation, Chem.Commun, 2006,2042-2044) with fast detecting breathing gas non-volatile compounds (H.Chen, A.Wortmann, W.H.Zhang, R.Zenobi.Rapid in vivofingerprinting of nonvolatile compounds in breath by extractive electrospray ionizationquadrupole time-of-flight mass spectrometry.Angew.Chem.Int.Ed.2007,46,580-583; H.Chen, S.Yang, A.Wortmann, R.Zenobi.Neutral Desorption Sampling of LivingObjects for Rapid Analysis by Extractive Electrospray Ionization Mass Spectrometry, Angew.Chem.Int.Ed.2007,119,7735-7738), have good development prospect aspect the quick mass spectrophotometry of complicated substrate material.The principle of EESI and structure such as Fig. 8, neutral sample (such as people's breath) is introduced from another sample feeding pipe perpendicular to the ESI ionization source, human body not near the high-voltage electrostatic field of ESI with contact the organic extractants such as methyl alcohol, realized separating of sample and electric field, avoided electric shock and be subjected to the danger of poisonous reagent contamination, damage; EESI also need not sample pretreatment, and can carry out directly fast real-time online mass spectroscopy to the various difficult volatilizations such as the not measurable gas of DESI, gasoloid, liquid, colloid, full-bodied environmental sample; And since sample feeding pipe perpendicular to mass spectrometer sample introduction cone mouth, even the environmental sample of complicated substrate also is difficult for plug ion transfer tube or pollutant's spectrometer, direct express-analysis such as urine sample, continuous sample introduction a few hours can not cause the mass signal total ion current to descend yet, and therefore are particularly suitable for the pretreated direct mass spectrophotometry of n.s. of complicated body.The early-stage Study achievement of technique is subject to the extensive concern of international several media at Chem.Commun. after Angew.Chem.Int.Ed. delivers, obtain the people's such as ESI inventor John Fen En, DESI inventor R.G.Cooks high evaluation.Yet in using, also there is shortcoming in simple EESI, and exactly owing to there not being the surface desorption device, it can not be used for directly measuring the material of solid surface, therefore can not carry out direct on-line analysis to live body surface complex sample.
Summary of the invention
The object of the present invention is to provide and a kind ofly can extract the matching used neutral desorption apparatus of ionization source with electron spray, under the prerequisite that high-voltage electric field or charged particle etc. and detected object are isolated from time and space, realize the harmless real-time online mass spectrophotometry of the original position of solid sample.Thereby the range of application of expansion EESI.
Neutral desorption apparatus of the present invention mainly comprises a tiltedly draft tube and the sample efferent duct to placing, and be fixed in the framework, and the entrance of the outlet of draft tube and sample efferent duct is close and stretch out outside the framework.
Wherein, draft tube and sample efferent duct are kapillary.
Wherein, the entrance of described draft tube is communicated with to the air pump of wherein carrying neutral gas, and the outlet of sample efferent duct is communicated with the sample feeding pipe of EESI.
Described draft tube and sample efferent duct are 45～150 ° of angles.
In the above neutral desorption apparatus, the skin of described draft tube can also be provided with heating jacket.
In the above neutral desorption apparatus, can establish in addition a liquid-feeding tube, the outlet of liquid-feeding tube outlet and draft tube and the entrance of sample efferent duct are close.
Another purpose of the present invention is to provide a kind of neutral stripping gas phase chromatography or neutral desorb gas chromatography-mass spectrography analytic approach.The method is used above neutral desorption apparatus collected specimens, by the outlet of sample efferent duct sample flow is introduced gas chromatograph.
Concrete, be neutral desorption extractive electrospray lonization mass spectrometry method.The method may further comprise the steps:
Step 1: the sample hose outlet of the above neutral desorption apparatus is linked to each other with the sample feeding pipe of electron spray extraction ionization source, and electron spray extraction ionization source is connected with mass spectrometer;
Step 2: the sample hose entrance of neutral desorption apparatus is aimed at solid sample to be checked surface, distance 5～12mm;
Step 3: to the draft tube input neutral gas of neutral desorption apparatus, gas flow rate is 15～40psi;
Step 4: impose 3～6KV high pressure to electron spray extraction ionization source simultaneously and make sample ionization;
Step 5: open the mass spectrometer scanning system, obtain testing result.
