CN106053588A - Rapid detection method of alkylphenol ethoxylate on basis of ion mobility spectrometry - Google Patents
Rapid detection method of alkylphenol ethoxylate on basis of ion mobility spectrometry Download PDFInfo
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- CN106053588A CN106053588A CN201610390336.2A CN201610390336A CN106053588A CN 106053588 A CN106053588 A CN 106053588A CN 201610390336 A CN201610390336 A CN 201610390336A CN 106053588 A CN106053588 A CN 106053588A
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/622—Ion mobility spectrometry
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a rapid detection method of alkylphenol ethoxylate on the basis of ion mobility spectrometry. The rapid detection method comprises steps as follows: (A), manufacture of an ion sputtering coating capillary tube spray ionization device: the manufacture comprises preparation of a coated borosilicate glass capillary tube and assembling of the ion sputtering coating capillary tube spray ionization device; (B) rapid detection with ion mobility spectrometry: a to-be-detected sample solution is transferred to the coated borosilicate glass capillary tube, the coated borosilicate glass capillary tube is put at the front end of an electric spray sample injection port of an ion mobility spectrometry host, parameters of the ion mobility spectrometry host are set, a sample is ionized and detected by a Faraday cup detector after being separated in a migration tube, and corresponding graphs are obtained. By means of the rapid detection method of alkylphenol ethoxylate on the basis of ion mobility spectrometry, the detection cost is greatly reduced and the detection efficiency is improved while the data detection accuracy is ensured, and the possible rapid alkylphenol ethoxylate detection method is provided for real-time online detection.
Description
Technical field
The present invention relates to a kind of detection method, particularly relate to a kind of based on ion mobility spectrometry quickly detect alkyl phenol
The method of polyoxyethylene ether.
Background technology
Alkylphenol polyoxyethylene is widely used in the necks such as weaving, plastics, rubber, daily-use chemical industry, medicine, papermaking, electronics
Territory, is mainly used as textile auxiliary, detergent, emulsifying agent, wetting agent, stabilizer etc., after fatty alcohol-polyoxyethylene ether
Another big class nonionic surfactant.In alkylphenol polyoxyethylene most with NPE, account for 80～
85%, OPEO accounts for about 15%.The biodegradation metabolite of alkylphenol polyoxyethylene is as in one point
Secrete chaff interference, can accumulate in vivo, and be recycled into human body by food chain, human cancer cell is increased and reproductive performance
All can produce and have a strong impact on, environment and human health are had potentially hazardous property.
And prior art lacks the detection method that can quickly detect alkylphenol polyoxyethylene.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and guarantees to detect while data accuracy, is substantially reduced detection
Cost, improves detection efficiency, and provides the possible method quickly detecting alkylphenol polyoxyethylene for real-time online detection.
The method for quick of a kind of alkylphenol polyoxyethylene based on ion mobility spectrometry, comprises the steps:
(A) ion sputtering film coating capillary pipe spray ionization device is made: include the system of plated film borosilicate glass capillary tube
The standby assembling with ion sputtering film coating capillary pipe spray ionization device；
(B) ion mobility spectrometry is used to be used for quickly detecting: testing sample solution is transferred to plated film borosilicate glass
Capillary tube, is placed on the electric spray sample introduction mouth front end of ion mobility spectrometry main frame, sets ion mobility spectrometry host parameter, sample
Ionized, enter after migration tube separates and detect through Faraday cup detector, obtain corresponding collection of illustrative plates.
The method for quick of alkylphenol polyoxyethylene of the present invention, wherein, described alkylphenol polyoxyethylene
Including NPE and OPEO；
The parameter of described ion mobility spectrometry main frame is set as:
Source voltage: 2500V, electron spray positive ion mode；
Migration tube voltage: 8000V；
Migration tube temperature: 180 DEG C；
Gas preheater temperature: 180 DEG C；
Spectrum width: 26ms；
Ion fence gate pulse width: 200 μ s；
Ion fence gate voltage: 40V；
Drift gas velocity: 1.00L/min；
Exhaust pump flow velocity: 0.60L/min.
