CN109632937A - A kind of wooden capillary electrospray ionisation device and analysis method - Google Patents
A kind of wooden capillary electrospray ionisation device and analysis method Download PDFInfo
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Abstract
A kind of wooden capillary electrospray ionisation device and analysis method, the device are made of four part such as wooden capillary, three-way connector, flue, sample cell.The wooden capillary that the present invention uses is nonmetallic materials, non-conductive, and ionization caused by electric discharge is greatly reduced during electron spray and is inhibited, and reduces the complication of sample caused by electrochemical reaction, makes testing result closer to the truth of sample.
Description
Technical field
The present invention relates to analysis technical fields, and in particular to a kind of wooden capillary electrospray ionisation device and analysis side
Method.
Background technique
Since multiple types compound can be analyzed, especially by thermally labile, the analysis of not volatile large biological molecule
It comes true, electrospray ionization mass spectrometry becomes one of current most widely used mass-spectrometric technique.Electrospray ionisation method uses hair
Tubule is as spray head (emitter), and sample solution enters spray head by pipeline, and high voltage is applied inside spray head, sample
Product solution is formed by spraying under electric field action at spray head tip, forms droplet by spraying, the solvent in droplet, which constantly evaporates, leads
Cause droplet constantly burst, eventually form ion enter mass spectrum be detected.Since metal has ductility, hardness larger, it is easy to
Processing, and good conductivity, therefore commercialization mass spectrograph is all made of stainless steel capillary as EFI fog spray head at present.But it is golden
Belong to capillary to have the disadvantages that as EFI fog spray head
(1) Metallic Nozzle At The Ingot is easy to cause signal to inhibit.The tip of Metallic Nozzle At The Ingot is easy electric discharge under high voltages, and this electric discharge causes
Signal inhibits, and reduces detection sensitivity.Especially in the negative ion mode discharge voltage and spray voltage very close to, cause to bear from
Mass signal is heavily suppressed under subpattern, and the signal strength 1-2 order of magnitude usually lower than positive ion mode, this causes to bear
The application of ion mode electrospray ionization mass spectrum is far below positive ion mode.
(2) Metallic Nozzle At The Ingot causes spectrogram to complicate.The electricity unrelated with analysis may occur in Metallic Nozzle At The Ingot for sample solution
Chemical reaction causes compound in sample solution that a variety of reactions such as hydrolysis, polymerization occur, therefore spectrogram is unable to accurate response sample
The truth of solution.In addition, electric current a part that applied voltage generates is used for and analyzes unrelated electrochemical reaction, to subtract
Lack spraying electric current, caused to ionize insufficient, reduces detection sensitivity.
(3) under the conditions of high flow rate or high water phase, signal is seriously reduced.Metal surface is smooth, it is not easy to by wet with solvent,
And there is no micropore, cause the contact area of solution and metal to reduce yet, reduce ionizing efficiency.These properties lead to spray liquid
It drips larger, reduces detection sensitivity, it is even more serious in the case where high flow rate or high water phase, seriously affect liquid chromatography mass
Sensitivity when combination.
Summary of the invention
In view of the above-mentioned problems, the present invention proposes wooden capillary electrospray ionisation device and analysis method, skill of the invention
Art design has a characteristic that
Feature one: signal can reduce as spray head using non-conducting material and inhibit.Wood materials are not electric conductors, as EFI
The electric discharge that fog spray head material not will lead to signal inhibits, to improve detection sensitivity.
Feature two: spectrogram can be made simple as spray head using nonmetallic materials.Wooden capillary is as EFI fog spray head
The complex reaction that electrochemical reaction initiation can be greatly reduced, becomes spectrogram simply, and the electric current that applied voltage generates all is used
In by spraying, ionizing efficiency is largely increased, therefore substantially increases detection sensitivity.
Feature three: high flow rate or high aqueous sample are resistant to.Wooden capillary itself is non-conductive, but by after wet with solvent just
At the good conductor of electricity, wooden capillary surface is porous structure, considerably increases the contact area of solution and spray head, improves
Ionizing efficiency.These properties cause spray droplet to become smaller, and improve sensitivity, and signal is still in the case where high flow rate or high water phase
It is so very strong.
