CN108037174A - A kind of sharp slide ionization apparatus and its application based on tip electron spray - Google Patents
A kind of sharp slide ionization apparatus and its application based on tip electron spray Download PDFInfo
- Publication number
- CN108037174A CN108037174A CN201711272781.XA CN201711272781A CN108037174A CN 108037174 A CN108037174 A CN 108037174A CN 201711272781 A CN201711272781 A CN 201711272781A CN 108037174 A CN108037174 A CN 108037174A
- Authority
- CN
- China
- Prior art keywords
- slide
- tip
- sharp
- mass
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- 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
- G01N27/68—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 electric discharge to ionise a gas
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention relates to a kind of sharp slide ionization apparatus based on tip electron spray and its application, sharp slide, electrode, objective table, sharp slide is made of glass material, sharp slide is cylindrical, sharp slide front end is provided with tip, sharp slide is placed on objective table and is fixed with copper wire, copper wire is as electrode one ends wound in the middle and back of sharp slide, the electrode other end is grounded, sharp slide is polished to obtain by glass dropper front end by sand paper, tip thickness≤0.3mm of sharp slide front end, width≤0.2mm, the tip of sharp slide and mass spectrometric injection port or so are aligned and form the voltage of 1000 5000V, distance >=10mm between it；The configuration of the present invention is simple, be easy to structure, easy to operate quick, anti-cross contamination, it can be advantageously used in the direct injection analysis of sample solution, solve the problems, such as the complicated components such as existing tip electron spray base material filter paper, leaf, toothpick, tissue fibers, analyte can be caused necessarily to pollute.
Description
[technical field]
The present invention relates to electrospray techniques field, specifically a kind of sharp slide ion makeup based on tip electron spray
Put and its apply.
[background technology]
Tip electron spray is a kind of new mass-spectrometric technique, the technology be in the environment of unlimited atmospheric pressure to sample into
The direct mass spectral analysis of row.This method utilizes the high pressure produced between mass spectrum and the device of ground connection to cause the ion in sample in point
End enters mass spectrum injection port after producing electron spray, ionization, realizes mass spectral analysis.Complicated sample is not required in tip spray technique
Preparation process, it is not necessary to carrier gas produces electron spray, and have high throughput, simplicity, in real time, the features such as quick, cost is low.Meanwhile
The advantages of mass spectrographic high sensitivity and high analyte speed is also possessed in tip spraying.This technology makes workflow more simple, carries
The high ease for use of mass spectrometer.With the development that tip is sprayed, the tip spray technique of more and more species is developed,
Such as：Paper spray technique, toothpick spray technique, foliar spray technology, porous polymer needle point spray technique, the fiber of different materials
Spray technique, blade spray technique etc..
Liu et al.[1]Sample is placed on triangle filter paper, electron spray is formed with 3.5kV, medicament for the eyes is analyzed with paper Spray Mass Spectrometry
Benzalkonium chloride in water and disinfectant, has also set up determining for benzalkonium chloride main homologue C12-BAC, C14-BAC and C16-BAC
Analysis method.Huang etc.[2]The dried blood sample (DBS) of preparation is placed on aluminium sheet, is analyzed with probe heating paper electrospray mass spectrometry
Propranolol therein.Using Isotopic Internal Standard, the wider range of linearity (1.0-500ng mL are obtained-1) and relatively low detection
Limit (is less than 0.4ng mL-1).Wang etc.[3]Polystyrene (PS) is coated on paper and analyzes drug sample as substrate, makes sensitivity
Improve 10-546 times.Meher etc.[4]By the use of paper handkerchief as base material, when 4 millimeters of upper several microlitres of small pieces cotton paper towel drop of diameter
Sample solution when being placed in mass spectrometric entrance, the high voltage applied at mass spectrometer inlet can make the thin fibre on paper
Dimension forms electron spray.To paper spraying ionization technique researches show that：The geometrical property of paper, spray voltage, the angle at paper tip and
Size etc. all has considerable influence to paper spraying ionization[5]。
Foliar spray ionization technique is similar to paper spray method.Falcone etc.[6]Analyzed with foliar spray mass-spectrometric technique
Infect emerald ash snout moth's larva (EAB) when leaf in compound change.Leaf is cut into triangle and ensures tip by them, is directly divided
Analyse 23 health and infect the foliage samples of EAB.Under ion mode, the mass spectra peak of healthy ash tree (ash tree) leaf is
M/z 45.55,471.5 and 487.5, and the mass spectra peak for having infected EAB ash leaves is m/z 181 and 217.