For using ion mobility spectrometry to detect the sample containing alkylphenol polyoxyethylene, use volume row further
Resistance chromatography mass spectrometry is confirmed.
The method for quick of alkylphenol polyoxyethylene of the present invention, wherein, described ion sputtering film coating capillary
Pipe spraying ionization device includes ion mobility spectrometry main frame, plated film borosilicate glass capillary tube, support, metal clip and power line；
Described ion mobility spectrometry main frame includes electric spray sample introduction mouth, is provided with lens, described plated film boron at described electric spray sample introduction mouth
In place of the front end of silicate glass capillary tube is positioned close to described lens, the front end of described support is provided with fixed part, described
Fixed part is connected with described plated film borosilicate glass capillary tube, and the rear end of described plated film borosilicate glass capillary tube is with described
Metal clip is connected, and described metal clip is connected with the High voltage output interface of described ion mobility spectrometry main frame by described power line；Institute
State plated film borosilicate glass capillary tube to be made up of borosilicate glass capillary tube and setting film layer on its external wall, described film
Layer is metal material.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry of the present invention, wherein, described
Metal material is high-purity gold, silver or platinum；The preparation method of described plated film borosilicate glass capillary tube includes borosilicate glass
The preparation of capillary tube and plated film；
Described plated film comprises the steps: the borosilicate glass capillary tube prepared is lain in a horizontal plane in ion sputtering instrument
On specimen holder, described borosilicate glass capillary tube surface distance sputtering head 6cm, it is positioned over specimen holder centre position, for preventing
Described borosilicate glass capillary tube rolls, and fixes with carbon paste, and covers tightly sample cover, evacuation；Sputter gas is high-purity argon gas,
Purity is more than 99.9%, and pressure is 0.1Mpa, arranges sputtering target material, sputtering current, sputtering time；For the first time after sputtering,
The described borosilicate glass capillary tube sputtering side is rotated, repeats sputter step, until whole described borosilicate glass
Glass capillary tube outer wall has completed sputter procedure the most.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry of the present invention, wherein, described
Metal material is High Purity Gold, and the thickness of described film layer is 30～40nm, and sheet resistance is 30 ohms per squares, uses gold in sputter procedure
Sputtering target material, sputtering current is 30mA, and sputtering time is 180s.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry of the present invention, wherein, described
Metal material is silver, and the thickness of described film layer is 30～40nm, and sheet resistance is 30 ohms per squares, uses silver sputtering in sputter procedure
Target, sputtering current is 35mA, and sputtering time is 180s.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry of the present invention, wherein, described
Metal material is platinum, and the thickness of described film layer is 21～28nm, and sheet resistance is 32 ohms per squares, uses platinum sputtering in sputter procedure
Target, sputtering current is 35mA, and sputtering time is 180s.
The method for quick of alkylphenol polyoxyethylene of the present invention, wherein, described ion sputtering film coating capillary
Pipe spraying ionization device also includes that safety interlock, described safety interlock are arranged on described ion mobility spectrometry main frame,
And near described electric spray sample introduction mouth；Distance between front end and the described lens of described plated film borosilicate glass capillary tube is
3～5mm；The a length of 5cm of described plated film borosilicate glass capillary tube, the front end i.e. internal diameter at tip is 5～15 μm, described plating
The rear end external diameter of film borosilicate glass capillary tube is 1.5mm, and internal diameter is 0.86mm；
The preparation method of described borosilicate glass capillary tube comprises the steps: standard wall borosilicate glass blank
Being placed in described microelectrode to draw in instrument, arrange described microelectrode and draw the parameters of instrument, described microelectrode draws the every of instrument
Parameter is set to: heating-up temperature 450 DEG C, value of thrust 0N, 5 DEG C/s of speed, circulation time 1s, air pressure 600hpa.