In order to achieve the object of the present invention, the present invention adopts the following technical scheme:
Step 1: by an internal diameter being 10-250 μm, the wooden capillary (2) that tip outer diameter is 1-5cm close to internal diameter, length
It is placed at mass spectrometer inlet (1) 0.1-6cm, the angle of wooden capillary (2) spray head and mass spectrometer inlet (1) axis is 0-
90°。
Step 2: wooden capillary (2) are soaked using water, making alive makes it constitute circuit with mass spectrograph.Sample is molten
Liquid and nitrogen are transported in wooden capillary (2), nitrogen flow rate 0-600L/h.Sample solution is internal in wooden capillary (2)
Be ionized, under gas auxiliary, formed at wooden capillary (2) tip it is spraying, the ion of generation by mass spectrometer inlet (1) into
Enter mass spectrograph to be detected.
In order to realize that wooden capillary Electrospray Ionization Mass Spectrometry method provided by the invention, the present invention provide a kind of wooden hair
Tubule electrospray ionisation device (as shown in Figure 1):
The device is made of four parts such as wooden capillary (2), three-way connector (3), flue (4), sample cells (5).
Mass spectrometer inlet (1) is located at right end；Left end is wooden capillary (2), and the tip of wooden capillary (2) is placed on
At mass spectrometer inlet (1), the distance apart from mass spectrometer inlet (1) is 0.1-6cm, and wooden capillary spray head (2) enters with mass spectrograph
The angle of mouth (1) axis is 0-90 °.Wooden capillary (2) internal diameter is 10-250 μm, length 1-5cm, and the outer diameter at tip is close
It can be connected with solution line in the tail end shape and size of internal diameter, capillary (2), capillary (2) middle section can be to appoint
Meaning shape.The tail portion of wooden capillary (2) is connected with three-way connector (3), the other both ends of three-way connector (3) respectively as
Gas and sample inlet are connected with flue (4) and sample cell (5), and high voltage is applied directly on wooden capillary (2).
Specific test analysis process:
1) wooden capillary is soaked with water, making alive；
2) mass spectrograph is opened, mass signal is scanned；
3) sampling system is opened, sample solution is transported to wooden capillary (2) by sample cell (5) and three-way connector (3),
Gas switch is opened, nitrogen is transported to wooden capillary (2) by flue (4) and three-way connector (3), adjusts wooden hair
The position of tubule (2) and gas flow make signal reach most strong；
3) writing scan data are to get the mass spectrogram for arriving sample ions.
Technology explanation
Illustrate 1: the internal diameter of wooden capillary (2) described in step 1 is 10-250 μm, and electron spray air-flow compares within this range
Stablize, can adapt to the demand of different sample flows.Not only for the internal diameter of capillary to having an impact by spraying, outer diameter also has shadow to spraying
Ring, increase spray voltage threshold value, in the biggish situation of solution flow velocity, the spray droplet that the biggish capillary of outer diameter generates also compared with
Greatly, it will lead to signal reduction, therefore as far as possible the front end of wooden capillary trimmed sharper, make outer diameter as far as possible close to internal diameter.
Capillary electron spray is only related with outer diameter with the internal diameter of capillary tip, therefore wooden capillary rest part shape does not weigh
Want, as long as therefore can be connected with three-way connector (3), convenient for operation.
The length of wooden capillary (2) also has an impact for electron spray, and long capillary can't improve its performance, instead
Solution pressure in capillary can be made to increase, to improve the technical requirements to capillary production, in addition too long pipeline can also
Bigger dead volume is generated in liquid chromatography mass combination analysis, so as to cause peak stretching, reduces the sensitivity of analysis.Cause
The length of this wooden capillary (2), which is limited in 5cm or less, would not generate biggish pressure and dead volume, certainly too short also to lead
Cause it is inconvenient, therefore within the scope of 1-5cm.
