CN103149283A - Analyzing device and analyzing method for trace impurities in organic pure substance - Google Patents
Analyzing device and analyzing method for trace impurities in organic pure substance Download PDFInfo
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- CN103149283A CN103149283A CN2013100365152A CN201310036515A CN103149283A CN 103149283 A CN103149283 A CN 103149283A CN 2013100365152 A CN2013100365152 A CN 2013100365152A CN 201310036515 A CN201310036515 A CN 201310036515A CN 103149283 A CN103149283 A CN 103149283A
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Abstract
The invention discloses an analyzing device and an analyzing method for trace impurities in an organic pure substance. The device comprises a liquid chromatograph, a cutting valve, an ionization source and a mass spectrometer, wherein the ionization source is based on plasma bodies and comprises an atomizer and a corona spray point. The liquid chromatograph is sequentially connected with the cutting valve, the atomizer, the corona spray point and the mass spectrometer. The method includes that a sample is sent into the liquid chromatograph and sequentially passes through the cutting valve and the ionization source based on the plasma bodies and the impurities in the sample are ionized and sent into the mass spectrometer. By utilization of the chemical ionization source based on the plasma bodies, not only can polarity impurity molecules and weak polarity impurity molecules be ionized, but also non-polar molecules can be ionized. Impurity ions of which main components are cut are sent into the mass spectrometer and then can be analyzed in terms of quality accordingly so that qualitative information of the impurity molecules is obtained.
Description
Technical field
The present invention relates to the analytical technique of mass spectrum field, furtherly, relate to trace impurity analytical equipment and analytical approach in a kind of organic pure material.
Background technology
Stoichiometry is the science that specializes in chemistry is measured, and is the technical support of chemical measurement, is to realize the unification of chemical measurement unit, value technical foundation accurately and reliably.The research of standard substance is one of stoichiometric important research content, and the sterling standard substance is the basis of solution and the research of complicated substrate standard substance, and the pure material purity determination is the key of sterling Developments of certified reference samples.Developed country such as the U.S. (NIST), Germany (BAM), Britain (LGC), Japan (NMIJ), Australia countries such as (NARL) recognize that generally the measurement capability of sterling is the important foundation of standard substance research.Amount of substance advisory committee of International Bureau of Wieghts and Measurements (BIPM) (CCQM) once repeatedly organized the international comparison of organic compound purity determination ability, such as CCQM-P20A benzoic acid, antifebrin purity determination; CCQM-P20B P-xylene purity determination; The CCQM-P20C Atrazine; The CCQM-P20D chlopyrifos; CCQM-K55b drinox etc.Can find out, international metering thinks that all the time the organic compound purity determination is the basis of organic standard substance research, adhere to organizing every year the purity comparison of organic compound, and progressively form a research series, from the base standard material, Organic chemical products of beginning to agricultural chemicals, difficulty is increasing successively, requires more and more higher to the measurement capability of analyzing.
At first, the purity definite value of organic pure material adopts the chromatogram normalization method, suppose that namely in pure material, major component is similar to contaminant characteristics, has identical response signal in the definite value process, yet the generally response of major component and impurity is also inconsistent, so normalization method can affect the accuracy of purity definite value result.Present International Bureau of Wieghts and Measurements is carrying out the mode of impurity deduction pure material is being carried out definite value, at first the impurity in the sterling material is carried out qualitative and quantitative analysis, obtains the purity of pure material major component by the mode of reducing.Therefore, impurity analysis is the key of pure substance standard material development accurately.Often adopt inductivity coupled plasma mass spectrometry (ICP-MS) technology to carry out qualitative, quantitative measurment for the inorganic constituents in impurity; Often adopt Ka Erfei to amend the law to measure for traces of moisture in impurity; Measure and adopt head space-gas chromatography/mass spectrometry technology to carry out quantitative and qualitative analysis to the volatile organic matter in impurity; And be the bottleneck of impurity measurement in pure material to the quantitative and qualitative analysis with the similar organic impurities of major component structure.