Toothpick spraying ionization technique is another tip spray method.Hu etc.[7]Sprayed using toothpick to sedative and weight-reducing
Food etc. carries out adulteration analyte, develops a kind of high throughput rapid analysis method.They insert one group of 20 toothpick at a distance of 3.0mm
Enter in unit of plastic, for the analysis of 144 kinds of health products, display toothpick spraying ionization mass spectrometry is the one kind for identifying adulterated medicine
Simple and reliable method.
Bedair etc.[8]It then have studied the spraying of porous polymer (PPM) micro-fluidic chip tip.They are respectively with poly- diformazan
Radical siloxane (PDMS), polymethyl methacrylate (PMMA) and cyclic olefine copolymer (COC) make chip.Porous polymer makes
It there are multiple paths in microchannel, can prevent from blocking, improve stability and the sensitivity of ion stream.Using COC chips, with
Polypropylene glycol is sample, optimal electrospray conditions (RSD<5%) it is that methanol containing 50-70%, flow velocity are in mobile phasemin-1.PPM sprayings can be additionally used in protein pre-concentration and desalination.Wong etc.[9]Respectively with hydrophobic and close
Water porous polymer tip materials analyze different samples, and display hydrophobic material has more preferable detection sensitivity to polarity sample,
And water wetted material is adapted to analyze nonpolar sample.Gibson etc.[10]The makrolon micro-structure for then comparing 3,6,9 and 12 holes is fine
The tip electrospray ionization mass spectrum effect of dimension.
Recently, Tascon[11]Etc. have studied a kind of coated chip spraying (CBS) technology.They apply in blade front end area
On polymer beads as micro-extraction, carry out electric spray sample introduction using insert tip, the high throughput (96 of humoral sample can be carried out
Orifice plate) mass spectral analysis.Performing 96 orifice plate-CBS extraction operations at the same time can shorten to the average total score of each sample analysis time less
In 55 seconds.And added in urine sample and plasma sample with this technical research 18 kinds of medicines while quantitative analysis method.
In previous experiments[12]In, slide electron spray research is carried out with hesperetin solution, as a result, be cut into 60 ° using front end
During angle, distance can carry out Electrospray Ionization Mass Spectrometry in 2.0 ± 0.2mm, voltage for 4500V.The front end of glass slide used
Thickness is 1.0mm, width 0.3mm.Since front end is larger, particularly thickness is big, it is necessary to which nearer distance could produce EFI
Mist, experimental implementation require height, are not easy to promote and apply.
Bibliography：
1.Liu J J,Deng W J,Yu M Q,Wen R Z,Yao S Z,Chen B.Rapid analysis of
benzalkonium chloride using paper spray mass spectrometry.Journal of
Pharmaceutical and Biomedical Analysis,2017,145:151-157.
2.Huang H,Wu Q,Zeng L,Wan L,Lai S Q,Yin X J,Huang J F,Yang B C,Liu J
C,.Heating paper spray mass spectrometry for enhanced detection of
propranolol in dried blood samples,Anal.Methods,2017,29:4282-4287.
3.Wang T,Zheng Y J,Wang X T,Daniel E A,Zhang Z P.Sub-ppt Mass
Spectrometric Detection of Therapeutic Drugs in Complex Biological Matrixes
Using Polystyrene-Microsphere-Coated Paper Spray.Anal.Chem.,2017,89:7988-
7995.
4.Meher A K,Chen Y C,Tissue paper assisted spray ionization mass
spectrometry.RSC Adv.,2015,5:94315–94320.
5.Yang Q, Wang H, Maas J D, Chappell W J, Manicke N E, Cooks R G, Ouyang
Z.Int.J.,Paper spray ionization devices for direct,biomedical analysis using
mass spectrometry.Mass spectrom.,2012,312:201-207.
6.Falcone C E,Cooks R G.Molecular recognition of emerald ash borer
infestation using leaf spray mass spectrometry.Rapid Commun.Mass Spectrom.,
2016,30:1304–1312.
7.Hu B,Huang Y Y,Yin G,Zhang G F,Zhang L Y,Wang T J,Yao Z P.Rapid
detection of adulterated drugs in herbal dietary supplements by wooden-tip
electrospray ionization mass spectrometry.Anal.Methods.,2016,8:6840–6846.
8.Bedair M F,Oleschuk R D,Fabrication of Porous Polymer Monoliths in
Polymeric Microfluidic Chips as an Electrospray Emitter for Direct Coupling
to Mass Spectrometry.Anal.Chem.,2006,78:1130-1138.
9.Wong M Y M,Tang H W,Man S H,Lam C W,Che C M,Ng K M.Electrospray
ionization on porous spraying tips for direct sample analysis by mass
spectrometry:enhanced detection sensitivity and selectivity using
hydrophobic/hydrophilic materials as spraying tips.Rapid Commun.Mass
Spectrom.,2013,27:713-721.