The tip of capillary spray head is molten with used voltage, sample solution flow velocity, sample at a distance from mass spectrometer inlet (1)
The relating to parameters such as liquid composition, the internal diameter of capillary tip and outer diameter, it is therefore desirable to optimize according to the actual situation, usual distance
The distance of mass spectrometer inlet (1) is 0.1-6cm.
The angle of wooden capillary (2) spray head and mass spectrum entrance (1) axis can be 0-90 °, sample solution flow velocity compared with
Small, in the case that solution matrix are less, wooden capillary (2) spray head can be with mass spectrum inlet axis point-blank, spray head
(2) tip face mass spectrometer inlet (1), i.e. angle are equal to 0 °.But in the situation that solution flow velocity is larger, matrix is more complicated
Under, this arrangement mode may cause ion source and be contaminated.When the angle of wooden capillary (2) and mass spectrum entrance (1) axis
When greater than 0 °, can by matrix granule, the drop not gasified and the substance not ionized deflect away, being allowed to cannot
Into ion source, to reduce the pollution to ion source and the interference to target compound.
Illustrate 2: step 2 is soaked wooden capillary (2) using water, and water enters wooden micropore, to make wooden capillary
Managing (2) has conductive capability, adds a high voltage, is allowed to form potential difference with mass spectrometer inlet (1), forms electric field, this is to make
The premise that sample is ionized in wooden capillary (2).Wood is although non-conductive, but by well conducting after wet with solvent, because
It is very convenient to apply voltage as metal capillary for this, as long as being clipped on wooden capillary (2) using electricity.
In the case where solution flow velocity is higher or the higher situation of ratio of water, solution cannot be made to generate spray by electric field force merely
Mist, being passed through nitrogen can assist gasifying.The flow velocity of nitrogen is related with the complexity that sample solution gasifies, usual flow velocity is larger,
The flow velocity of nitrogen is also larger in the higher situation of the ratio of water, conversely, the flow velocity of nitrogen is smaller or even can completely close.
Nitrogen mixes in wooden capillary (2) with the sample solution being ionized, at wooden capillary (2) tip
It is formed by spraying, is by spraying a series of electrification droplets, these electrification droplets are under electric field action to shifting at mass spectrometer inlet (1)
Dynamic, the solvent of droplet surface constantly evaporates in the process, and liquid-drop diameter becomes smaller, and droplet surface amount of charge is constant, works as drop
When surface charge repulsion is equal to the surface tension of drop, i.e., so-called Rayleigh limit, drop starts to burst, and forms smaller liquid
Drop repeats this process, ultimately forms sample ions, and sample ions enter mass spectrometer inlet (1) and are detected.
The utility model has the advantages that
1. the present invention, as EFI fog spray head, can be substantially reduced as caused by electric discharge using the wooden capillary of non-conducting material
Signal inhibits.Compared with Metallic Nozzle At The Ingot, wooden capillary electron spray cation signal intensity ratio metal capillary spray head is one high
The order of magnitude, negative ion signals intensity 2 orders of magnitude higher than metal capillary spray head, solve electrospray ionization mass spectrum for a long time bear from
The relatively low problem of subpattern signal improves the performance and service efficiency of instrument.
2. wooden capillary can greatly reduce electrochemistry as EFI fog spray head compared with metal capillary electron spray
Complex chemical reaction caused by reacting, makes spectrogram become simple.In addition, wooden capillary electron spray energy ratio metal capillary electricity
It is spraying higher, to reduce the various adductions reaction that sample molecule generates during gasification and ionization, more realistically instead
Sample message is answered.
3. wooden porous feature keeps wooden capillary ionizing efficiency higher, spray droplet is smaller, compares metal capillary
Electron spray is more resistant to high sample flow rate and high proportion water phase, to solve at present during liquid chromatography mass combination due to height
The problem of mass signal caused by sample flow rate and high water phase reduces.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of wooden capillary electrospray ionisation device.
In figure: 1- mass spectrometer inlet；The wooden capillary of 2-；3- three-way connector；4- flue；5- sample cell.