At present, in high purity material, the analytical approach of impurity mainly contains: gas chromatography/mass spectrometry technology, liquid chromatography/mass spectrometry coupling technique.But existing application of gas chromatorgraphy/mass technology exists obviously not enough to the qualitative ability of impurity.Owing to needing in the gas chromatography detachment process that sample is heated to several Baidu, the gas chromatography/mass spectrometry technology can only be analyzed the organic substance of Heat stability is good, the organic substance of poor heat stability can decompose in the gas chromatography detachment process, thereby affects final quantitative and qualitative analysis result.For the liquid chromatography/mass spectrometry coupling technique, carry out at normal temperatures chromatographic resolution, can not cause the sample thermal decomposition, and the sample after chromatographic resolution need be ionized before entering mass spectrum, be namely charged ion from neutral molecular change.But the commercialization ion gun that is used at present liquid chromatograph mass spectrography has two kinds: electric spray ion source and Atmosphere Pressure Chemical Ionization (APCI) source, electron spray is suitable for the ionization of polar molecule, the Atmosphere Pressure Chemical Ionization (APCI) source can be used for the ionization of polarity and low pole molecule, and for the ionization of non-polar molecule, these two kinds of commercialization ion guns just seem helpless.
Summary of the invention
For solving problems of the prior art, the invention provides trace impurity analytical equipment and analytical approach in a kind of organic pure material.The present invention adopts the organic impurities molecule that not only can ionize polarity and low pole based on the chemical ionization source of plasma, simultaneously ionizable nonpolar organic molecule; Foreign ion can carry out corresponding quality analysis after entering mass spectrometer, thereby obtains the qualitative information of impurity molecule.
One of purpose of the present invention is to provide trace impurity analytical equipment in a kind of organic pure material.
Comprise: liquid chromatograph, the cutting valve, based on ionization source and the mass spectrometer of plasma, described ionization source based on plasma comprises atomizer and corona discharge needle;
Liquid chromatograph connects cutting valve, atomizer, corona discharge needle and mass spectrometer successively.
Two of purpose of the present invention is to provide trace impurity analytical approach in a kind of organic pure material.
Comprise:
Sample is sent into liquid chromatograph, successively by the cutting valve, based on the ionization source of plasma, the impurity in sample is ionized, and sends into spectrometer analysis.
Specifically can comprise the following steps:
1) sample enters liquid chromatograph, and the major component in organic pure material is effectively separated with impurity;
2) by the cutting valve, the major component in organic pure material is excised, impurity enters the ionization source based on plasma;
3) impurity is vaporized through atomizer in the ionization source based on plasma; The nitrogen that is rich in water vapor produces plasma through corona discharge needle the time; Be ionized after the Plasma Interaction that vaporized impurity molecule and corona discharge needle produce, then send into mass spectrometer analysis.
The present invention can be by the following technical solutions:
The inventive system comprises: liquid chromatograph, cutting valve, the ionization source based on plasma, mass spectrometer; Described device can excise the major component in pure material, avoids major component to enter ion gun contaminated ion source and mass spectrometer; Chemical ionization source based on plasma can ionize simultaneously to polarity, low pole, nonpolar impurity molecule;
After organic pure material sample was introduced into liquid chromatograph, liquid chromatography can effectively be separated with impurity the major component in organic pure material;
With the excision of the major component in organic pure material, avoid major component to enter mass spectrometer by the cutting valve;
Utilize the inert gases such as nitrogen as carrier gas, water vapor to be introduced ion gun (need not carrier gas in the larger environment of humidity), corona discharge needle produces the plasma that is rich in positive ion, negative ion and electronics under high voltage;
After the trash flow of organic pure material goes out liquid chromatograph, be vaporized under the effect of atomizer, form gasoloid; The plasma that the sample gas colloidal sol that neutral spraying produces and corona discharge produce collides in three dimensions, makes electric charge on neutral sample band, namely is ionized;
Chemical ionization source based on plasma can ionize simultaneously to polarity, low pole, nonpolar impurity molecule; Be introduced into mass spectrometer after impurity molecule is ionized under the acting in conjunction of electric field force and vacuum and carry out quality analysis; Foreign ion by quality analysis after, the accurate mass of comprehensive ion and tandem mass spectrum technology etc. is completed the organic impurities qualitative analysis in organic pure material.