10.Gibson G T T,Wright R D,Oleschuk R D.Multiple electrosprays
generated from a single polycarbonate microstructured fibre.Mass Spectrom.,
2012,47:271-276.
11.Tascon M,Gomez-Ríos G A,Reyes-Garcés N,Poole J,Boyac1E,Pawliszyn
J.High-Throughput Screening andof Target Compounds in
Biofluids by Coated Blade Spray-Mass Spectrometry.Anal.Chem.,2017,89,8421-
8428.
12. Han Yu is good, Huang Yuyu, Zhang Yaoli, Gong Can, the spraying of Xu Xu surface of glass slide is ionized in direct mass spectrum sample introduction analysis
State's chemistry can Second China National mass spectral analysis symposium (Hangzhou, 2015)
13.Smith D P H,The Electrohydrodynamic Atomization of Liquids.IEEE
Trans Ind Appl IA.,1986,22:527-535.
14.Pramanik B N,Ganguly A K,Gross M L.Applied Electrospray Mass
Spectrometry,1ed.New York,2002.
[content of the invention]
A kind of sharp slide ion based on tip electron spray is provided present invention aim to solve above-mentioned deficiency
Makeup is put, its is simple in structure, is easy to structure, easy to operate quick, anti-cross contamination, can be advantageously used in the straight of sample solution
Sample analysis is tapped into, solves the complicated components such as existing tip electron spray base material filter paper, leaf, toothpick, tissue fibers, can
The problem of causing necessarily to pollute to analyte.
A kind of sharp slide ionization apparatus based on tip electron spray, including sharp slide 1, electricity are designed to achieve the above object
Pole 2, objective table 3, the point slide 1 are made of glass material, and the point slide 1 is cylindrical, and 1 front end of the point slide is set
Tip is equipped with, the point slide 1 is placed on objective table 3 and is fixed with copper wire, and 2 one ends wound of electrode is in sharp slide 1
Middle and back, 2 other end of the electrode ground connection.
Further, the electrode 2 is copper electrode, silver electrode or platinum electrode.
Further, the sharp slide 1 is polished to obtain by glass dropper front end by sand paper, 1 front end of the point slide
Tip thickness≤0.3mm, tip width≤0.2mm of 1 front end of the point slide, the tip of the point slide 1 and mass spectrograph 4
Injection port or so is aligned and forms the voltage of 1000-5000V, between the point tip of slide 1 and the injection port of mass spectrograph 4
Distance is >=10mm.
Further, the objective table 3 be adjustable-angle device, it is described point slide 1 tip obliquely 7.5 ° it is right
Quasi- injection port.
Further, the distance between injection port of the tip of the sharp slide 1 and mass spectrograph 4 is 10mm.
Present invention also offers a kind of sharp slide ionization apparatus based on tip electron spray in mass spectrum direct injection analysis
In application, comprise the following steps：1) first, sharp slide is fixed on objective table and adjusts the height of objective table, makes point
The tip of slide and mass spectrometric injection port or so are aligned, tip 7.5 ° of alignment injection ports obliquely, sharp slide apart from mass spectrum into
Sample mouth distance >=10mm；2) and then by electrode it is wrapped on sharp slide and is grounded, testing sample solution is added drop-wise to sharp slide
Contacted on surface and with grounding electrode；3) finally, mass spectrograph is opened to be analyzed.
Further, the testing sample solution solubility is 0.1mg/ml, and sample to be tested is neutral, alkalescence or acidic chemical
Sample.
Further, the mass spectrograph is fourier transform mass spectrometer, the mass spectral analysis condition of fourier transform mass spectrometer
For：If being tested under positive ion mode, its Mass Spectrometry Conditions is dry gas, 200 DEG C of flow velocity 1.0ml/min, temperature, voltage
4.5kV, ion accumulation time 0.2sec, flight time 0.8ms；If being tested under negative ion mode, its Mass Spectrometry Conditions is,
200 DEG C, voltage 4.5kV, ion accumulation time 0.5sec of flow velocity 1.0ml/min, temperature, flight time 0.6ms.
Further, when using positive ion mode detection, testing sample solution is the methanol solution containing 1% formic acid；When
When being detected using negative ion mode, testing sample solution is the methanol aqueous solution containing 1% ammonium hydroxide.