The method for quick of alkylphenol polyoxyethylene of the present invention, wherein, described size exclusion chromatograph-mass spectrum
Chromatographic parameter in method is set as:
Chromatographic column: water solublity/oil-soluble dual-purpose size exclusion chromatograph post；
Flowing phase: acetonitrile-water system gradient elution, gradient elution program is shown in Table 1:
Table 1 gradient elution program
Flow velocity: 0.20mL/min；
Column temperature: 50 DEG C；
Sample size: 10 μ L.
Mass spectrometry parameters in described size exclusion chromatograph-mass spectrography is set as:
Electric spray ion source: positive ion mode；
Data acquisition scheme: Salbutamol Selected Ion Monitoring；
Capillary voltage: 3.50kV；
Sampling taper hole voltage: 5V；
Radio-frequency lens voltage: 0.3V；
Ion source temperature: 120 DEG C；
Go solvent gas temperature: 350 DEG C；
Remove solvent gas flow: 350L/h；
Taper hole throughput: 50L/h；
Collision cell entrance potential: 50eV；
Collision cell voltage: 2eV；
Collision cell exit potential: 50eV；
Photomultiplier voltage: 650V.
According to the architectural feature of alkylphenol polyoxyethylene compound, it is easily and sodium ion forms stable adduct,
Even if not being especially added with sodium ion, a small amount of sodium ion effect that alkylphenol polyoxyethylene also can be ubiquitous with environment, real
Existing ionizing, thus observe more abundant [M Na]+Quasi-molecular ion peak.Select different polymerization degree alkylphenol-polyethenoxy
[the M Na] of ether+Ion is monitored analyzing as monitoring ion.The described NPE of different polymerization degree and not
It is shown in Table 2 and table 3 with the mass spectral analysis parameter of the described OPEO of the degree of polymerization.
The mass spectral analysis parameter of the NPE of table 2 different polymerization degree
The mass spectral analysis parameter of the OPEO of table 3 different polymerization degree
The method for quick of present invention alkylphenol polyoxyethylene based on ion mobility spectrometry unlike the prior art it
Place is:
It is accurate that the method for quick of present invention alkylphenol polyoxyethylene based on ion mobility spectrometry guarantees to detect data
While property, greatly reduce testing cost, improve detection efficiency, and provide possible quick detection for real-time online detection
The method of alkylphenol polyoxyethylene.
Use ion sputtering film coating capillary tube can carry electric current by metal coating from capillary tube outer wall, in capillary tube
Sample solution spraying ionization, simple operation, spraying ionization effective, even and if capillary tube in only have a small amount of solution time still may be used
Realize the spraying ionization of solution.Thus can avoid using metal microelectrode to insert capillary tube, as used metal microelectrode, then capillary
Sample solution in pipe has to last for keeping contacting, when sample solution is consumed to divide with metal microelectrode front end with metal microelectrode
From rear, then cannot continue spraying ionization.
Method for quick to the alkylphenol polyoxyethylene based on ion mobility spectrometry of the present invention below in conjunction with the accompanying drawings
It is described further.
Accompanying drawing explanation
Fig. 1 is the overall structure schematic diagram of intermediate ion sputter coating capillary pipe spray ionization device of the present invention；
Fig. 2 is the structural representation of the main part of intermediate ion sputter coating capillary pipe spray ionization device of the present invention；
Fig. 3 is the partial enlarged drawing in Tu2Zhong T district；
Fig. 4 is that in the embodiment of the present invention, average degree of polymerization is the ion migration spectrogram of the OPEO of 10；
Fig. 5 is that in the embodiment of the present invention, average degree of polymerization is the ion migration spectrogram of the NPE of 9；
Fig. 6 is that in the embodiment of the present invention, average degree of polymerization is the ion migration spectrogram of the NPE of 14；
Fig. 7 is that in the embodiment of the present invention, average degree of polymerization is the ion migration spectrogram of the NPE of 15；
Fig. 8 is that in the embodiment of the present invention, average degree of polymerization is the ion migration spectrogram of the NPE of 18；
Fig. 9 is that in the embodiment of the present invention, average degree of polymerization is the ion migration spectrogram of the NPE of 20；
Figure 10 is the size exclusion chromatograph of NPE-mass spectrum confirmation spectrogram in the embodiment of the present invention；
Figure 11 is the size exclusion chromatograph of OPEO-mass spectrum confirmation spectrogram in the embodiment of the present invention；
Figure 12 is that (most advanced and sophisticated internal diameter is 5～15 μ for the optical microscope zoomed-in view of borosilicate glass capillary tube in the present invention
m)；
The English Chinese occurred in all accompanying drawings of the present invention compares as follows:
Intensity: signal intensity；Drift Time: migration time；Ms: millisecond；Time: the time.