In the described mass spectrometric analysis method, neutral gas described in the step 3 is for being selected from the innocuous gas such as water vapour, nitrogen, air.
Adopt above design, neutral reagent (such as air, nitrogen, water vapor etc.) is creatively used in the neutral desorb of the present invention, and molecular beam directly clashes into the determinand sample surfaces, thereby the material that will be adsorbed on this sample surfaces desorbs.Owing to being subject to the impact of fluid, the determinand that desorbs is along with air-flow is brought in the EESI ion gun, thus the generation ionization, the ion of generation determinand.Owing to high-voltage electric field or charged particle etc. and detected object were isolated from time and space, so the testing sample surface can not be subject to the interference of external electric field.Neutral desorption apparatus of the present invention, compact conformation designs ingeniously, easy to use, can carry out sample collection for various test sample flexibly; The neutral desorption extractive electrospray lonization mass spectrometry method of the present invention not only has advantages of high sensitivity and high specific, and does not change the physiological and pathological state of testing sample (such as biosome), also sample is not polluted or damages.Therefore, the method is particularly suitable for biological sample, food, medicine, environmental sample to complexity etc. and analyzes real-time, especially can carry out the original position in-vivo analysis to biosome.
The neutral desorption apparatus of the present invention can also as sample collection and the drawing-in system of gas chromatography or gas chromatograph-mass spectrometer, greatly to simplify the sample pretreatment process of gas chromatography, be realized the original position express-analysis in addition.
Description of drawings
Fig. 1 is the neutral desorption apparatus principle schematic of the present invention;
Fig. 2 is a kind of neutral desorption apparatus graph structure signal of the present invention.
But Fig. 3 be the present invention's solubilizer neutral desorption apparatus formation and principle of work schematic diagram;
Fig. 4 is that the neutral desorption electrospray extraction of the present invention MALDI-MS is measured the TNT on human body skin surface and the MS spectrogram of RDX;
Fig. 4 A is the secondary MS spectrogram of TNT among Fig. 4;
Fig. 4 B is the secondary MS spectrogram of RDX among Fig. 4;
Fig. 5 is ND-EESI-MS principal component analysis (PCA) (PCA) result's of three kinds of differing maturity strawberries three-dimensional plot;
Fig. 6 is the mass spectrogram that neutral desorb extraction electrospray ionization mass spectrum (ND-EESI-MS) is measured the different freshness flesh of fish: a: do not expose the freezing flesh of fish at room temperature; B: expose the freezing flesh of fish after at room temperature 1 day; C: expose the freezing flesh of fish after at room temperature 2 days;
Fig. 7 A is that neutral desorption electrospray extraction MALDI-MS is measured the caffeine (m/z195) on human body skin surface and the one-level mass spectrogram of nicotine (m/z163);
Fig. 7 B is the second order ms figure of caffeine m/z195;
Fig. 8 is EESI source primary structure and fundamental diagram.
Embodiment
Describe formation and the principle of work of the neutral desorption apparatus of the present invention in detail below in conjunction with accompanying drawing.
Fig. 1, Fig. 2 show basic comprising and the principle of work of the neutral desorption apparatus of the present invention system.In mass spectrophotometry, described neutral desorption apparatus uses as the sample drawing-in system, it mainly comprises a draft tube I and sample efferent duct II, draft tube I and sample efferent duct II are kapillary, the oblique placement of two kapillaries is fixed in the framework 1, the entrance of the outlet of draft tube I and sample efferent duct II near and stretch out outside the framework, be 45～150 ° of angles between draft tube I and the sample efferent duct II, position and angle that two kapillaries are placed can be adjusted by the spring 11 and the bolt 12 that arrange in the framework 1; The entrance of draft tube I is communicated with can be to the air pump of wherein carrying neutral gas, and the outlet of sample efferent duct II is communicated with the sample feeding pipe (not shown) of EESI.
