The present invention relates to an analysis method, an adhesive tape, and a pen.
Although many methods for atmospheric pressure ionization are known, methods as DART (Direct Analysis in Real Time) (Registered U.S. Trademark) or DESI (Desorption Electrospray Ionization) is recently drawing attention (see Patent Document 1).
DART is a method that adds protons (being generated by Penning ionization of atoms or molecules in which atoms or molecules of an electronic excited state collide with water in the atmosphere) to a sample and ionizes the sample. For example, in a case of using helium (He (23S) of a metastable excited state, a sample M can be ionized by performing the following.
He(23S))+H2O→H2O+*+He(11S)+e−
H2O+*+H2O→H3O++OH*
H3O++nH2O→[(H2O)nH]+
[(H2O)nH]++M→MH++nH2O
Here, “He(23S)” indicates helium of a triplet metastable excited state, “H2O+*” indicates a radical of H2O, and “MH+” is an example of an object ionized by adding protons to a sample.
DESI is a method that adheres an ionized solution to a sample and desorbs ions.
When measuring a sample by using DART or DESI, there is a case where a mass spectrometer is to be calibrated by using a calibration reagent. Further, when detecting a position of a chemical substance while moving a sample to which the chemical substance is adhered by using DART or DESI, there is a case where a reference position cannot be arbitrarily set.
In view of the above-described conventional art, the present invention is aimed to provide an analysis method, an adhesive tape and a pen used for the analysis method that allow setting a reference position for detecting a position of a chemical substance adhered to a sample using DART or DESI and allowing calibration of a mass spectrometer.
According to a first feature of the present invention, an analysis method is characterized by including the steps of forming a layer including a calibration reagent, that can generate ions by using a DART ion source apparatus, in a predetermined area of a sample, and performing mass spectrometry on the ions generated from an area of the sample including the layer by using DART or DESI while moving the sample having the layer formed therein.
According to a second feature of the present invention, it is characterized by including forming the adhesive tape including the calibration reagent.
According to a third feature of the present invention, it is characterized by including forming the layer including the calibration agent by using a pen filled with an ink including the calibration reagent.
According to a fourth feature of the present invention, it is characterized in that the calibration reagent includes one or both of polyethylene glycol having a mass spectrum including equally spaced peaks (PEG 60-PEG 2000) or a fatty acid having a carbon number of 4-36.
According to a fifth feature of the present invention, an adhesive tape is characterized by including a calibration reagent that can generate ions by using a DART ion source apparatus.
According to a sixth feature of the present invention, it is characterized in that the calibration reagent includes one or both of polyethylene glycol having a mass spectrum including equally spaced peaks (PEG 60-PEG 2000) or a fatty acid having a carbon number of 4-36.
According to a seventh feature of the present invention, a pen is characterized by including an ink filled in the pen and including a calibration reagent that can generate ions by using a DART ion source apparatus.
According to an eighth feature of the present invention, it is characterized in that the calibration reagent includes one or both of polyethylene glycol having a mass spectrum including equally spaced peaks (PEG 60-PEG 2000) or a fatty acid having a carbon number of 4-36.
The present invention can provide an analysis method, an adhesive tape and a pen used for the analysis method that allow setting a reference position for detecting a position of a chemical substance adhered to a sample using DART or DESI and allowing calibration of a mass spectrometer.
Next, embodiments for carrying the present invention are described with reference to the accompanying drawings.
Gi=v(yi−yi0); [Formula I]
in a case where “v[mm/s]” is the speed of moving the sample stage 10 in the y-axis direction, “yi0[s]” is the highest point of a peak derived from the calibration reagent of a mass chromatogram where x=xi, and “yi[s]” is a starting point of a peak derived from the chemical substance. Here, the mass spectrometer 30 can be calibrated by using a mass spectrum of a peak derived from the calibration reagent of the mass chromatogram.
The calibration reagent is not limited in particular as long as ions can be generated by using the DART ion source apparatus 20. However, in view of the accuracy of calibration, it is preferable to use, for example, polyethylene glycol having a mass spectrum including equally spaced peaks (PEG 60-PEG 2000) or a fatty acid having a carbon number of 4-36, or use two or more types of the above.
The adhesive tape T including the calibration reagent may be obtained by, for example, applying a solution having a calibration reagent dissolved in a solvent to a commonly known adhesive tape.
For example, neon of a metastable excited state, argon of a metastable excited state, or nitrogen of a metastable excited state may be used instead of helium (He (23S)) of a metastable excited state.
The sample is not limited to the rectangular flat plate B having the chemical substance C adhered thereto as long as ions can be generated by using the DART ion source apparatus 20.
The ink including the calibration reagent is obtained by adding, for example, a solution having a calibration reagent dissolved in a solvent to a commonly known ink. Further, the pen P may be obtained by, for example, filling the ink including the calibration reagent into a commonly known pen.
As a method for forming a layer including a calibration reagent, the present invention is not limited to the methods illustrated in
Further, ions may be desorbed by adding an ionized solvent to a sample by using a DESI ion source instead of using the DART ion source apparatus 20.
Although the solvent for ionization is not limited in particular, the solvent may be, for example, methanol, a methanol solution, acetonitrile, or an acetonitrile solution.
It is to be noted that the solvent for ionization may include an acidic substance or a basic substance.