Detailed description of the invention
Embodiment 1
One, instrument and device
(EXCELLIMS company of the U.S., model is GA2100 to ion mobility spectrometry main frame, uses front tryptophan and citric acid
Rectify an instrument under negative ions pattern respectively), move including ion fence gate controller, air filter, high-resolution ion
Move analyzer, Faraday cup detector, instrument controlling and data handling system；Standard wall borosilicate glass blank (external diameter
1.5mm, internal diameter 0.86mm)；Microelectrode draws instrument (SUTTER company of the U.S., model is P-1000)；Ion sputtering instrument (Britain
Cressington company, model is 108Auto type).
Two, reagent and material
Methanol (Fisher company of the U.S.) is chromatographically pure；(U.S. Sigma-Aldrich, with first for tryptophan and citric acid
Alcohol is made into 10 μ g/mL and carries out instrumental correction)；NPE (average degree of polymerization is 9) and OPEO
(average degree of polymerization is 10) is purchased from ChemService company of the U.S.) with the standard reserving solution that methanol is solvent preparation 1mg/mL, divide
It is diluted to 25 μ g/mL with homogeneous solvent during analysis test.NPE and the characteristic ion of OPEO
Migrate spectrogram and see Fig. 4 and Fig. 5 respectively.
Three, experimental technique:
(A) ion sputtering film coating capillary pipe spray ionization device is made: include the system of plated film borosilicate glass capillary tube
The standby assembling with ion sputtering film coating capillary pipe spray ionization device；
As shown in FIG. 1 to 3, ion sputtering film coating capillary pipe spray ionization device includes ion mobility spectrometry main frame 1, plated film
Borosilicate glass capillary tube 3, support 4, metal clip 5 and power line 6；Ion mobility spectrometry main frame 1 includes electric spray sample introduction mouth,
Lens it are provided with at electric spray sample introduction mouth, in place of the front end of plated film borosilicate glass capillary tube 3 is positioned close to lens, support
The front end of 4 is provided with fixed part 2, and fixed part 2 is connected with plated film borosilicate glass capillary tube 3, plated film borosilicate glass hair
The rear end of tubule 3 is connected with metal clip 5, and metal clip 5 is by the High voltage output interface phase of power line 6 with ion mobility spectrometry main frame 1
Even；Plated film borosilicate glass capillary tube 3 is made up of borosilicate glass capillary tube and setting film layer on its external wall, film layer
For metal material.
Ion sputtering film coating capillary pipe spray ionization device also includes that safety interlock 7, safety interlock 7 are arranged on
On ion mobility spectrometry main frame 1, and near electric spray sample introduction mouth；Between front end and the lens of plated film borosilicate glass capillary tube 3
Distance be 3～5mm；The a length of 5cm of plated film borosilicate glass capillary tube 3, the front end i.e. internal diameter at tip is 5～15 μm,
The rear end external diameter of plated film borosilicate glass capillary tube 3 is 1.5mm, and internal diameter is 0.86mm.