In the collected specimens process, please in conjunction with shown in Figure 1, with the outlet of draft tube I and the entrance solid sample close to be measured surface of sample efferent duct II, molecular beam directly clashes into the determinand sample surfaces with the neutral reagent (such as air, nitrogen, water vapor etc.) that penetrates from draft tube I, thereby the material that will be adsorbed on this sample surfaces desorbs; Because be subject to the impact of fluid, the determinand that desorbs is along with air-flow is brought in the EESI ion gun by sample efferent duct II.Determinand and then in the EESI ion gun ionization occurs, the ion that produces determinand enters mass spectrometer and detects.
For making test substance easier from surface desorption out, heating jacket 13 can be provided with at the skin of draft tube I, referring to shown in Figure 1.
The another kind of embodiment of this neutrality desorption apparatus is referring to shown in Figure 3, on the basis of above-mentioned formation, to add again a liquid-feeding tube III, the outlet of its outlet and draft tube I and the entrance of sample efferent duct II are close, wherein can pass into solvent such as water, methyl alcohol etc., purpose is determinand in the dissolving surface, makes determinand easier from surface desorption out.
Use above-mentioned neutral desorption apparatus, can realize the neutral desorption electrospray of solid sample is extracted MALDI-MS analysis (ND-EESI-MS) in conjunction with electron spray extraction ionization source.The method may further comprise the steps:
Step 1: the sample efferent duct II outlet of the above neutral desorption apparatus is linked to each other with the sample feeding pipe of electron spray extraction ionization source, and electron spray extraction ionization source is connected with mass spectrometer;
Step 2: the sample efferent duct II entrance of neutral desorption apparatus is aimed at solid sample to be checked surface, distance 5～12mm;
Step 3: to the draft tube I input neutral gas of neutral desorption apparatus, gas flow rate is 15～40psi;
Step 4: impose 3～6KV high pressure to electron spray extraction ionization source simultaneously and make sample ionization;
Step 5: open the mass spectrometer scanning system, obtain testing result.
When the neutral desorption apparatus that uses with liquid-feeding tube III, open simultaneously liquid-feeding tube in the step 3 solvent in the liquid-feeding tube is sprayed to sample.
Neutral gas in the draft tube of mentioning in the above method is for being selected from the innocuous gas such as water vapour, nitrogen, air.Solvent in the liquid-feeding tube is for being selected from water, methyl alcohol etc.
Describe application of the present invention in detail below in conjunction with concrete detection example, analyze by neutral desorption electrospray extraction MALDI-MS (ND-EESI-MS), to the degree of ripeness of complicated substrate sample explosive, fruit, the checks such as freshness of vegetables aquatic products have obtained good result.
Detection to complicated substrate sample explosive
In recent years, in the world wide, the terrorist activity that the terrorist utilizes explosive to carry out is and increases progressively trend.At present, countries in the world are increasing to the demand of new use for explosive quality testing survey technology, especially to the original position of trace explosive in the complex sample, directly, fast, sensitivity, high selectivity, online, the demand of Non-Destructive Testing is more urgent.Simultaneously, explosive can enter in the body by respiratory system, digestive system and skin, forms and is important environmental contaminants thereby biosome is produced multiple toxicity (as causing that neurasthenia, blood change mutually etc.).Therefore, the original position fast detecting research of explosive is significant.Conventional detection method can't detect online to non-nitro explosive (such as TATP, HMTD etc.).In adopting the Mass Spectrometer Method method, electron spray ionisation (ESI) and Atmosphere Pressure Chemical Ionization (APCI) (APCI) mass spectrum commonly used also need more loaded down with trivial details sample pretreatment, then could detect with GC-MS and LC-MS.And the explosive that uses the neutral desorb extraction electrospray ionization mass spectrometry of the present invention (ND-EESI-MS) to detect on the different surfaces can be avoided sample pretreatment fully, realizes that real-time online detects.
In the experiment, at first utilize neutral desorb extraction electrospray ionization mass spectrometry (ND-EESI-MS) to seven kinds of explosives (TNT, RDX, HMX, TNB, TATP, HMTD, NG etc., be Powdered standard items) carry out respectively quick mass spectrophotometry, obtain the mass spectrogram of these several explosives; In order to get rid of the false positive of measurement result, and then these explosives have been carried out the series winding mass spectrophotometry obtained the secondary spectrogram.According to the characteristic peak of these secondary spectrograms, the assessment of checking property the repeatability of method, data show that ND-EESI-MS can carry out quick nondestructive to different explosives in need not the sample pretreatment situation and detect.