The present invention is compared with the existing technology, there is provided it is a kind of for mass spectral analysis based on the sharp slide of tip electron spray from
Son makeup is put, including sharp slide and electrode of tip thickness≤0.3mm and width≤0.2mm etc., and sharp slide is placed on loading
Be fixed on platform with copper wire, electrode is wrapped in the middle and back of sharp slide and ground connection, the tip of sharp slide when in use with matter
The capillary glass tube entrance alignment of spectrometer, distance is >=10mm, can carry out mass spectrograph direct injected using it to realize to chemistry
The analysis of sample solution, this method are not required carrier gas to produce electron spray, simple in structure, be easy to structure, be easy to operate quick, anti-
Cross contamination, can be advantageously used in the direct injection analysis of sample solution, to sample and mass spectrometric interface without complexity
Limitation, can be directly connected to different types of mass spectrograph and use, solve existing tip electron spray base material filter paper, leaf,
The complicated components such as toothpick, tissue fibers, the problem of may causing necessarily to pollute to analyte, and further improve experiment knot
Fruit；In addition, the glass material that the present invention selects utilizes the M+Na of the sodium ion in glass also reinforced portion sample as matrix+
Peak, under the conditions of meta-alkalescence, the electric osmose of glass surface generation, is also beneficial to solution under positive ion mode and is helped to tip movement
In generation electron spray, and the sample solution on sharp slide can survey side with frontier inspection and be added dropwise, and solvent can be added dropwise, and detection loading is very square
Just, it is also easy to clean after test, is worthy of popularization.
According to Smith[13,14] propose formula (1), the high pressure Von (kV) of electron spray and the radius r of electron spray pin occurs
(μm), surface tension [24] γ (N/m) of solvent is related, also with the spraying needle point and distance d to electrode (mass spectrum sample holes)
(mm) it is related：
As it can be seen that improving distance d can be realized by reducing radius r or the diameter of spray needle.Compared to paper spraying and
Toothpick is sprayed, and glass slide is difficult to cut out satisfied tiny tip with glass cutter because of its thickness.To obtain tiny slide tip, this
Invention carefully polishes slide tip using sand paper, obtains thickness≤0.3mm, slide point of the width less than or equal to 0.2mm
End, it is achieved thereby that satisfied tip EFI fog effect.
[brief description of the drawings]
Fig. 1 is the structure diagram of the present invention；
Fig. 2 is the first mass spectrometric figure of the quinine direct injection analysis of Application Example 1 of the present invention；
Fig. 3 is the first mass spectrometric figure of the hesperetin direct injection analysis of Application Example 2 of the present invention；
Fig. 4 is the first mass spectrometric figure of the tartaric acid direct injection analysis of Application Example 3 of the present invention；
Fig. 5 is the first mass spectrometric figure of the phenylalanine direct injection analysis of Application Example 4 of the present invention；
In figure：1st, sharp slide 2, electrode 3, objective table 4, mass spectrograph.
[embodiment]
The present invention is made with reference to specific embodiment further explained below：
The present invention includes：Sharp slide 1, electrode 2, objective table 3, sharp slide 1 are made of glass material, and sharp slide 1 is in circle
Column, sharp 1 front end of slide are provided with tip, and sharp slide 1 is placed on objective table 3 and is fixed with copper wire, and 2 one ends wound of electrode exists
The middle and back of sharp slide 1,2 other end of electrode ground connection；Wherein, electrode 2 is copper electrode, silver electrode or platinum electrode；Sharp slide 1
By glass dropper front end, by sand paper, carefully polishing obtains, tip thickness≤0.3mm of sharp 1 front end of slide, sharp 1 front end of slide
Tip width≤0.2mm, the tip of sharp slide 1 and injection port of mass spectrograph 4 or so are aligned and form the voltage of 1000-5000V,
The distance between the tip of sharp slide 1 and the injection port of mass spectrograph 4 are >=10mm, are preferably 10mm；Objective table 3 is adjustable angle
The device of degree, the tip of sharp slide 1 are directed at injection port for 7.5 ° obliquely.
