CN106053588B - A kind of rapid detection method of the alkyl phenol polyoxyethylene ether based on ion mobility spectrometry - Google Patents
A kind of rapid detection method of the alkyl phenol polyoxyethylene ether based on ion mobility spectrometry Download PDFInfo
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- CN106053588B CN106053588B CN201610390336.2A CN201610390336A CN106053588B CN 106053588 B CN106053588 B CN 106053588B CN 201610390336 A CN201610390336 A CN 201610390336A CN 106053588 B CN106053588 B CN 106053588B
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The invention discloses a kind of rapid detection methods of the alkyl phenol polyoxyethylene ether based on ion mobility spectrometry, include the following steps：(A) ion sputtering film coating capillary pipe spray ionization device is made：The assembling of preparation and ion sputtering film coating capillary pipe spray ionization device including plated film borosilicate glass capillary tube；(B) it is used for quickly detecting using ion mobility spectrometry：Testing sample solution is transferred to plated film borosilicate glass capillary tube, it is placed on the electric spray sample introduction mouth front end of ion mobility spectrometry host, sets ion mobility spectrometry host parameter, sample is ionized, it is detected through Faraday cup detector after being detached into migration tube, obtains corresponding collection of illustrative plates.While the rapid detection method of alkyl phenol polyoxyethylene ether of the present invention based on ion mobility spectrometry ensures detection data accuracy, substantially reduce testing cost, detection efficiency is improved, and the method that possible quick detection alkyl phenol polyoxyethylene ether is provided is detected for real-time online.
Description
Technical field
The present invention relates to a kind of detection methods, more particularly to a kind of quick detection alkyl phenol based on ion mobility spectrometry
The method of polyoxyethylene ether.
Background technology
Alkyl phenol polyoxyethylene ether is widely used in the necks such as weaving, plastics, rubber, daily-use chemical industry, medicine, papermaking, electronics
Domain is mainly used as textile auxiliary, detergent, emulsifier, wetting agent, stabilizer etc., is after fatty alcohol polyoxyethylene ether
Another major class nonionic surface active agent.It is most with nonylphenol polyoxyethylene ether in alkyl phenol polyoxyethylene ether, account for 80~
85%, octyl phenol polyoxyethylene ether accounts for 15% or so.The biodegradable metabolin of alkyl phenol polyoxyethylene ether is as a kind of interior point
Chaff interferent is secreted, can be accumulated in vivo, and human body is recycled by food chain, to human cancer cell's growth and fecundity
It will produce and seriously affect, there is potentially hazardous property to environment and human health.
And lack the detection method that can quickly detect alkyl phenol polyoxyethylene ether in the prior art.
Invention content
While ensuring detection data accuracy the technical problem to be solved in the present invention is to provide one kind, detection is substantially reduced
Cost improves detection efficiency, and detects the method for providing possible quick detection alkyl phenol polyoxyethylene ether for real-time online.
A kind of rapid detection method of the alkyl phenol polyoxyethylene ether based on ion mobility spectrometry, includes the following steps：
(A) ion sputtering film coating capillary pipe spray ionization device is made：Include the system of plated film borosilicate glass capillary tube
Standby and ion sputtering film coating capillary pipe spray ionization device assembling；
(B) it is used for quickly detecting using ion mobility spectrometry：Testing sample solution is transferred to plated film borosilicate glass
Capillary is placed on the electric spray sample introduction mouth front end of ion mobility spectrometry host, sets ion mobility spectrometry host parameter, sample
It is ionized, it is detected through Faraday cup detector after being detached into migration tube, obtains corresponding collection of illustrative plates.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention, wherein the alkyl phenol polyoxyethylene ether
Including nonylphenol polyoxyethylene ether and octyl phenol polyoxyethylene ether；
The parameter setting of the ion mobility spectrometry host is：
Source voltage：2500V, electron spray positive ion mode；
Migrate tube voltage：8000V；
Migration tube temperature：180℃；
Gas preheater temperature：180℃；
Spectrum width：26ms；
Ion fence gate pulse width：200μs；
Ion fence gate voltage：40V；
Drift about gas velocity：1.00L/min；
It is vented flow rate pump：0.60L/min.