The calibration reagent is not limited in particular as long as ions can be generated by using a DESI ion source. However, in view of the accuracy of calibration, it is preferable to use, for example, polyethylene glycol having a mass spectrum including equally spaced peaks (PEG 60-PEG 2000) or a fatty acid having a carbon number of 4-36), or use two or more types of the above.
The sample is not limited in particular as long as ions can be generated by using the DESI ion source.
Embodiments
[Manufacturing of Adhesive Tape T]
After forming multiple 1 mm×17 mm incisions in a label sheet for an inkjet printer (manufactured by Kokuyo Co., Ltd.), a mixture of 5 mL of a methanol solution (1 g/L) of polyethylene glycol 200 (manufactured by Wako Pure Chemical Industries, Ltd.) having an average molecular weight of 180-220 and 5 mL of a methanol solution (1 g/L) of a polyethylene glycol 400 (manufactured by Kanto Chemical Co. Inc.) having an average molecular weight of 380-420 is evenly sprayed to the label sheet. Thereby, the adhesive tape T is obtained.
[Manufacturing of Pen P]
0.5 mL of polyethylene glycol 200 (manufactured by Wako Pure Chemical Industries, Ltd.) having an average molecular weight of 180-220 and 0.5 mL of polyethylene glycol 400 (manufactured by Kanto Chemical Co. Inc.) having an average molecular weight of 380-420 are added to a supplementary ink for an Artline Wetrite (red) (Shachihata Kogyo Co., Ltd.) and agitated. Thereby, ink is obtained.
The obtained ink is filled into an Artline Wetrite (red) (Shachihata Kogyo Co., Ltd.). Thereby, the pen P is obtained.
[First Embodiment]
After applying an external pharmaceutical preparation 1 including urea, lidocaine, and diphenhydramine to a slide glass, analysis is performed using the analysis method of
Here, a DART SVP (manufactured by AMR Inc.) is used as the DART ion source apparatus 20, and the temperature of a gas heater is set to 500° C. Further, a MicrOTOFQII (manufactured by Bruker Daltonics K.K.) is used as the mass spectrometer 30, and the measurement mode is set to positive ion mode.
It can be understood from
It can be understood from
It can be understood from
Analysis is performed in a similar manner as the first embodiment except that the adhesive tape T is adhered to a work glove instead of the slide glass, so that the interval of the intermediate point between the area to which the external pharmaceutical preparation 1 is applied in the y-axis direction and the adhesive tape T in the y-axis direction becomes 24 mm.
It can be understood from
It can be understood from
Analysis is performed in a similar manner as the first embodiment except that a box is used instead of the slide glass and an external pharmaceutical preparation 2 including diphenhydramine is used instead of the external pharmaceutical preparation 1, so that the interval of the intermediate point between the area to which the external pharmaceutical preparation 2 is applied in the y-axis direction and the adhesive tape T in the y-axis direction becomes 40.8 mm.
It can be understood from
It can be understood from
10 μL of a methanol solution (1 g/L) of dimethyl phthalate (hereinafter referred to as “solution 1”), 10 μL of a methanol solution (1 g/L) of diethyl phthalate (hereinafter referred to as “solution 2”), and 10 μL of a methanol solution (1 g/L) of di-isopropyl phthalate (hereinafter referred to as “solution 3”) are applied to a slide glass in a straight-line manner at intervals of 24 mm. Then, analysis is performed by using the analysis method illustrated in
It can be understood from
It can be understood from
It can be understood from
Further, the present invention is not limited to these embodiments, but variations and modifications may be made without departing from the scope of the present invention.
Number | Date | Country | Kind |
---|---|---|---|
2010-227728 | Oct 2010 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/JP2011/072993 | 10/5/2011 | WO | 00 | 4/2/2013 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2012/046774 | 4/12/2012 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
20020160428 | Sundrehagen | Oct 2002 | A1 |
20080067348 | Musselman | Mar 2008 | A1 |
20090090855 | Kobold et al. | Apr 2009 | A1 |
20090242752 | Murakami et al. | Oct 2009 | A1 |
20090266980 | Sano | Oct 2009 | A1 |
20120028342 | Ismagilov et al. | Feb 2012 | A1 |
Number | Date | Country |
---|---|---|
S64-23158 | Jan 1989 | JP |
10-293127 | Nov 1998 | JP |
2004-527760 | Sep 2004 | JP |
2007-298328 | Nov 2007 | JP |
2008-180659 | Aug 2008 | JP |
2009-243902 | Oct 2009 | JP |
WO 2007055293 | May 2007 | WO |
Entry |
---|
Haunschmidt et al. “Rapid identification of stabilisers in polypropylene using time-of-flight mass spectrometry and DART as ion source”, The Analyst, 2010, 135 pp. 80-85. |
International Search Report mailed on Nov. 22, 2011. |
Manuela Haunschmidt, Christian W. Klampfl , Wolfgang Buchberger and Robert Hertsens, Rapid identification of stabilisers in polypropylene using time-of-flight mass spectrometry and DART as ion source, Analyst, vol. 135 No. 1, Jan. 2010, p. 80-85. |
Japanese Office Action dated Oct. 21, 2014. |
Number | Date | Country | |
---|---|---|---|
20130187034 A1 | Jul 2013 | US |