Fig. 2 is baicalein metal capillary positive ion mode electrospray ionization mass spectrum figure；
Fig. 3 is the wooden capillary positive ion mode electrospray ionization mass spectrum figure of baicalein；
Fig. 4 is rheum emodin metal capillary negative ion mode electrospray ionization mass spectrum figure；
Fig. 5 is the wooden capillary negative ion mode electrospray ionization mass spectrum figure of rheum emodin；
Fig. 6 is myoglobins metal capillary positive ion mode electrospray ionization mass spectrum figure；
Fig. 7 is the wooden capillary positive ion mode electrospray ionization mass spectrum figure of myoglobins；
Fig. 8 is the ion signal intensity contrast curve of lower metal capillary electron spray different in flow rate and wooden capillary electron spray；
The ion signal intensity contrast figure of wooden capillary electron spray and metal capillary electron spray under Fig. 9 different solvents ratio
Specific embodiment
Embodiment 1
The production of wooden capillary (2): taking a small wood, longitudinally split, and carves a ditch at center using icking tool or laser
Slot, then wooden stick is reconsolidated together according to the situation before splitting, it is fixed using adhesive tape, that is, forms wooden capillary (2).It will
The front end of wooden capillary (2) is trimmed to point, makes its outer diameter as far as possible close to internal diameter.The tail end of wooden capillary (2) is also repaired
It is cut into point, enables to connect with solution line.
A kind of wooden capillary electrospray ionisation device (as shown in Figure 1): by wooden capillary (2), three-way connector
(3), four parts such as flue (4), sample cell (5) form.
Mass spectrometer inlet (1) is located at right end；Left end is wooden capillary (2), and the tip of wooden capillary (2) is placed on
At mass spectrometer inlet (1), distance apart from mass spectrometer inlet (1) is 0.1-6cm, wooden capillary (2) and mass spectrometer inlet (1)
The angle of axis is 0-90 °.Wooden capillary (2) internal diameter is 10-250 μm, length 1-5cm, and the outer diameter at tip is close to interior
Diameter.The tail end of capillary (2) is sharpened, and can be connected with three-way connector (3).Capillary (2) middle section can be
Arbitrary shape.The tail portion of wooden capillary (2) is connected with three-way connector (3), and the other both ends of three-way connector (3) are made respectively
For gas and sample inlet, it is connected with flue (4) and sample cell (5), high voltage is applied directly on wooden capillary (2).
Specific test analysis process:
1) wooden capillary is soaked with water, making alive；
2) mass spectrograph is opened, mass signal is scanned；
3) sampling system is opened, sample solution is transported to wooden capillary (2) by sample cell (5) and three-way connector (3),
Gas switch is opened, nitrogen is transported to wooden capillary (2) by flue (4) and three-way connector (3), adjusts wooden hair
The position of tubule (2) and gas flow make signal reach most strong；
4) writing scan data are to get the mass spectrogram for arriving sample ions.
Embodiment 2
The present embodiment is using wooden capillary electrospray ionisation device and mass spectrometer system (Thermo LCQ Fleet) is combined to analyze
Baicalein, and compared with metal capillary electron spray.Wooden capillary electrospray ionisation device is using described in embodiment 1
Wooden capillary electrospray ionisation device (Fig. 1), metal capillary electrospray device is using commercialization electrospray mass spectrometer
The electrospray device that (Thermo LCQ Fleet) is provided (for stainless steel material).
Sample solution is placed in syringe, by sample cell (5), three-way connector (3) inject wooden capillary (2) or
Metal capillary, sample flow rate are 5 μ L/min.In order to compare the two performance, auxiliary gas is not opened, and other parameters are adjusted to letter
It is number most strong.The operating method of wooden capillary electron spray is same as Example 1, using positive ionization electrospray mode.