Will be based on chemical ionization source and the liquid chromatography coupling process of plasma, need to consider that in liquid chromatography, flow rate of mobile phase and composition mate to reach best atomizing effect mutually with the atomization gas flow velocity, and need to regulate corona voltage and the nitrogen flow rate that is rich in water vapor etc. according to the composition of mobile phase and flow velocity.
Organic pure material is written into the liquid-phase chromatographic column of liquid chromatograph by mobile phase by the sample drawing-in system, because each component in sample solution has different partition factors in two-phase (solid phase and liquid phase), when doing relative motion in two-phase, assigning process through repeated multiple times absorption-desorption, each component produces larger difference on translational speed, be separated into single component and flow out in post successively, thereby can separate with impurity the major component in organic pure material.After the major component in organic pure material flows out liquid-phase chromatographic column, by the cutting valve, major component is excised, avoid major component to pollute ionization source and mass spectrometer.In ion gun, utilize the inert gases such as nitrogen as carrier gas, water vapor to be introduced ion gun (need not carrier gas in the larger environment of humidity), apply the high voltage of several kilovolts on corona discharge needle, so produce the plasma that is rich in positive ion, negative ion and electronics around spray point.Impurity in organic pure material is vaporized under the effect of atomization gas (as nitrogen) after flowing out from liquid-phase chromatographic column, forms the very little gasoloid of particle diameter.The sample gas colloidal sol that neutral spraying produces bumps in three dimensions with the plasma that corona discharge produces, and makes that on the neutral molecule band, electric charge becomes ion, namely is ionized, and Ionized process is the process of electric charge transfer, belongs to chemi-ionization process.Because plasma has than the high ionization ability, can ionize simultaneously polarity, low pole, nonpolar impurity molecule based on the chemical ionization source of plasma.Be introduced into mass spectrometer after impurity molecule in organic pure material is ionized under the acting in conjunction of electric field force and vacuum and carry out quality analysis.Foreign ion by quality analysis after, the Information in Mass Spectra of the acquisitions such as the accurate mass of comprehensive ion and tandem mass spectrum technology can be completed the qualitative analysis of trace organic impurities in organic pure material.After having had qualitative analysis to do the basis, can carry out accurate quantitative analysis to it and measure.
Description of drawings
Trace impurity analytical equipment schematic diagram in Fig. 1 organic pure material of the present invention
Description of reference numerals:
The 1-liquid chromatograph; 2-cuts valve; The 3-atomizer; The 4-drying nitrogen; The 5-corona discharge needle; 6-is rich in the nitrogen of water vapor; The 7-mass spectrometer;
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment:
As shown in Figure 1, trace impurity analytical equipment in a kind of organic pure material comprises: liquid chromatograph 1, the cutting valve 2, based on ionization source and the mass spectrometer 7 of plasma, described ionization source based on plasma comprises atomizer 3 and corona discharge needle 5;
Liquid chromatograph 1 connects cutting valve 2, atomizer 3, corona discharge needle 5 and mass spectrometer 7 successively.
During test,
1) sample enters liquid chromatograph, and the major component in organic pure material is effectively separated with impurity;
2) by the cutting valve, the major component in organic pure material is excised, impurity enters the ionization source based on plasma;
3) impurity is vaporized through atomizer; The nitrogen that is rich in water vapor produces plasma through corona discharge needle the time; Be ionized after the Plasma Interaction that vaporized impurity molecule and corona discharge needle produce, then send into mass spectrometer analysis.