Utilize again subsequently ND-EESI-MS that the detection of explosive TNT, RDX is carried out on the various surfaces such as the clothing of being infected with explosive, skin.Method is: with the sample 5～8mm place of sample hose entrance on distance clothing or skin of neutral desorption apparatus, open the ND-EESI-MS system, obtain sample detection spectrogram (Fig. 4), show that the ND-EESI-MS system has detected corresponding explosive.Secondary spectrogram Fig. 4 A shows to detect in the thing TNT, and Fig. 4 B shows to detect in the thing RDX.
For routine inspection, can take to use neutral desorption apparatus to detecting the mode of thing (such as clothing or skin) scanning, obtain continuously the detection spectrogram, and contrast with the standard items spectrogram, then can accurately filter out corresponding spectrogram, thereby determined whether explosive, which kind of explosive is arranged and explosive is arranged wherein, this will provide new solution for the fast on-line analyzing method of the anti-terrorism safety checks such as airport, railway station.
The detection of fruit maturity
For most fruits and vegetables, degree of ripeness is the key factor that determines storage time and final quality, and therefore for fruit harvesting aftertreatment and qualitative control, it is particularly important that the detection of degree of ripeness just seems, the demanding sensitivity of analysis that desirable degree of ripeness detects, specificity, high flux, and want to can't harm, nontoxic, pollution-free detection, detection for the degree of ripeness such as fruit, freshness, except organoleptic detection, also have many analytical chemistry methods, but all difficulty satisfies above-mentioned requirements.The present invention with the sample hose entrance of neutral desorption apparatus at distance fruit sample 5～12mm to be measured place, utilize neutral desorb extraction electrospray ionization mass spectrometry (ND-EESI-MS) that the taste that various fruit give out is carried out quick fingerprint map analyzing, utilize the fruit MS finger-print that obtains to carry out the principal component analysis (PCA) (PCA) of multivariate statistical analysis, can distinguish banana, grape and the strawberry in different maturity stages.According to PCA clump figure, assessed to checking property the repeatability of method, data show that EESI-MS can need not carry out the quick nondestructive detection to quality and the degree of ripeness of fruit under the sample pretreatment situation.Fig. 5 is 3 kinds of differing maturity (ripe, unripe, over mature) the ND-EESI-MS spectrogram of strawberry is through principal component analysis (PCA) (PCA) result's three-dimensional plot, therefrom can find out, 1,2,3,4,5, No. 6 is the strawberry that does not have maturation (unripe), 7, the 8,9,10, the 12nd, the strawberry of ripe (ripe), 13, the 14,15,16,17, the 18th, the strawberry of overdone (over mature) illustrates that the identification that ND-EESI-MS analyzes for the Strawberry ripening degree is successfully.
The detection of fish freshness
With the fruit maturity detection type seemingly, at distance flesh of fish sample 3～8mm to be measured place, application ND-EESI-MS can detect fish freshness with the sample hose entrance of neutral desorption apparatus.Fig. 6 has shown the mass spectrogram of the different freshnesss flesh of fish of neutral desorb extraction electrospray ionization mass spectrum (ND-EESI-MS) mensuration, and wherein: a shows the freezing flesh of fish (20 ℃) that does not expose at room temperature; B shows at room temperature (22 ℃) freezing flesh of fish after 1 day of exposure; C shows the freezing flesh of fish that exposes after at room temperature 2 days.Relatively find out between spectrogram, the flesh of fish of different freshnesss has obvious differentiation, (a) spectrogram shows that fresh meat has a small amount of microorganism and invaded among the figure, has detected a small amount of dactylogram peak such as low intensive dimethyl acetamide (m/z 73) and (m/z 122) and (m/z 88); (b) one day the freezing flesh of fish of exposure detects the microbial metabolic products such as histamine (m/z 112) and putrescine (m/z 89); (c) finger-print quantity increases in, detects protonated tyrasamine (m/z 137), and tryptamines (m/z 160) and spermine (m/z 202) etc. show the biogenic amine that has new microbial metabolism material to produce, and are the stale flesh of fish.Show that it is more that impurity substances produces along with open-assembly time passes, freshness is also poorer.