It can be observed that the peak of metal capillary electron spray generation is more complicated from Fig. 2, there are the protonations of baicalein
Peak ([M+H]+, m/z 271) plus sodium peak ([M+Na]+, m/z 293), dimer plus sodium peak ([2M+Na]+, m/z 563), two
Polymers adds potassium peak ([2M+K]+, m/z 579), trimer plus sodium peak ([3M+Na]+, m/z 833) and trimer plus potassium
Peak ([3M+K]+, m/z 849), wherein the signal of two polyions is most strong, the signal of three polyions is also apparent from.However, wooden hair
The peak (Fig. 3) that tubule electron spray generates is relatively easy, and the protonation peak of baicalein is unique strong peak, and the signal of polymerization plasma is very
Low, the energy ratio metal material for illustrating that wooden capillary spray head generates is high, it is suppressed that the polymerization of target compound, therefore lead to wood
The signal (90000) that matter capillary electron spray generates is obviously stronger than the signal (10000) that metal capillary electron spray generates.
Embodiment 3
The present embodiment is using wooden capillary electrospray ionisation device and mass spectrometer system (Thermo LCQ Fleet) is combined to analyze
Rheum emodin, and compared with metal capillary electron spray.Wooden capillary electrospray ionisation device is using described in embodiment 1
Wooden capillary electrospray ionisation device (Fig. 1), metal capillary electrospray device is using commercialization electrospray mass spectrometer
The electrospray device that (Thermo LCQ Fleet) is provided (for stainless steel material).
Sample solution is placed in syringe, by sample cell (5), three-way connector (3) inject wooden capillary (2) or
Metal capillary, sample flow rate are 5 μ L/min.In order to compare the two performance, auxiliary gas is not opened, and other parameters are adjusted to letter
It is number most strong.The operating method of wooden capillary electron spray is same as Example 1, using negative electrospray mode.
The signal of the wooden capillary electron spray (Fig. 5) of rheum emodin will much be better than metal capillary electron spray (Fig. 4), signal
About high 2 orders of magnitude of intensity.Under normal conditions, it is existing to be easy to happen electric discharge under Negative electrospray ionization mode for metal capillary
As this electric discharge can seriously inhibit mass signal, therefore negative ion mode is usually smaller by one than positive ion mode EFI fog signal
A order of magnitude.Wooden is the non-conductor of electricity, and wooden electric conductivity is from the sample solution analyzed, therefore its electric discharge phenomena
Weaker than metal, signal inhibits also serious without metal capillary electron spray, and wooden capillary electron spray (Fig. 5) generates apparent
Rheum emodin dimer deprotonation ion (m/z 539) has confirmed this point just.By observing Fig. 4 it can be found that metal capillary
Complicated cell reaction has occurred in pipe electron spray, produces a series of small peaks, and wooden capillary electron spray (Fig. 5) does not have.
Wooden capillary generates high-intensitive mass signal in the negative ion mode, generates signal unlike metal capillary electron spray
Inhibit solve the problems, such as that current negative ion mode electrospray ionization mass spectrum signal is relatively low very well with the chemical reaction of complexity, it can be into one
Step improves the performance and efficiency of electrospray ionization mass spectrum.
Embodiment 4
The present embodiment is using wooden capillary electrospray ionisation device and mass spectrometer system (Thermo LCQ Fleet) is combined to analyze
Protein, and compared with metal capillary electron spray.Wooden capillary electrospray device is using described in embodiment 1 wooden
Capillary electrospray device (Fig. 1), metal capillary electrospray device is using commercialization electrospray mass spectrometer (Thermo LCQ
Fleet) the electrospray device provided (for stainless steel material).
Using myoglobins as sample, sample solution is placed in syringe, is infused by sample cell (5), three-way connector (3)
Enter wooden capillary (2) or metal capillary, sample flow rate is 5 μ L/min.In order to compare the two performance, auxiliary gas does not have
It opens, it is most strong that other parameters are adjusted to signal.The operating method of wooden capillary electron spray is same as Example 1, using just from
Sub- electrospray mode.