Described metal material is high-purity gold, silver or platinum；The preparation method of described plated film borosilicate glass capillary tube 3 includes
The preparation of borosilicate glass capillary tube and plated film；
Described plated film comprises the steps: the borosilicate glass capillary tube prepared is lain in a horizontal plane in ion sputtering instrument
On specimen holder, described borosilicate glass capillary tube surface distance sputtering head 6cm, it is positioned over specimen holder centre position, for preventing
Described borosilicate glass capillary tube rolls, and fixes with carbon paste, and covers tightly sample cover, evacuation；Sputter gas is high-purity argon gas,
Purity is more than 99.9%, and pressure is 0.1Mpa, arranges sputtering target material, sputtering current, sputtering time；For the first time after sputtering,
The described borosilicate glass capillary tube sputtering side is rotated, repeats sputter step, until whole described borosilicate glass
Glass capillary tube outer wall has completed sputter procedure the most.
The preparation method of borosilicate glass capillary tube comprises the steps: to be placed in standard wall borosilicate glass blank
Microelectrode draws in instrument, arranges microelectrode and draws the parameters of instrument, and microelectrode draws the parameters of instrument and is set to: heating temperature
Spend 450 DEG C, value of thrust 0N, 5 DEG C/s of speed, circulation time 1 second, air pressure 600hpa.
The parameter of sputter procedure be set to following several in one:
Metal material is High Purity Gold, and the thickness of described film layer is 30～40nm, and sheet resistance is 30 ohms per squares, sputter procedure
Middle use gold sputtering target material, sputtering current is 30mA, and sputtering time is 180s.
Metal material is silver, and the thickness of described film layer is 30～40nm, and sheet resistance is 30 ohms per squares, makes in sputter procedure
With silver sputtering target material, sputtering current is 35mA, and sputtering time is 180s.
Metal material is platinum, and the thickness of described film layer is 21～28nm, and sheet resistance is 32 ohms per squares, makes in sputter procedure
Using platinum sputtering target material, sputtering current is 35mA, and sputtering time is 180s.
(B) ion mobility spectrometry is used to be used for quickly detecting:
Employing ion mobility spectrometry detects: testing sample solution is transferred to plated film borosilicate glass capillary tube 3, by it
Being positioned over the electric spray sample introduction mouth front end of ion mobility spectrometry main frame 1, set ion mobility spectrometry main frame 1 parameter, sample is ionized,
Enter after migration tube separates and detect through Faraday cup detector, obtain corresponding collection of illustrative plates.Testing sample solution need to fill to plated film boron
The tip of silicate glass capillary tube 3, and bubble can not be produced.
Ion mobility spectrometry main frame 1 parameter is set as:
Source voltage: 2500V, electron spray positive ion mode；
Migration tube voltage: 8000V；
Migration tube temperature: 180 DEG C；
Gas preheater temperature: 180 DEG C；
Spectrum width: 26ms；
Ion fence gate pulse width: 200 μ s；
Ion fence gate voltage: 40V；
Drift gas velocity: 1.00L/min；
Exhaust pump flow velocity: 0.60L/min.
Size exclusion chromatograph-mass spectrometry method is used to confirm:
Chromatographic parameter in size exclusion chromatograph of the present invention-mass spectrum confirmation method is set as:
Chromatographic column: water solublity/oil-soluble dual-purpose size exclusion chromatograph post；
Flowing phase: acetonitrile-water system gradient elution, gradient elution program is shown in Table 1:
Flow velocity: 0.20mL/min；
Column temperature: 50 DEG C；
Sample size: 10 μ L.
Table 1 gradient elution program
Mass spectrometry parameters in size exclusion chromatograph of the present invention-mass spectrum confirmation method is set as:
Electric spray ion source: positive ion mode；
Data acquisition scheme: Salbutamol Selected Ion Monitoring；
Capillary voltage: 3.50kV；
Sampling taper hole voltage: 5V；
Radio-frequency lens voltage: 0.3V；
Ion source temperature: 120 DEG C；
Go solvent gas temperature: 350 DEG C；
Remove solvent gas flow: 350L/h；
Taper hole throughput: 50L/h；
Collision cell entrance potential: 50eV；
Collision cell voltage: 2eV；
Collision cell exit potential: 50eV；
Photomultiplier voltage: 650V.