For detecting the sample containing alkyl phenol polyoxyethylene ether using ion mobility spectrometry, further volume is used to arrange
Resistance chromatography mass spectrometry is confirmed.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention, wherein the ion sputtering film coating capillary
Pipe spraying ionization device includes ion mobility spectrometry host, plated film borosilicate glass capillary tube, holder, metal clip and power cord；
The ion mobility spectrometry host includes electric spray sample introduction mouth, and lens, the plated film boron are provided at the electric spray sample introduction mouth
The front end of silicate glass capillary is positioned close in place of the lens, and the front end of the holder is provided with fixed part, described
Fixed part is connected with the plated film borosilicate glass capillary tube, the rear end of the plated film borosilicate glass capillary tube with it is described
Metal clip is connected, and the metal clip is connected by the power cord with the High voltage output interface of the ion mobility spectrometry host；Institute
It states plated film borosilicate glass capillary tube to be made of the film layer of borosilicate glass capillary tube and setting on its external wall, the film
Layer is metal material.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention based on ion mobility spectrometry, wherein described
Metal material is high-purity gold, silver or platinum；The preparation method of the plated film borosilicate glass capillary tube includes borosilicate glass
The preparation of capillary and plated film；
The plated film includes the following steps：The borosilicate glass capillary tube prepared is lain in a horizontal plane in into ion sputtering instrument
On specimen holder, the borosilicate glass capillary tube surface distance sputter head 6cm is positioned over specimen holder centre position, to prevent
The borosilicate glass capillary tube rolls, and is fixed, and cover tightly sample cover, is vacuumized with carbon paste；Sputter gas is high-purity argon gas,
Purity is more than 99.9%, pressure 0.1Mpa, setting sputtering target material, sputtering current, sputtering time；After sputtering for the first time,
The borosilicate glass capillary tube rotation of side will be sputtered, sputter step has been repeated, until the entire borosilicate glass
Sputtering process is completed in glass capillary outer wall.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention based on ion mobility spectrometry, wherein described
Metal material is High Purity Gold, and the thickness of the film layer is 30~40nm, and sheet resistance is 30 ohms per squares, and gold is used in sputtering process
Sputtering target material, sputtering current 30mA, sputtering time 180s.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention based on ion mobility spectrometry, wherein described
Metal material is silver, and the thickness of the film layer is 30~40nm, and sheet resistance is 30 ohms per squares, and silver sputtering is used in sputtering process
Target, sputtering current 35mA, sputtering time 180s.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention based on ion mobility spectrometry, wherein described
Metal material is platinum, and the thickness of the film layer is 21~28nm, and sheet resistance is 32 ohms per squares, is sputtered using platinum in sputtering process
Target, sputtering current 35mA, sputtering time 180s.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention, wherein the ion sputtering film coating capillary
Pipe spraying ionization device further includes safety interlock, and the safety interlock is arranged on the ion mobility spectrometry host,
And close to the electric spray sample introduction mouth；The distance between the front end of the plated film borosilicate glass capillary tube and the lens are
3~5mm；The length of the plated film borosilicate glass capillary tube is 5cm, and the internal diameter at front end, that is, tip is 5~15 μm, the plating
The rear end outer diameter of film borosilicate glass capillary tube is 1.5mm, internal diameter 0.86mm；
The preparation method of the borosilicate glass capillary tube includes the following steps：By standard wall borosilicate glass blank
It is placed in the microelectrode to draw in instrument, the parameters that the microelectrode draws instrument is set, the microelectrode draws the items of instrument
Parameter is set as：450 DEG C, value of thrust 0N of heating temperature, rate 5 DEG C/s, circulation time 1s, air pressure 600hpa.