Fig. 6 and Fig. 7 is respectively the metal capillary electron spray of myoglobins and the cation mould of wooden capillary electron spray
Formula mass spectrogram.Myoglobins generates a series of ion of different charges as can be observed from Figure.Wooden capillary electron spray produces
Raw multiple-charged ion peak is to movement at high charge, and strongest mass spectra peak is+16 peaks (m/z 1060), and metal capillary is electric
Spraying (Fig. 6) highest peak is+14 peaks (m/z 1211), illustrates the charging efficiency of wooden capillary electron spray than metal capillary
Electron spray is high.Wooden have a porosity, porous to can increase electrode area, thus improve ionizing efficiency.Wooden capillary EFI
High an order of magnitude of signal intensity ratio metal capillary electron spray that mist generates, this research significance weight for life science
Greatly.
Embodiment 5
The present embodiment investigates wooden capillary electrospray ionisation device to the tolerance of sample high flow rate, and with metal capillary
Pipe electron spray compares.Wooden capillary electrospray device uses wooden capillary electrospray device (Fig. 1) described in embodiment 1
And mass spectrometer system (Thermo LCQ Fleet) is combined, metal capillary electrospray device is using commercialization electrospray mass spectrometer
The electrospray device that (Thermo LCQ Fleet) is provided (for stainless steel material).
Using glycine betaine as sample, sample solution is placed in syringe, is injected by sample cell (5), three-way connector (3)
Wooden capillary (2) or metal capillary.In order to compare the two performance, auxiliary gas is not opened, and other parameters are adjusted to letter
It is number most strong.The glycine betaine methanol solution flow velocity of 0.1 mg/ml be respectively set as 5 μ l/ min, 10 μ l/ min, 15 μ l/ min,
20μl/ min,25μl/ min,30μl/ min,35μl/ min,40μl/ min.The operating method of wooden capillary electron spray
It is same as Example 1, using positive ionization electrospray mode.
As shown in figure 8, wooden capillary EFI fog signal is significantly stronger than metal capillary electron spray under identical flow velocity.
With the increase of flow velocity, the signal that wooden capillary electron spray generates also enhances therewith, and what metal capillary electron spray generated
Signal then gradually weakens.Illustrate that wooden capillary electron spray is suitble to the detection of big flow velocity sample, higher sample flow can be resistant to
Speed.Although wooden non-conductive, porosity leads to have good electric conductivity when conveying sample solution, and porosity improves
The area of wooden capillary, improves ionizing efficiency.In addition, the diameter of spray droplet can be also effectively reduced in porosity, to have
Conducive to raising Ionization Efficiency.Secondly wooden itself electrochemical reaction to occur, all electric currents are all used in ionized sample
Compound, and electrochemical reaction can occur for metal itself, only one part of current is used for ionized sample, therefore ionizing efficiency is not so good as
It is wooden.In the case where electric discharge inhibition does not occur, electric current is stronger, and mass signal is stronger.Therefore, wooden capillary electron spray is than gold
Belong to capillary electron spray to be more suitable in conjunction with liquid chromatography technology.When test sample, first with liquid chromatogram high score from
Then ability utilizes the resistance to high flow rate characteristic of wooden capillary electron spray, and combine gas auxiliary gasification, can effectively improve
The sensitivity of high flow rate sample detection solves the problems, such as current liquid chromatography mass combination high flow rate sample sensitivity decline.
Embodiment 6
The present embodiment investigates wooden capillary electrospray ionisation device to the tolerance of high aqueous sample, and with metal capillary
Pipe electron spray compares.Wooden capillary electrospray ionisation device uses wooden capillary electrospray ionisation described in embodiment 1
Device (Fig. 1) simultaneously combines mass spectrometer system (Thermo LCQ Fleet), and metal capillary electrospray device is using commercialization EFI
The electrospray device that mist mass spectrograph (Thermo LCQ Fleet) provides (for stainless steel material).