Present invention also offers a kind of sharp slide ionization apparatus based on tip electron spray in mass spectrum direct injection analysis
In application, it comprises the following steps：1) first, sharp slide is fixed on objective table and adjusts the height of objective table, is made
The tip of sharp slide and mass spectrometric injection port or so are aligned, and tip 7.5 ° of alignment injection ports obliquely, sharp slide is apart from mass spectrum
Injection port distance >=10mm；2) and then by electrode it is wrapped on sharp slide and is grounded, testing sample solution is added drop-wise to sharp glass
Contacted on piece surface and with grounding electrode；3) finally, open mass spectrograph to be analyzed, select to examine according to the negative ions of detection
Survey pattern, carries out mass spectral analysis.Wherein, mass spectrograph is fourier transform mass spectrometer, in the embodiment of the present invention in Fu used
Leaf transformation mass spectrograph is the solariX 70FT-MS type fourier transform mass spectrometers of German Brooker company, above-mentioned Fourier
The mass spectral analysis condition of Transform Mass Spectrometry instrument is：If being tested under positive ion mode, its Mass Spectrometry Conditions is dry gas, flow velocity
200 DEG C, voltage 4.5kV, ion accumulation time 0.2sec of 1.0ml/min, temperature, flight time 0.8ms；If anion
Tested under pattern, its Mass Spectrometry Conditions is 200 DEG C, voltage 4.5kV of flow velocity 1.0ml/min, temperature, and ion accumulation time is
0.5sec, flight time 0.6ms, other parameters use fourier transform mass spectrometer system default value.Testing sample solution
Solubility is 0.1mg/ml.When using positive ion mode detection, testing sample solution is the methanol solution containing 1% formic acid；When adopting
When being detected with negative ion mode, testing sample solution is the methanol-water (1 containing 1% ammonium hydroxide:1) solution.Sample to be tested is neutral, alkali
Property or acidic chemical sample, such as quinine, hesperetin, styrax, L- (-)-tartaric acid, mandelic acid, 2,5-dihydroxybenzoic acid,
Only illustrated in the embodiment of the present invention with hesperetin, L- (-)-tartaric acid, mandelic acid, but be not intended to limit and utilize the present invention
A kind of achievable tip spraying Direct Analysis device to the measure of other chemical substances to be measured.
Embodiment 1
A kind of sharp slide ionization apparatus of achievable tip spraying Direct Analysis, including sharp slide 1, electrode 2；Sharp slide
It is fixed on objective table and adjusts height, the tip of sharp slide 1 be directed at the injection port of mass spectrograph 4 or so when in use, sharp
Portion is directed at injection port for 7.5 ° obliquely, and sharp slide 1 is apart from 3 injection port 10mm of mass spectrum.Electrode 2 is grounded again, then will be to be measured molten
Drop is added in sharp 1 surface of slide；Sharp slide 1 is carefully polishing to its tip thickness≤0.3mm for glass dropper front end by sand paper,
Width≤0.2mm；Electrode 2 is copper electrode；Mass spectrograph 3 is fourier transform mass spectrometer, for German Brooker company
SolariX 70FT-MS types, the mass spectral analysis condition of the solariX 70FT-MS are as follows：SolariX is set
70FT-MS is positive ion detection pattern.Dry gas：Flow velocity 1.0ml/min, 200 DEG C of temperature；Voltage 4.5kV, ion accumulation time
For 0.2sec, flight time 0.8ms.Other parameters use fourier transform mass spectrometer system default value.
Application Example 1
Sharp slide ionization apparatus using a kind of achievable tip spraying Direct Analysis of embodiment 1 divides quinine
Analysis, step are as follows：Sample to be tested quinine 3mg is taken to be dissolved in 3ml methanol (containing 1% formic acid), ultrasonic dissolution；Sample is diluted 10 again
Times to 0.1mg/ml detecting；Sharp slide 1 is fixed on objective table 3, the tip of sharp slide 1 when in use with mass spectrograph 4
Injection port or so alignment, tip 7.5 ° of alignment injection ports obliquely, distance is 10mm, then electrode 2 is grounded, then will be to be measured
Solution is added dropwise on sharp 1 surface of slide, is finally opened mass spectrograph 3 and is analyzed.
As shown in Figure 2, this experiment quinine appearance is [M+H] to the quinine first mass spectrometric figure of gained after above-mentioned mass spectral analysis+
=325.19119, theoretical value [M+H]+=325.19105, it can be seen that quinine measurement value is 325.19119 from attached drawing 2, with
Theoretical value error is only 0.4ppm.Show to be quinine [M+H] in attached drawing 2+Peak, shows real-time using the achievable mass spectrograph of the present invention
Direct injection analysis determination sample, its evaluated error is small, and measurement result is accurate.
Application Example 2
Hesperetin is carried out using a kind of sharp slide ionization apparatus of achievable tip spraying Direct Analysis of embodiment 1
Analysis, step are as follows：Sample to be tested hesperetin 3mg is taken to be dissolved in 3ml methanol (containing 1% formic acid), ultrasonic dissolution；It is again that sample is dilute
10 times are released to 0.1mg/ml to detect；Sharp slide 1 is fixed on objective table 3, the tip of sharp slide 1 when in use with mass spectrum
Injection port of instrument 4 or so is aligned, and tip is directed at injection port for 7.5 ° obliquely, and distance is 10mm, then electrode 2 is grounded, and then will
Solution to be measured is added dropwise on sharp 1 surface of slide, is finally opened mass spectrograph 4 and is analyzed.