According to the architectural feature of alkylphenol polyoxyethylene compound, it is easily and sodium ion forms stable adduct,
Even if not being especially added with sodium ion, a small amount of sodium ion effect that alkylphenol polyoxyethylene also can be ubiquitous with environment, real
Existing ionizing, thus observe more abundant [M Na]+Quasi-molecular ion peak.Select different polymerization degree alkylphenol-polyethenoxy
[the M Na] of ether+Ion is monitored analyzing as monitoring ion.The NPE of different polymerization degree is with difference poly-
The mass spectral analysis parameter of right OPEO is shown in Table 2 and table 3 respectively.
The mass spectral analysis parameter of the NPE of table 2 different polymerization degree
The mass spectral analysis parameter of the OPEO of table 3 different polymerization degree
In Fig. 6～Fig. 9 respectively embodiment of the present invention, average degree of polymerization is the Nonyl pheno of 14,15,18 and 20
The ion migration spectrogram of ether；Figure 10 and Figure 11 be respectively in the embodiment of the present invention NPE of different polymerization degree and
The size exclusion chromatograph of OPEO-mass spectrum confirmation spectrogram.
Four, result and analysis
1, the preparation of borosilicate glass capillary tube
The preparation of borosilicate glass capillary tube it is critical only that the size that its most advanced and sophisticated internal diameter draws, and internal diameter too conference causes sample
Product spray effect is poor, and Ionization Efficiency is low, thus has a strong impact on target substance sensitivity；The least, easily cause tip clogs,
Sample solution is difficult to spray, and causes instrumental sensitivity to decline even no signal equally.Therefore, the present invention draws by optimizing microelectrode
The key parameter of instrument processed, such as heating-up temperature and speed etc., draws a series of capillary tube, calculates under an optical microscope in its tip
Footpath is worth, and the capillary tube of the most advanced and sophisticated 5～15 μm internal diameter sizes of selection is as spraying source, to reach optimum ionisation effect.Figure 12 is this
The optical microscope zoomed-in view (most advanced and sophisticated internal diameter is 5～15 μm) of borosilicate glass capillary tube in invention.
2, the preparation of plated film borosilicate glass capillary tube
Plated film borosilicate glass capillary tube coating sputter, be gold to be sputtered under argon atmosphere, spread and deposit to hair
The process on tubule surface.Gold is the amount of diffusion, i.e. rate of corrosion from target, is not depend on the pressure of argon or the distance of sample,
And depend on sputtering current.It should be noted that and be 40mA at sputtering current, when sputtering time is 4500s, the rate of corrosion meeting of gold
Cause target fault.When sputtering each time, gold deposition amount on the capillary to depend on two conditions, and one is the pressure of argon
Power, two is the target distance to sample.So, gold plate sputtering condition should be optimized, and is finally reached the shortest sputtering time and obtains
Obtain optimal coating effect.Last set Sputtering Ar pressure is 0.1Mpa, and capillary surface distance sputtering head is 6cm, spatters simultaneously
Radio stream is 30mA, and sputtering time is 180s.
3, migration tube and the optimization of sample introduction temperature
Have studied the change of migration tube and sample introduction temperature and each PM signals intensity affected situation, due to sample introduction gas and
Arranging of migration tube temperature need to keep consistent as far as possible, to reduce the ion characteristic migration caused due to heat exchange or other factors
The problems such as time poor reproducibility, therefore, this experiment is when optimizing two kinds of parameters, it is set to identical value is investigated.Set one
Series of temperatures (160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C), records the signal strength values of each ion, test result indicate that,
Improve migration tube and the temperature of sample introduction gas within the specific limits, it is possible to reduce under atmospheric environment, ion is believed by air humidity or temperature
The impact of number intensity, reduces halfwidth and the position skew of quasi-molecular ions, thus improves quasi-molecular ions resolution；When temperature arranges too high
Time, system can be caused unstable, and the too high ion diffusion caused of temperature and collision loss are the most serious, cause ion to be believed
Number weaken.Test result indicate that, show as signal the strongest at 180 DEG C, therefore, the method for the present invention will be moved during analyzing
Move pipe and sample introduction temperature is simultaneously set to 180 DEG C.