The rapid detection method of alkyl phenol polyoxyethylene ether of the present invention, wherein the size exclusion chromatograph-mass spectrum
Chromatographic parameter in method is set as：
Chromatographic column：The dual-purpose size exclusion chromatograph column of water solubility/oil-soluble；
Mobile phase：Acetonitrile-water system gradient elution, gradient elution program are shown in Table 1：
1 gradient elution program of table
Flow velocity：0.20mL/min；
Column temperature：50℃；
Sample size：10μL.
Mass spectrometry parameters in the size exclusion chromatograph-mass spectrography are set as：
Electric spray ion source：Positive ion mode；
Data acquisition scheme：Salbutamol Selected Ion Monitoring；
Capillary voltage：3.50kV；
Sample orifice potential：5V；
Radio-frequency lens voltage：0.3V；
Ion source temperature：120℃；
Remove solvent temperature degree：350℃；
Go solvent stream amount：350L/h；
Taper hole throughput：50L/h；
Collision cell entrance potential：50eV；
Collision cell voltage：2eV；
Collision cell exit potential：50eV；
Photoelectric multiplier voltage：650V.
According to the structure feature of alkyl phenol polyoxyethylene ether compound, it is easy to form stable adduct with sodium ion,
It is real even if can be acted on a small amount of sodium ion ubiquitous in environment if not being especially added with sodium ion alkyl phenol polyoxyethylene ether
It now ionizes, to observe [M ﹢ Na] compared with high abundance+Quasi-molecular ion peak.Select different polymerization degree alkylphenol-polyethenoxy
[the M ﹢ Na] of ether+Ion is monitored analysis as monitoring ion.The nonylphenol polyoxyethylene ether of different polymerization degree and not
Mass spectral analysis parameter with the octyl phenol polyoxyethylene ether of the degree of polymerization is shown in Table 2 and table 3.
The mass spectral analysis parameter of the nonylphenol polyoxyethylene ether of 2 different polymerization degree of table
The mass spectral analysis parameter of the octyl phenol polyoxyethylene ether of 3 different polymerization degree of table
The present invention is based on the rapid detection method of the alkyl phenol polyoxyethylene ether of ion mobility spectrometry unlike the prior art it
Be in：
The present invention is based on the rapid detection methods of the alkyl phenol polyoxyethylene ether of ion mobility spectrometry to ensure that detection data is accurate
Property while, greatly reduce testing cost, improve detection efficiency, and possible quick detection is provided for real-time online detection
The method of alkyl phenol polyoxyethylene ether.
Electric current can be conveyed from capillary outer wall by metal coating using ion sputtering film coating capillary, in capillary
The spraying of sample solution ionizes, simple operation, and spraying ionization effect is good, and still may be used when even if only having a small amount of solution in capillary
Realize the spraying ionization of solution.Thus metal microelectrode can be such as used, then capillary from using metal microelectrode to be inserted into capillary
Sample solution in pipe has to last for being kept in contact with metal microelectrode, when sample solution is consumed to and metal microelectrode front end point
From rear, then it can not continue spraying ionization.
Below in conjunction with the accompanying drawings to the rapid detection method of the alkyl phenol polyoxyethylene ether based on ion mobility spectrometry of the present invention
It is described further.