As shown in Figure 3, this experiment hesperetin appearance is [M+ to the hesperetin first mass spectrometric figure of gained after above-mentioned mass spectral analysis
H]+=373.13002, theoretical value [M+H]+=373.12818, it can be seen that hesperetin measured value is from attached drawing 3
373.13002 it is only 4.9ppm with theoretical value error.Show to be hesperetin [M+H] in attached drawing 3+Peak, showing can using the present invention
Realize the real-time direct injection analysis determination sample of mass spectrograph, its evaluated error is small, and measurement result is accurate.
Embodiment 2
A kind of device of achievable tip spraying Direct Analysis, including sharp slide 1, electrode 2；Sharp slide is fixed on objective table
On 3 and adjust height, the tip of sharp slide 1 is aligned with the injection port of mass spectrograph 4 or so when in use, 7.5 ° obliquely of tip
Injection port is directed at, sharp slide 1 is grounded apart from 4 injection port 10mm of mass spectrum, then by electrode 2, and then solution to be measured is added dropwise in sharp glass
1 surface of piece；Sharp slide 1 is carefully polishing to its tip thickness 0.2mm, width 0.13mm for glass dropper front end by sand paper；Institute
It is copper electrode to state electrode 2；Mass spectrograph 3 is fourier transform mass spectrometer, for the solariX 70FT-MS of German Brooker company
Type, the mass spectral analysis condition of the solariX 70FT-MS are as follows：It is anionic textiles pattern to set solariX 70FT-MS：Stream
200 DEG C of fast 1.0ml/min, temperature；Voltage 4.5kV, ion accumulation time 0.5sec, flight time 0.6ms.Other parameters
Use fourier transform mass spectrometer system default value.
Application Example 3
Carried out using a kind of sharp slide ionization apparatus paratartaric acid of achievable tip spraying Direct Analysis of embodiment 2
Analysis, step are as follows：Sample to be tested tartaric acid 3mg is taken to be dissolved in 3ml methanol aqueous solutions (containing 1% ammonium hydroxide), ultrasonic dissolution；Again will
Sample dilutes 10 times to 0.1mg/ml detecting；Sharp slide 1 is fixed on objective table 3, the tip of sharp slide 1 is when in use
It is aligned with the injection port of mass spectrograph 4 or so, tip 7.5 ° of alignment injection ports obliquely, distance is 10mm, then electrode 2 is grounded,
Then solution to be measured is added dropwise on sharp 1 surface of slide, finally opens mass spectrograph 4 and analyzed.
As shown in Figure 4, this experiment tartaric acid appearance is the first mass spectrometric figure of the tartaric acid of gained after above-mentioned mass spectral analysis
[M-H]-=149.00914, theoretical value [M-H]-=149.00806, it can be seen that tartaric acid measured value is from attached drawing 4
149.00914 it is only 0.7ppm with theoretical value error.Show to be tartaric acid [M-H] in attached drawing 4-Peak, showing can using the present invention
Realize the real-time direct injection analysis determination sample of mass spectrograph, its evaluated error is small, and measurement result is accurate.
Application Example 4
Mandelic acid is carried out using a kind of sharp slide ionization apparatus of achievable tip spraying Direct Analysis of embodiment 2
Analysis, step are as follows：Sample to be tested phenylalanine-3,4-quinone mg is taken to be dissolved in 3ml methanol-waters (1:1) solution (ammonium hydroxide for containing 1%), ultrasound
Dissolving；Sample is diluted 10 times to 0.1mg/ml detecting again；Sharp slide 1 is fixed on objective table 3, the point of sharp slide 1
End be directed at the injection port of mass spectrograph 4 or so when in use, and tip 7.5 ° of alignment injection ports obliquely, distance is 10mm, then general
Electrode 2 is grounded, and then solution to be measured is added dropwise on sharp 1 surface of slide, is finally opened mass spectrograph 4 and is analyzed.
As shown in Figure 5, this experiment phenylalanine goes out the first mass spectrometric figure of the phenylalanine of gained after above-mentioned mass spectral analysis
Peak is [M-H]-=164.07306, theoretical value [M-H]-=164.07060, it can be seen that phenylalanine measurement value from attached drawing 5
It is only 1.5ppm with theoretical value error for 164.07306.Show to be phenylalanine [M-H] in attached drawing 5-Peak, shows to utilize this hair
The bright real-time direct injection analysis determination sample of achievable mass spectrograph, its evaluated error is small, and measurement result is accurate.
In conclusion a kind of sharp slide ionization apparatus of achievable tip spraying Direct Analysis provided by the invention, should
Device is not required carrier gas, simple in structure, be easy to structure, easy to operate quick, anti-cross contamination, in that context it may be convenient to molten for sample
The mass spectral analysis of liquid, to sample and mass spectrometric interface without complicated limitation, can be directly connected to different types of mass spectrograph makes
With, and to the qualitative error very little of sample, realize the direct qualitative analysis to sample.