4, detection limit
Under experiment optimal condition, n nonylphenol polyoxyethylene ether and OPEO carry out detection and analyze,
Being 3 calculating detection limits by signal to noise ratio, the detection of NPE and OPEO is limited to 1 μ g/mL.
Embodiment described above is only to be described the preferred embodiment of the present invention, the not model to the present invention
Enclose and be defined, on the premise of designing spirit without departing from the present invention, the those of ordinary skill in the art technical side to the present invention
Various deformation that case is made and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (10)
1. the method for quick of an alkylphenol polyoxyethylene based on ion mobility spectrometry, it is characterised in that: include as follows
Step:
(A) make ion sputtering film coating capillary pipe spray ionization device: include plated film borosilicate glass capillary tube preparation and
The assembling of ion sputtering film coating capillary pipe spray ionization device；
(B) ion mobility spectrometry is used to be used for quickly detecting: testing sample solution is transferred to plated film borosilicate glass capillary
Pipe, is placed on the electric spray sample introduction mouth front end of ion mobility spectrometry main frame, sets ion mobility spectrometry host parameter, sample through from
Sonization, enters after migration tube separates and detects through Faraday cup detector, obtain corresponding collection of illustrative plates.
The method for quick of alkylphenol polyoxyethylene the most according to claim 1, it is characterised in that: described alkyl phenol
Polyoxyethylene ether includes NPE and OPEO；
The parameter of described ion mobility spectrometry main frame is set as:
Source voltage: 2500V, electron spray positive ion mode；
Migration tube voltage: 8000V；
Migration tube temperature: 180 DEG C；
Gas preheater temperature: 180 DEG C；
Spectrum width: 26ms；
Ion fence gate pulse width: 200 μ s；
Ion fence gate voltage: 40V；
Drift gas velocity: 1.00L/min；
Exhaust pump flow velocity: 0.60L/min；
The method for quick of described alkylphenol polyoxyethylene also comprises the steps: for using ion mobility spectrometry detection
Go out the sample containing alkylphenol polyoxyethylene, use size exclusion chromatograph-mass spectrography to confirm further.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 2, it is special
Levy and be: described ion sputtering film coating capillary pipe spray ionization device includes ion mobility spectrometry main frame (1), plated film borosilicate glass
Glass capillary tube (3), support (4), metal clip (5) and power line (6)；Described ion mobility spectrometry main frame (1) includes electric spray sample introduction
Mouthful, at described electric spray sample introduction mouth, it being provided with lens, the front end of described plated film borosilicate glass capillary tube (3) is arranged on to be leaned on
In place of nearly described lens, the front end of described support (4) is provided with fixed part (2), described fixed part (2) and described plated film borosilicic acid
Salt capillary glass tube (3) is connected, and the rear end of described plated film borosilicate glass capillary tube (3) is connected with described metal clip (5), institute
State metal clip (5) to be connected with the High voltage output interface of described ion mobility spectrometry main frame (1) by described power line (6)；Described plating
Film borosilicate glass capillary tube (3) is made up of borosilicate glass capillary tube and setting film layer on its external wall, described film
Layer is metal material.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 3, it is special
Levy and be: described metal material is high-purity gold, silver or platinum；The preparation method bag of described plated film borosilicate glass capillary tube (3)
Include preparation and the plated film of borosilicate glass capillary tube；
Described plated film comprises the steps: the borosilicate glass capillary tube prepared is lain in a horizontal plane in ion sputtering instrument sample
On seat, described borosilicate glass capillary tube surface distance sputtering head 6cm, it is positioned over specimen holder centre position, described for preventing
Borosilicate glass capillary tube rolls, and fixes with carbon paste, and covers tightly sample cover, evacuation；Sputter gas is high-purity argon gas, purity