Description of the drawings
Fig. 1 is the overall structure diagram of intermediate ion sputter coating capillary pipe spray ionization device of the present invention；
Fig. 2 is the structural schematic diagram of the main part of intermediate ion sputter coating capillary pipe spray ionization device of the present invention；
Fig. 3 is the partial enlarged view in the areas Tu2Zhong T；
Fig. 4 is the ion transfer spectrogram for the octyl phenol polyoxyethylene ether that average degree of polymerization is 10 in the embodiment of the present invention；
Fig. 5 is the ion transfer spectrogram for the nonylphenol polyoxyethylene ether that average degree of polymerization is 9 in the embodiment of the present invention；
Fig. 6 is the ion transfer spectrogram for the nonylphenol polyoxyethylene ether that average degree of polymerization is 14 in the embodiment of the present invention；
Fig. 7 is the ion transfer spectrogram for the nonylphenol polyoxyethylene ether that average degree of polymerization is 15 in the embodiment of the present invention；
Fig. 8 is the ion transfer spectrogram for the nonylphenol polyoxyethylene ether that average degree of polymerization is 18 in the embodiment of the present invention；
Fig. 9 is the ion transfer spectrogram for the nonylphenol polyoxyethylene ether that average degree of polymerization is 20 in the embodiment of the present invention；
Figure 10 is size exclusion chromatograph-mass spectrum confirmation spectrogram of nonylphenol polyoxyethylene ether in the embodiment of the present invention；
Figure 11 is size exclusion chromatograph-mass spectrum confirmation spectrogram of octyl phenol polyoxyethylene ether in the embodiment of the present invention；
Figure 12 be the present invention in borosilicate glass capillary tube light microscope enlarged view (tip internal diameter be 5~15 μ
m)；
The Chinese control of the English occurred in all attached drawings of the present invention is as follows：
Intensity：Signal strength；Drift Time：Transit time；ms：Millisecond；Time：Time.
Specific implementation mode
Embodiment 1
One, instrument and device
(EXCELLIMS companies of the U.S., model GA2100 use tryptophan and citric acid to ion mobility spectrometry host using preceding
Rectify an instrument under negative ions pattern respectively), including ion fence gate controller, air filter, high-resolution ion move
Move analyzer, Faraday cup detector, instrument controlling and data processing system；Standard wall borosilicate glass blank (outer diameter
1.5mm, internal diameter 0.86mm)；Microelectrode draws instrument (SUTTER companies of the U.S., model P-1000)；Ion sputtering instrument (Britain
Cressington companies, model 108Auto types).
Two, reagent and material
Methanol (Fisher companies of the U.S.) is chromatographically pure；Tryptophan and citric acid (U.S. Sigma-Aldrich, with first
Alcohol is made into 10 μ g/mL and carries out instrumental correction)；Nonylphenol polyoxyethylene ether (average degree of polymerization 9) and octyl phenol polyoxyethylene ether
(average degree of polymerization 10) is purchased from ChemService companies of the U.S.) using methanol as the standard reserving solution of solvent preparation 1mg/mL, point
When analysis test 25 μ g/mL are diluted to homogeneous solvent.The characteristic ion of nonylphenol polyoxyethylene ether and octyl phenol polyoxyethylene ether
Migration spectrogram is shown in Fig. 4 and Fig. 5 respectively.
Three, experimental method：
(A) ion sputtering film coating capillary pipe spray ionization device is made：Include the system of plated film borosilicate glass capillary tube
Standby and ion sputtering film coating capillary pipe spray ionization device assembling；
As shown in FIG. 1 to 3, ion sputtering film coating capillary pipe spray ionization device includes ion mobility spectrometry host 1, plated film
Borosilicate glass capillary tube 3, holder 4, metal clip 5 and power cord 6；Ion mobility spectrometry host 1 includes electric spray sample introduction mouth,
Lens are provided at electric spray sample introduction mouth, the front end of plated film borosilicate glass capillary tube 3 is positioned close in place of lens, holder
4 front end 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, the High voltage output interface phase that metal clip 5 passes through power cord 6 and ion mobility spectrometry host 1
Even；Plated film borosilicate glass capillary tube 3 is made of the film layer of borosilicate glass capillary tube and setting on its external wall, film layer
For metal material.
Ion sputtering film coating capillary pipe spray ionization device further includes safety interlock 7, and the setting of safety interlock 7 exists
On ion mobility spectrometry host 1, and close to electric spray sample introduction mouth；Between the front end and lens of plated film borosilicate glass capillary tube 3
Distance be 3~5mm；The length of plated film borosilicate glass capillary tube 3 is 5cm, and the internal diameter at front end, that is, tip is 5~15 μm,
The rear end outer diameter of plated film borosilicate glass capillary tube 3 is 1.5mm, internal diameter 0.86mm.