Sample solution is placed in syringe, by sample cell (5), three-way connector (3) inject wooden capillary (2) or
Metal capillary.In order to compare the two performance, auxiliary gas is not opened, and it is most strong that other parameters are adjusted to signal.By glycine betaine mark
Quasi- product be dissolved separately in methanol, the methanol-water (80:20, V/V) containing 0.1% glacial acetic acid, the methanol-water containing 0.1% glacial acetic acid (60:
40, V/V) methanol-water (40:60, V/V), containing 0.1% glacial acetic acid, contains the methanol-water (20:80, V/V) containing 0.1% glacial acetic acid
The pure water of 0.1% glacial acetic acid, the alkali solution of beet for the 0.1mg/ml being configured to use metal capillary electron spray and wooden hair respectively
Tubule electron spray carries out sample detection.The operating method of wooden capillary electron spray is same as Example 1, using cation EFI
Mist mode.
Using metal capillary electron spray and wooden capillary electron spray to the sweet tea for being dissolved in different proportion solvent (methanol/water)
Dish alkali standard items are detected, and analysis result as shown in Figure 9 has been obtained.As shown in figure 9, the raising of the ratio with dampening, gold
Belonging to capillary electron spray and the mass signal of wooden capillary electron spray reduces.This is because the surface tension of water is larger, lead
Cause forms biggish spray droplet, is unfavorable for the gasification of sample, so that signal be made to reduce.It is from Fig. 9 it could be observed that identical
The mass signal of wooden capillary electron spray is stronger than the mass signal of metal capillary electron spray in the case of watr-proportion sample.
Because the cellular structure of wooden capillary can make the spray droplet generated smaller, this advantageously forms sample ions, therefore
The signal of generation is stronger.It could be observed that when the ratio of water in solvent is 20%, 40% and 60%, wooden capillary EFI
Mist generation signal strength is similar, and the signal strength of metal capillary electron spray then gradually reduces.When the ratio of water is 80%,
Mass signal is begun to decline.But even if in the case where pure water, the signal strength still phase of wooden capillary electron spray generation
When considerable, and the signal strength of metal capillary electron spray is very low.It is combined at present in liquid chromatography mass often frequently with gradient
Elution, but when gradient is larger, sensitivity is too in the detection to high water phase efflux for current metal capillary electron spray
It is low, and the characteristic of the resistance to high aqueous sample of wooden capillary electron spray is exactly able to solve this problem.
Claims (4)
1. a kind of wooden capillary Electrospray Ionization Mass Spectrometry method, comprising the following steps:
Step 1: a wooden capillary (2) is placed at mass spectrometer inlet,
Step 2: wooden capillary (2) making alive makes it constitute circuit with mass spectrometer inlet (1)；
Sample solution and nitrogen are transported in wooden capillary (2), sample solution is ionized inside wooden capillary (2),
Under gas auxiliary, formed by spraying at wooden capillary (2) tip, the ion of generation enters mass spectrum by mass spectrometer inlet (1)
Instrument is detected.
2. a kind of wooden capillary Electrospray Ionization Mass Spectrometry method as described in claim 1, it is characterized in that: used by step 2
Gas is nitrogen, flow velocity 0-600L/h.
3. a kind of wooden capillary electrospray ionisation device, the device is by wooden capillary (2), three-way connector (3), flue
(4), four parts such as sample cell (5) form；
Mass spectrometer inlet (1) is located at right end；Left end is wooden capillary (2), and the tip of wooden capillary (2) is placed on mass spectrum
At instrument entrance (1), the distance apart from mass spectrometer inlet (1) is 0.1-6cm, wooden capillary (2) and mass spectrometer inlet (1) axis
Angle be 0-90 °；The tail portion of wooden capillary (2) is connected with three-way connector (3), the other both ends of three-way connector (3)
It is connected respectively with flue (4) and sample cell (5), high voltage is applied directly on wooden capillary (2).
4. a kind of wooden capillary electrospray ionisation device as claimed in claim 3, it is characterized in that: the wooden capillary (2)
Internal diameter is 10-250 μm, length 1-5cm, and close to internal diameter, the tail end of capillary (2) is processed to point, makes the outer diameter at tip
Can be connected with three-way connector (3).
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| CN110455972B (en) * | 2019-08-21 | 2022-01-14 | 哈尔滨阿斯顿仪器有限公司 | Liquid chromatography-mass spectrometry combined analysis method and interface device used by same |
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| CN109632937B (en) | 2021-07-23 |
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