The present invention is simultaneously not limited to the embodiments described above, other any Spirit Essences and principle without departing from the present invention
Lower made change, modification, replacement, combination, simplification, should be equivalent substitute mode, be included in the protection model of the present invention
Within enclosing.
Claims (10)
- A kind of 1. sharp slide ionization apparatus based on tip electron spray, it is characterised in that：Including sharp slide (1), electrode (2), Objective table (3), the point slide (1) are made of glass material, and the point slide (1) is cylindrical, before the point slide (1) End is provided with tip, and the point slide (1) is placed on objective table (3) and is fixed with copper wire, and electrode (2) one ends wound exists The middle and back of sharp slide (1), electrode (2) other end ground connection.
- 2. the sharp slide ionization apparatus based on tip electron spray as claimed in claim 1, it is characterised in that：The electrode (2) it is copper electrode, silver electrode or platinum electrode.
- 3. the sharp slide ionization apparatus based on tip electron spray as claimed in claim 2, it is characterised in that：The point slide (1) polish to obtain by sand paper by glass dropper front end, the tip thickness≤0.3mm of described point slide (1) front end, the point glass Tip width≤the 0.2mm of piece (1) front end, tip and the injection port of mass spectrograph (4) of the point slide (1) or so is directed at simultaneously shape Into the voltage of 1000-5000V, the distance between the tip of the point slide (1) and the injection port of mass spectrograph (4) are >=10mm.
- 4. the sharp slide ionization apparatus based on tip electron spray as claimed in claim 3, it is characterised in that：The objective table (3) it is the device of adjustable-angle, the tip of the point slide (1) is directed at injection port for 7.5 ° obliquely.
- 5. the sharp slide ionization apparatus based on tip electron spray as claimed in claim 4, it is characterised in that：The point slide (1) the distance between tip and injection port of mass spectrograph (4) are 10mm.
- 6. a kind of sharp slide ionization apparatus based on tip electron spray as any one of claim 1 to 5 is in mass spectrum Application in direct injection analysis.
- 7. application as claimed in claim 6, it is characterised in that comprise the following steps：1) first, sharp slide is fixed on objective table and adjusts the height of objective table, makes tip and the mass spectrograph of sharp slide Injection port or so alignment, tip 7.5 ° of alignment injection ports obliquely, sharp slide is apart from mass spectrum injection port distance >=10mm；2) and then by electrode be wrapped on sharp slide and be grounded, by testing sample solution be added drop-wise in sharp surface of glass slide and with Grounding electrode contacts；3) finally, mass spectrograph is opened to be analyzed.
- 8. application as claimed in claim 7, it is characterised in that：The testing sample solution solubility is 0.1mg/ml, treats test sample Product are neutral, alkalescence or acidic chemical sample.
- 9. application as claimed in claim 8, it is characterised in that the mass spectrograph is fourier transform mass spectrometer, and Fourier becomes Changing mass spectrometric mass spectral analysis condition is：If being tested under positive ion mode, its Mass Spectrometry Conditions is dry gas, flow velocity 1.0ml/ 200 DEG C, voltage 4.5kV, ion accumulation time 0.2sec of min, temperature, flight time 0.8ms；If under negative ion mode Test, its Mass Spectrometry Conditions is 200 DEG C, voltage 4.5kV, ion accumulation time 0.5sec of flow velocity 1.0ml/min, temperature, flight Time is 0.6ms.