The metal material is high-purity gold, silver or platinum；The preparation method of the plated film borosilicate glass capillary tube 3 includes
The preparation of borosilicate glass capillary tube and plated film；
The plated film includes the following steps：The borosilicate glass capillary tube prepared is lain in a horizontal plane in into ion sputtering instrument
On specimen holder, the borosilicate glass capillary tube surface distance sputter head 6cm is positioned over specimen holder centre position, to prevent
The borosilicate glass capillary tube rolls, and is fixed, and cover tightly sample cover, is vacuumized with carbon paste；Sputter gas is high-purity argon gas,
Purity is more than 99.9%, pressure 0.1Mpa, setting sputtering target material, sputtering current, sputtering time；After sputtering for the first time,
The borosilicate glass capillary tube rotation of side will be sputtered, sputter step has been repeated, until the entire borosilicate glass
Sputtering process is completed in glass capillary outer wall.
The preparation method of borosilicate glass capillary tube includes the following steps：Standard wall borosilicate glass blank is placed in
Microelectrode is drawn in instrument, and setting microelectrode draws the parameters of instrument, and the parameters that microelectrode draws instrument are set as：Heating temperature
450 DEG C, value of thrust 0N, 5 DEG C/s of rate of degree, circulation time 1 second, air pressure 600hpa.
The parameter of sputtering process be set as it is following it is several in one kind：
Metal material is High Purity Gold, and the thickness of the film layer is 30~40nm, and sheet resistance is 30 ohms per squares, sputtering process
It is middle to use golden sputtering target material, sputtering current 30mA, sputtering time 180s.
Metal material is silver, and the thickness of the film layer is 30~40nm, and sheet resistance is 30 ohms per squares, is made in sputtering process
With silver-colored sputtering target material, sputtering current 35mA, sputtering time 180s.
Metal material is platinum, and the thickness of the film layer is 21~28nm, and sheet resistance is 32 ohms per squares, is made in sputtering process
With platinum sputtering target material, sputtering current 35mA, sputtering time 180s.
(B) it is used for quickly detecting using ion mobility spectrometry：
It is detected using ion mobility spectrometry：Testing sample solution is transferred to plated film borosilicate glass capillary tube 3, by it
It is positioned over the electric spray sample introduction mouth front end of ion mobility spectrometry host 1,1 parameter of setting ion mobility spectrometry host, sample is ionized,
It is detected through Faraday cup detector after being detached into migration tube, obtains corresponding collection of illustrative plates.Testing sample solution need to be filled to plated film boron
The tip of silicate glass capillary 3, and bubble cannot be generated.
1 parameter setting of ion mobility spectrometry host is：
Source voltage：2500V, electron spray positive ion mode；
Migrate tube voltage：8000V；
Migration tube temperature：180℃；
Gas preheater temperature：180℃；
Spectrum width：26ms；
Ion fence gate pulse width：200μs；
Ion fence gate voltage：40V；
Drift about gas velocity：1.00L/min；
It is vented flow rate pump：0.60L/min.
It is confirmed using size exclusion chromatograph-mass spectrometry method：
Chromatographic parameter in size exclusion chromatograph of the present invention-mass spectrum confirmation method is set as：
Chromatographic column：The dual-purpose size exclusion chromatograph column of water solubility/oil-soluble；
Mobile phase：Acetonitrile-water system gradient elution, gradient elution program are shown in Table 1：
Flow velocity：0.20mL/min；
Column temperature：50℃；
Sample size：10μL.
1 gradient elution program of table
Mass spectrometry parameters in size exclusion chromatograph of the present invention-mass spectrum confirmation method are set as：
Electric spray ion source：Positive ion mode；
Data acquisition scheme：Salbutamol Selected Ion Monitoring；
Capillary voltage：3.50kV；
Sample orifice potential：5V；
Radio-frequency lens voltage：0.3V；
Ion source temperature：120℃；
Remove solvent temperature degree：350℃；
Go solvent stream amount：350L/h；
Taper hole throughput：50L/h；
Collision cell entrance potential：50eV；
Collision cell voltage：2eV；
Collision cell exit potential：50eV；
Photoelectric multiplier voltage：650V.