The detection of human body surface caffeine, nicotine
Do not change the physiological and pathological state of testing sample (such as biosome) for neutral desorb sampling, the characteristics that also sample do not polluted or damages, the present invention utilizes neutral desorb extraction electrospray ionization mass spectrum (ND-EESI-MS) can measure the compositions such as the caffeine on human body skin surface, nicotine, detect spectrogram referring to shown in Figure 7, started the new method of the online in-vivo analysis of quick non-destructive.
More than experimental results demonstrate, the present invention utilizes neutral desorb extraction electrospray ionization mass spectrum (ND-EESI-MS) detection technique, owing to using neutral desorption apparatus sampling, high-voltage electric field or charged particle etc. and detected object were isolated from time and space, greatly widened the range of application of mass spectrophotometry, not only kept the advantage that original mass spectrophotometry is sensitive, quick, real-time online detects, also realized the harmless mass spectrophotometry of the original position of sample, and the method can be applied to the online in-vivo analysis of non-destructive; On the other hand, the inventive method is particularly suitable for the detection of solid sample be need not to do any pre-service to detecting thing, broken through technically the bottleneck that original numerous mass spectrophotometry meets with, the present invention is particularly suitable for biological sample, food, medicine, environmental sample to complexity etc. and analyzes real-time, especially can carry out the original position in-vivo analysis to biosome.
Claims (7)
1. neutral desorption apparatus, it is characterized in that, the material that will be adsorbed on sample surfaces with neutral reagent desorbs, mainly comprise a tiltedly draft tube and the sample efferent duct to placing, be fixed in the framework, and the entrance of the outlet of draft tube and sample efferent duct near and stretch out outside the framework, the entrance of described draft tube is communicated with to the air pump of wherein carrying neutral reagent gas, the outlet of sample efferent duct is communicated with the sample feeding pipe of EESI; Draft tube and sample efferent duct are kapillary.
2. described neutral desorption apparatus according to claim 1 is characterized in that, described draft tube and sample efferent duct are 45～150 ° of angles.
3. described neutral desorption apparatus according to claim 1 and 2 is characterized in that, the skin of described draft tube is provided with heating jacket.
4. described neutral desorption apparatus according to claim 1 and 2 is characterized in that, other establishes a liquid-feeding tube, and the outlet of liquid-feeding tube outlet and draft tube and the entrance of sample efferent duct are close.
5. described neutral desorption apparatus according to claim 3 is characterized in that, other establishes a liquid-feeding tube, and the outlet of liquid-feeding tube outlet and draft tube and the entrance of sample efferent duct are close.
6. neutral desorption extractive electrospray lonization mass spectrometry method, it is characterized in that, right to use requires 1 to 5 arbitrary described neutral desorption apparatus collected specimens and by the outlet of sample efferent duct sample flow is introduced electron spray extraction ionization source, specifically may further comprise the steps:
Step 1: the sample efferent duct outlet of the above neutral desorption apparatus is linked to each other with the sample feeding pipe of electron spray extraction ionization source, and electron spray extraction ionization source is connected with mass spectrometer;
Step 2: the entrance of the sample efferent duct of neutral desorption apparatus is aimed at solid sample to be checked surface, distance 5～12mm;
Step 3: to the draft tube input neutral gas of neutral desorption apparatus, gas flow rate is 15～40psi;
Step 4: impose 3～6KV high pressure to electron spray extraction ionization source simultaneously and make sample ionization;
Step 5: open the mass spectrometer scanning system, obtain testing result.
7. described analytical approach according to claim 6 is characterized in that, further right to use requires liquid-feeding tube described in 5, opens simultaneously liquid-feeding tube in the step 3 solvent in the liquid-feeding tube is sprayed to sample; Described neutral gas is the innocuous gas that comprises water vapour, nitrogen, air, and described solvent is water or methyl alcohol.
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