More than 99.9%, pressure is 0.1Mpa, arranges sputtering target material, sputtering current, sputtering time；For the first time after sputtering, by
The described borosilicate glass capillary tube of sputtering side rotates, and repeats sputter step, until whole described borosilicate glass hair
Tubule outer wall has completed sputter procedure the most.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 4, it is special
Levying and be: described metal material is High Purity Gold, the thickness of described film layer is 30～40nm, and sheet resistance is 30 ohms per squares, sputtering
During use gold sputtering target material, sputtering current is 30mA, and sputtering time is 180s.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 4, it is special
Levy and be: described metal material is silver, and the thickness of described film layer is 30～40nm, and sheet resistance is 30 ohms per squares, sputter procedure
Middle use silver sputtering target material, sputtering current is 35mA, and sputtering time is 180s.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 4, it is special
Levying and be: described metal material is platinum, the thickness of described film layer is 21～28nm, and sheet resistance is 32 ohms per squares, sputter procedure
Middle use platinum sputtering target material, sputtering current is 35mA, and sputtering time is 180s.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 4, it is special
Levying and be: described ion sputtering film coating capillary pipe spray ionization device also includes safety interlock (7), described safety interlocking fills
Put (7) to be arranged on described ion mobility spectrometry main frame (1), and near described electric spray sample introduction mouth；Described plated film borosilicate glass
Distance between front end and the described lens of glass capillary tube (3) is 3～5mm；Described plated film borosilicate glass capillary tube (3)
A length of 5cm, the front end i.e. internal diameter at tip is 5～15 μm, and the rear end external diameter of described plated film borosilicate glass capillary tube (3) is
1.5mm, internal diameter is 0.86mm；
The preparation method of described borosilicate glass capillary tube comprises the steps: to be placed in standard wall borosilicate glass blank
Described microelectrode draws in instrument, arranges described microelectrode and draws the parameters of instrument, and described microelectrode draws the parameters of instrument
It is set to: heating-up temperature 450 DEG C, value of thrust 0N, 5 DEG C/s of speed, circulation time 1s, air pressure 600hpa.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 2, it is special
Levy and be: the chromatographic parameter in described size exclusion chromatograph-mass spectrography is set as:
Chromatographic column: water solublity/oil-soluble dual-purpose size exclusion chromatograph post；
Flowing phase: acetonitrile-water system gradient elution, gradient elution program is shown in Table 1:
Table 1 gradient elution program
Flow velocity: 0.20mL/min；
Column temperature: 50 DEG C；
Sample size: 10 μ L.
The method for quick of alkylphenol polyoxyethylene based on ion mobility spectrometry the most according to claim 9, it is special
Levy and be: the mass spectrometry parameters in described size exclusion chromatograph-mass spectrography is set as:
Electric spray ion source: positive ion mode；
Data acquisition scheme: Salbutamol Selected Ion Monitoring；
Capillary voltage: 3.50kV；
Sampling taper hole voltage: 5V；
Radio-frequency lens voltage: 0.3V；
Ion source temperature: 120 DEG C；
Go solvent gas temperature: 350 DEG C；
Remove solvent gas flow: 350L/h；
Taper hole throughput: 50L/h；
Collision cell entrance potential: 50eV；
Collision cell voltage: 2eV；
Collision cell exit potential: 50eV；
Photomultiplier voltage: 650V；
The mass spectral analysis parameter of the NPE of table 2 different polymerization degree
The mass spectral analysis parameter of the OPEO of table 3 different polymerization degree
The described NPE of different polymerization degree and the mass spectrum of the described OPEO of different polymerization degree
Analytical parameters is shown in Table 2 and table 3.
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| CN107543861A (en) * | 2016-11-09 | 2018-01-05 | 中国检验检疫科学研究院 | A kind of plasticine testing sample preparation facilities for capillary pipe spray ionization detection |
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