According to the structure feature of alkyl phenol polyoxyethylene ether compound, it is easy to form stable adduct with sodium ion,
It is real even if can be acted on a small amount of sodium ion ubiquitous in environment if not being especially added with sodium ion alkyl phenol polyoxyethylene ether
It now ionizes, to observe [M ﹢ Na] compared with high abundance+Quasi-molecular ion peak.Select different polymerization degree alkylphenol-polyethenoxy
[the M ﹢ Na] of ether+Ion is monitored analysis as monitoring ion.The nonylphenol polyoxyethylene ether of different polymerization degree with it is difference poly-
The mass spectral analysis parameter of right octyl phenol polyoxyethylene ether is shown in Table 2 and table 3 respectively.
The mass spectral analysis parameter of the nonylphenol polyoxyethylene ether of 2 different polymerization degree of table
The mass spectral analysis parameter of the octyl phenol polyoxyethylene ether of 3 different polymerization degree of table
Fig. 6~Fig. 9 is respectively the Nonyl pheno that average degree of polymerization is 14,15,18 and 20 in the embodiment of the present invention
The ion transfer spectrogram of ether；Figure 10 and Figure 11 be respectively in the embodiment of the present invention nonylphenol polyoxyethylene ether of different polymerization degree and
The size exclusion chromatograph of octyl phenol polyoxyethylene ether-mass spectrum confirmation spectrogram.
Four, result and analysis
1, the preparation of borosilicate glass capillary tube
The preparation key of borosilicate glass capillary tube is that the size that its tip internal diameter is drawn, internal diameter too conference lead to sample
Product spray effect is poor, and Ionization Efficiency is low, to seriously affect target substance sensitivity；It is too small, it is easy to cause tip clogs,
Sample solution is difficult to spray, and instrumental sensitivity is equally caused to decline even no signal.Therefore, the present invention is drawn by optimizing microelectrode
The key parameter of instrument processed, such as heating temperature and rate, draw a series of capillaries, calculate under an optical microscope in its tip
Diameter value selects the capillary of 5~15 μm of inner diameter sizes in tip as spraying source, to reach optimum ionisation effect.Figure 12 is this
The light microscope enlarged view of borosilicate glass capillary tube in invention (tip internal diameter is 5~15 μm).
2, the preparation of plated film borosilicate glass capillary tube
Plated film borosilicate glass capillary tube coating sputters, and is to be sputtered golden under argon atmosphere, spreads and deposit to hair
The process on tubule surface.The amount that gold is spread from target, i.e. rate of corrosion are not depend on the pressure of argon gas or the distance of sample,
And depend on sputtering current.It is worth noting that, sputtering current is 40mA, when sputtering time is 4500s, golden rate of corrosion meeting
Lead to target failure.When sputtering each time, the amount of gold deposition on the capillary will depend on two conditions, first, the pressure of argon gas
Power, second is that distance of the target to sample.So gold plate sputtering condition should optimize, it is finally reached most short sputtering time and obtains
Obtain best coating effect.Last set Sputtering Ar pressure is 0.1Mpa, and capillary surface is 6cm apart from sputter head, is splashed simultaneously
Radio stream is 30mA, sputtering time 180s.
3, the optimization of migration tube and sample introduction temperature degree
Influence situation of the variation to each PM signals intensity for having studied migration tube and sample introduction temperature degree, due to sample introduction gas and
The setting of migration tube temperature need to be consistent as possible, be migrated with reducing the ion characteristic caused by heat exchange or other factors
The problems such as time poor reproducibility, therefore, this experiment, are set to identical value to investigate when optimizing two kinds of parameters.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, the experimental results showed that,
The temperature of migration tube and sample introduction gas is improved in a certain range, it is possible to reduce air humidity or temperature believe ion under atmospheric environment
The influence of number intensity, reduces the halfwidth and position offset of quasi-molecular ions, to improve quasi-molecular ions resolution ratio；When temperature setting is excessively high
When, system can be caused unstable, and the excessively high caused ion diffusion of temperature and collision loss are also all the more serious, and ion is caused to be believed
Number weaken.The experimental results showed that showing as that signal is most strong, and therefore, method of the invention will move in the analysis process at 180 DEG C
It moves pipe and sample introduction temperature degree is set as 180 DEG C simultaneously.