Concrete steps are as follows:
When 1, the new equipment of the present invention's design is used for organic pure material trace impurity analysis, first the toluene pure material is dissolved with methyl alcohol, for to avoid the sample contamination mass spectrometer, configure the sample solution (1 μ g/mL) of low concentration, obtain the chromatographic peak position of sample major component.
2, regulate cutting valve between liquid chromatography and ion gun, entering mass spectrum after all components that liquid chromatography flows out all is ionized by ion gun carries out quality analysis.
3, with mobile phase, sample is written into liquid-phase chromatographic column, by optimizing mobile phase composition, gradient isochromatic spectrum condition, acquisition sample major component is effectively separated with impurity.
4, enter mass spectrum after all components of liquid chromatography outflow is ionized by ion gun and carry out quality analysis, obtain complete total ions chromatogram.
5, because impurity content in sample is considerably less, for obtaining impurity signal preferably, the sample solution (100 μ g/mL) of the larger concentration of configuration.
6, larger concentration sample is introduced liquid chromatography, after major component flows out liquid-phase chromatographic column, cut valve position by software control, major component is cut away the inflow waste liquid bottle, avoided the larger major component of concentration to pollute mass spectrometer, entered mass spectrum after all impurity compositions are ionized by ion gun and carry out quality analysis.
7, by mass spectral:mass spectrographic high precision mass measurement and tandem mass spectrum technology, the impurity in organic pure material is carried out qualitative analysis.
8, possible impurity benzene and dimethylbenzene in purchase or synthetic sample, the means such as the mass spectrogram by chromatographic retention, high precision quality, tandem mass spectrum are proved conclusively the possible impurity of inferring.Contain the impurity such as a small amount of benzene and dimethylbenzene in the pure material of final definite toluene.
Claims (3)
1. trace impurity analytical equipment in an organic pure material is characterized in that:
Described device comprises: liquid chromatograph, the cutting valve, based on ionization source and the mass spectrometer of plasma, described ionization source based on plasma comprises atomizer and corona discharge needle;
Liquid chromatograph connects cutting valve, atomizer, corona discharge needle and mass spectrometer successively.
2. analytical approach that adopts trace impurity analytical equipment in organic pure material as claimed in claim 1 is characterized in that described method comprises:
Sample is sent into liquid chromatograph, successively by the cutting valve, based on the ionization source of plasma, the impurity in sample is ionized, and sends into spectrometer analysis.
3. trace impurity analytical approach in organic pure material as claimed in claim 2 is characterized in that described method comprises:
1) sample enters liquid chromatograph, and the major component in organic pure material is effectively separated with impurity;
2) by the cutting valve, the major component in organic pure material is excised, impurity enters the ionization source based on plasma;
3) impurity is vaporized through atomizer in the ionization source based on plasma, is ionized after the Plasma Interaction that produces with corona discharge needle, then sends into mass spectrometer analysis.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109975454A (en) * | 2019-03-26 | 2019-07-05 | 贵阳学院 | The mass spectrometric analysis method of ethynodiol diacetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1026607A (en) * | 1996-07-11 | 1998-01-27 | Denki Kagaku Kogyo Kk | Quantitative analysis method of silicone oil |
| CN102419354A (en) * | 2011-09-08 | 2012-04-18 | 宁波检验检疫科学技术研究院 | General rapid detection method for micromolecular poisonous and harmful substances in liquid milk |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1026607A (en) * | 1996-07-11 | 1998-01-27 | Denki Kagaku Kogyo Kk | Quantitative analysis method of silicone oil |
| CN102419354A (en) * | 2011-09-08 | 2012-04-18 | 宁波检验检疫科学技术研究院 | General rapid detection method for micromolecular poisonous and harmful substances in liquid milk |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109975454A (en) * | 2019-03-26 | 2019-07-05 | 贵阳学院 | The mass spectrometric analysis method of ethynodiol diacetate |
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Application publication date: 20130612 |