- 10. application as claimed in claim 9, it is characterised in that：When using positive ion mode detection, testing sample solution is Methanol solution containing 1% formic acid；When using negative ion mode detection, testing sample solution is water-soluble for the methanol containing 1% ammonium hydroxide Liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272781.XA CN108037174A (en) | 2017-12-06 | 2017-12-06 | A kind of sharp slide ionization apparatus and its application based on tip electron spray |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272781.XA CN108037174A (en) | 2017-12-06 | 2017-12-06 | A kind of sharp slide ionization apparatus and its application based on tip electron spray |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108037174A true CN108037174A (en) | 2018-05-15 |
Family
ID=62095864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711272781.XA Pending CN108037174A (en) | 2017-12-06 | 2017-12-06 | A kind of sharp slide ionization apparatus and its application based on tip electron spray |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108037174A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111413393A (en) * | 2019-12-20 | 2020-07-14 | 杭州师范大学 | Method for rapidly detecting formaldehyde content in food by high-throughput reaction paper spray mass spectrometry |
| CN112958055A (en) * | 2021-01-29 | 2021-06-15 | 山东师范大学 | Adsorbing material for water pollutants, preparation method and mass spectrum detection application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558230A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Nano-liter spraying device |
| CN102522311A (en) * | 2011-10-20 | 2012-06-27 | 中国科学院上海有机化学研究所 | Nano-spraying electrode as well as manufacturing method and application thereof |
| CN104316592A (en) * | 2014-11-05 | 2015-01-28 | 西安石油大学 | Biological sample spectral analysis method based on solute migration electrospray ionization technique |
| CN105895494A (en) * | 2016-06-29 | 2016-08-24 | 哈尔滨工业大学（威海） | Mass spectrum ion source device |
| CN106370718A (en) * | 2016-12-08 | 2017-02-01 | 中国食品药品检定研究院 | Rapid measurement method of drug dissolution rate |
-
2017
- 2017-12-06 CN CN201711272781.XA patent/CN108037174A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558230A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Nano-liter spraying device |
| CN102522311A (en) * | 2011-10-20 | 2012-06-27 | 中国科学院上海有机化学研究所 | Nano-spraying electrode as well as manufacturing method and application thereof |
| CN104316592A (en) * | 2014-11-05 | 2015-01-28 | 西安石油大学 | Biological sample spectral analysis method based on solute migration electrospray ionization technique |
| CN105895494A (en) * | 2016-06-29 | 2016-08-24 | 哈尔滨工业大学（威海） | Mass spectrum ion source device |
| CN106370718A (en) * | 2016-12-08 | 2017-02-01 | 中国食品药品检定研究院 | Rapid measurement method of drug dissolution rate |
Non-Patent Citations (2)
| Title |
|---|
| JIE JIANG等: "Droplet Spray Ionization from a Glass Microscope Slide: Real-Time Monitoring of Ethylene Polymerization", 《ANALYTICAL CHEMISTRY》 * |
| 韩玉良等: "玻片表面喷雾电离直接质谱进样分析", 《中国化学会第二届全国质谱分析学术报告会》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111413393A (en) * | 2019-12-20 | 2020-07-14 | 杭州师范大学 | Method for rapidly detecting formaldehyde content in food by high-throughput reaction paper spray mass spectrometry |
| CN112958055A (en) * | 2021-01-29 | 2021-06-15 | 山东师范大学 | Adsorbing material for water pollutants, preparation method and mass spectrum detection application thereof |
| CN112958055B (en) * | 2021-01-29 | 2022-09-09 | 山东师范大学 | Adsorbing material for water pollutants, preparation method and mass spectrum detection application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Klampfl et al. | Direct ionization methods in mass spectrometry: An overview | |
| Monge et al. | Mass spectrometry: recent advances in direct open air surface sampling/ionization | |
| US10895559B2 (en) | Open port sampling interface | |
| EP3201627B1 (en) | System for detecting gluten in food samples | |
| JPH11271277A (en) | Mass spectrometry and mass spectrograph for humor | |
| CN104956462B (en) | For analyzing the system and method for extracting sample | |
| US10782285B2 (en) | Device and method for chemical analysis | |
| CN113725063B (en) | Probes, cartridges, systems, and methods of sample analysis | |
| WO2012170301A1 (en) | Cassettes, systems, and methods for ion generation using wetted porous materials | |
| CN106483186A (en) | A kind of ionization massspectrum detection means and its application | |
| CN112213412A (en) | Method for detecting drug and metabolite thereof in hair | |
| JP2019124696A (en) | Analyzing extraction sample using immiscible extraction solvent | |
| CN107121487B (en) | A kind of normal pressure velocity of sound electrospray ionization device and its application | |
| CN108037174A (en) | A kind of sharp slide ionization apparatus and its application based on tip electron spray | |
| CN106807941B (en) | A kind of noble metal core-shell structure nanometer particle and its preparation and application | |
| CN106706774B (en) | The method that area normalization method measures crocin constituents in west safflower medicinal material | |
| Meher et al. | Electrospray modifications for advancing mass spectrometric analysis | |
| CN108037175A (en) | A kind of glass point dropper ionization apparatus and its application based on tip electron spray | |
| Mandal et al. | Biomolecular analysis and biological tissue diagnostics by electrospray ionization with a metal wire inserted gel-loading tip | |
| Yue-Guang et al. | Progress of sonic-spray ionization mass spectrometry and its applications | |
| CN106248773A (en) | Vitamin B in a kind of quickly mensuration multidimensional sheet1with ascorbic method | |
| CN110208358A (en) | A kind of high-frequency vibration atomization ionization probe device and method | |
| TW201245711A (en) | A method adapted for direct electrospray ionization mass spectrometry for the characterization of sample components | |
| CN104634885A (en) | Analysis and identification method for flavonoid constituent in callicarpa nudiflora | |
| Wong et al. | Droplet-based electrospray ionization mass spectrometry for qualitative and quantitative analysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180515 |