4, detection limit
In the case where testing optimal condition, n nonylphenol polyoxyethylene ether and octyl phenol polyoxyethylene ether are detected analysis,
It is 3 calculating detection limits by signal-to-noise ratio, the detection of nonylphenol polyoxyethylene ether and octyl phenol polyoxyethylene ether is limited to 1 μ g/mL.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
It encloses and is defined, under the premise of not departing from design spirit of the present invention, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of rapid detection method of the alkyl phenol polyoxyethylene ether based on ion mobility spectrometry, it is characterised in that：Including as follows
Step：
(A) ion sputtering film coating capillary pipe spray ionization device is made：Preparation including plated film borosilicate glass capillary tube and
The assembling of ion sputtering film coating capillary pipe spray ionization device；
(B) it is used for quickly detecting using ion mobility spectrometry：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 host, sets ion mobility spectrometry host parameter, sample pass through from
Sonization detects through Faraday cup detector after being detached into migration tube, obtains corresponding collection of illustrative plates.
2. the rapid detection method of alkyl phenol polyoxyethylene ether according to claim 1, it is characterised in that：The alkyl phenol
Polyoxyethylene ether includes nonylphenol polyoxyethylene ether and octyl phenol polyoxyethylene ether；
The parameter setting of the ion mobility spectrometry host is：
Source voltage：2500V, electron spray positive ion mode；
Migrate tube voltage：8000V；
Migration tube temperature：180℃；
Gas preheater temperature：180℃；
Spectrum width：26ms；
Ion fence gate pulse width：200μs；
Ion fence gate voltage：40V；
Drift about gas velocity：1.00L/min；
It is vented flow rate pump：0.60L/min；
The rapid detection method of the alkyl phenol polyoxyethylene ether further includes following steps：For being detected using ion mobility spectrometry
Go out the sample containing alkyl phenol polyoxyethylene ether, is further confirmed using size exclusion chromatograph-mass spectrography.
3. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 2 based on ion mobility spectrometry, special
Sign is：The ion sputtering film coating capillary pipe spray ionization device includes ion mobility spectrometry host (1), plated film borosilicate glass
Glass capillary (3), holder (4), metal clip (5) and power cord (6)；The ion mobility spectrometry host (1) includes electric spray sample introduction
Mouthful, be provided with lens at the electric spray sample introduction mouth, the front end setting of the plated film borosilicate glass capillary tube (3) by
In place of the nearly lens, the front end of the holder (4) is provided with fixed part (2), the fixed part (2) and the plated film borosilicic acid
Salt capillary glass tube (3) is connected, and the rear end of the plated film borosilicate glass capillary tube (3) is connected with the metal clip (5), institute
Metal clip (5) is stated by the power cord (6) to be connected with the High voltage output interface of the ion mobility spectrometry host (1)；The plating
Film borosilicate glass capillary tube (3) is made of the film layer of borosilicate glass capillary tube and setting on its external wall, the film
Layer is metal material.
4. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 3 based on ion mobility spectrometry, special
Sign is：The metal material is high-purity gold, silver or platinum；The preparation method packet of the plated film borosilicate glass capillary tube (3)
Include preparation and the plated film of borosilicate glass capillary tube；
The plated film includes the following steps：The borosilicate glass capillary tube prepared is lain in a horizontal plane in into ion sputtering instrument sample
On seat, the borosilicate glass capillary tube surface distance sputter head 6cm is positioned over specimen holder centre position, described to prevent
Borosilicate glass capillary tube rolls, and is fixed, and cover tightly sample cover, is vacuumized with carbon paste；Sputter gas is high-purity argon gas, purity
More than 99.9%, pressure 0.1Mpa, setting sputtering target material, sputtering current, sputtering time；It, will after sputtering for the first time
The borosilicate glass capillary tube rotation for sputtering side, repeats sputter step, until the entire borosilicate glass hair
Sputtering process is completed in tubule outer wall.
5. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 4 based on ion mobility spectrometry, special
Sign is：The metal material is High Purity Gold, and the thickness of the film layer is 30~40nm, and sheet resistance is 30 ohms per squares, sputtering
Golden sputtering target material, sputtering current 30mA, sputtering time 180s are used in the process.
6. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 4 based on ion mobility spectrometry, special
Sign is：The metal material is silver, and the thickness of the film layer is 30~40nm, and sheet resistance is 30 ohms per squares, sputtering process
It is middle to use silver-colored sputtering target material, sputtering current 35mA, sputtering time 180s.
7. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 4 based on ion mobility spectrometry, special
Sign is：The metal material is platinum, and the thickness of the film layer is 21~28nm, and sheet resistance is 32 ohms per squares, sputtering process
It is middle to use platinum sputtering target material, sputtering current 35mA, sputtering time 180s.
8. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 4 based on ion mobility spectrometry, special
Sign is：The ion sputtering film coating capillary pipe spray ionization device further includes safety interlock (7), the safety interlocking dress
It sets (7) to be arranged on the ion mobility spectrometry host (1), and close to the electric spray sample introduction mouth；The plated film borosilicate glass
The distance between the front end of glass capillary (3) and the lens are 3~5mm；The plated film borosilicate glass capillary tube (3)
Length is 5cm, and the internal diameter at front end, that is, tip is 5~15 μm, and the rear end outer diameter of the plated film borosilicate glass capillary tube (3) is
1.5mm, internal diameter 0.86mm；
The preparation method of the borosilicate glass capillary tube includes the following steps：Standard wall borosilicate glass blank is placed in
Microelectrode is drawn in instrument, and the parameters that the microelectrode draws instrument are arranged, and the microelectrode draws the parameters setting of instrument
For：450 DEG C, value of thrust 0N of heating temperature, rate 5 DEG C/s, circulation time 1s, air pressure 600hpa.
9. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 2 based on ion mobility spectrometry, special
Sign is：Chromatographic parameter in the size exclusion chromatograph-mass spectrography is set as：
Chromatographic column：The dual-purpose size exclusion chromatograph column of water solubility/oil-soluble；
Mobile phase：Acetonitrile-water system gradient elution, gradient elution program are shown in Table 1：
1 gradient elution program of table
Flow velocity：0.20mL/min；
Column temperature：50℃；
Sample size：10μL.
10. the rapid detection method of the alkyl phenol polyoxyethylene ether according to claim 9 based on ion mobility spectrometry, special
Sign is：Mass spectrometry parameters in the size exclusion chromatograph-mass spectrography are set as：
Electric spray ion source：Positive ion mode；
Data acquisition scheme：Salbutamol Selected Ion Monitoring；
Capillary voltage：3.50kV；
Sample orifice potential：5V；
Radio-frequency lens voltage：0.3V；
Ion source temperature：120℃；
Remove solvent temperature degree：350℃；
Go solvent stream amount：350L/h；
Taper hole throughput：50L/h；
Collision cell entrance potential：50eV；
Collision cell voltage：2eV；
Collision cell exit potential：50eV；
Photoelectric multiplier voltage：650V；
The mass spectral analysis parameter of the nonylphenol polyoxyethylene ether of 2 different polymerization degree of table
The mass spectral analysis parameter of the octyl phenol polyoxyethylene ether of 3 different polymerization degree of table
The mass spectrum of the nonylphenol polyoxyethylene ether of different polymerization degree and the octyl phenol polyoxyethylene ether of different polymerization degree
Analysis parameter is shown in Table 2 and table 3.
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