JPS58209854A - Liquid chromatograph mass spectrograph - Google Patents

Abstract

PURPOSE:To obtain a versatile liquid chromatograph mass spectrograph in which there is no need to vaporize a smaple before it is analyzed and components flowing out from a liquid chromatograph including a non-volatile sample and a thermally unstable smaple can be continuously ionized. CONSTITUTION:A high-speed neutral atom gun 14 is a system in which, at first, argon ions Ar<+> are produced with an ion gun, the thus produced argon ions are accelerated and converged by an accelerating voltage fo 2-10KV before being made incident upon a collision chamber which is charged with argon gas at a pressure of 10<-3>-10<-4> Torr, then the argon ions are converted into neutral argon atoms by electric-charge exhange reaction before the netural argon atoms are discharged at high speed. It is specially effective for ionization of a component which exists in a sample as a liquid phase. As a result, a sample component to be analyzed which flows out on the 45 deg. angle surface of the stainless-steel rod 12 of a receiving nozzle 11 is ionized by the irradiation of a high- speed argon atom beam discharged from the high-speed neutral electron gun 14, and the thus produced sample ions are extracted by counter electrodes 15 before being made incident upon a mass spectrograph 4.

Description

[Detailed description of the invention]

Chromatography is a useful analytical technique for separating and analyzing multi-component mixed samples and is widely used. Furthermore, a gas chromatograph/mass spectrometer coupled with a gas chromatograph K*It analyzer can not only obtain information on the molecular weight and molecular structure of each component separated by the gas chromatograph using the mass spectrometer; 1. It has the ability to detect ultra-trace components with high sensitivity by using it as a selective detector. It has such characteristics that it has been widely put into practical use. However, one problem with analysis using this gas chromatograph/mass spectrometer is that in order to introduce the sample to be analyzed into the gas chromatograph, it must be vaporized, so non-volatile samples must be vaporized. This severely limits its application to thermally unstable samples that would be destroyed by heating for vaporization. On the other hand, liquid chromatography does not have the same limitations as gas chromatography and can effectively analyze non-volatile samples and thermally unstable samples. Although it has been widely used in the analysis of this type of sample, the combination of a liquid chromatograph and a mass spectrometer has not yet been put into practical use for general purposes. This first thing. This is because it was not possible to continuously ionize the nonvolatile or thermally unstable sample liquid that flows out as separated components from the liquid chromatograph. The entire purpose of this invention is to solve and provide a practical liquid chroma graph/measuring analyzer f111, hereinafter referred to as this invention. This will be explained with reference to the embodiments shown in the drawings. FIG. 1 shows the installation/configuration of this invention. ] is a micro liquid chromatograph. The micro liquid chromatograph 1 has an inner diameter of 01 to 1. Orxx column is used, and the mobile phase flow rate is 1 ml to several]
Ots (1/min) 0.
5 +n g ~2. The mobile phase flow rate is low at 1/200~]/2000 compared to the mobile phase flow rate of Orull/fj. It has conditions suitable for removing the mobile phase solution necessary for coupling with the mass spectrometer 4. 2 is liquid chromatograph 1
3 is an interface for coupling with the mass spectrometer 4, and the mobile phase solution is removed in this part.The interface 2 ionizes the sample components from the liquid chromatograph I from which the mobile phase solution has been removed. An example of this interface 2 and the ionization chamber 3 (fast neutral atomic gun, counter electrode) will be explained with reference to FIG. 2. Then, 9. The interface 2 is of the vacuum atomization type, and 5 is an inlet nozzle made of stainless steel, ceramics, or glass, and a neprising gas passage 6 with a diameter of several nanometers is bored to communicate with the inlet Arancia. The tip 8 of the inlet nozzle 5 is narrowed with an opening of about 0.5Mφ.In addition, a stainless steel wire of about 013Wφ is passed through the napriding gas passage 6 of the inlet flange 5. A stainless steel pipe 9 with a diameter of 0.3 fimφ and an inner diameter of about 0.15 mφ is inserted, and this stainless steel pipe 9 is connected to the column outflow pipe of the liquid chromatograph 1. Therefore, the liquid chromatograph 2 effluent solution from the pipe 1 passes through this stainless steel pipe 9

[7. It is atomized at the tip 8 of the inlet nozzle 5 by nebulizing gas from around it. Note that 10 is a pipe for connecting a vacuum pump. Reference numeral 11 denotes a socket nozzle made of ceramics.The outlet IIItC to the mass spectrometer 4 is fitted with a stainless steel hood 12 whose tip is cut off at an angle of 45 degrees. 03~0.511111' in the center of the socket nozzle 11
A passageway 13 is bored through the rod 13 to allow the previously atomized sample component to be analyzed to flow out to the tip of the rod 2. The 1L 511 of inlet nozzle 5 and inlet nozzle 11 are generalized to optimize the removal of the mobile phase solution. 14 is a high-speed neutral atom needle, which first generates argon ions Ar with an ion gun, accelerates and converges them with an accelerating voltage of 2 to 10 KV, and argon gas becomes 10-3 to 10''To
A method in which argon is introduced into a collision chamber sealed at a pressure of rr, converted into neutral argon atoms through a charge exchange reaction, and emitted at high speed, and is particularly effective for ionizing sample components present in the liquid phase. It is. 15 is a counter electrode. Therefore, the stainless steel loft 12 of the socket nozzle 11
451XM? The sample components to be analyzed flowing into I are
The sample ions are ionized by irradiation with a high-speed argon atomic beam emitted from the high-speed neutral atomic needle 14 , and the generated sample ions are extracted by the counter electrode 15 and introduced into the mass spectrometer 4 . Note that 16 is a partition wall having an opening in the center through which the ion beam passes, and serves as an ionization chamber 3 and an ionization chamber 3 which are independently evacuated by a vacuum pump (not shown) K connected to exhaust pipes 17 and 18, respectively. The mass spectrometer 4 is isolated from the mass spectrometer 4 in vacuum. In the embodiment described above, since ionization by irradiation with fast neutral atoms generates both positive and negative ions, positive or negative ions can be generated by switching the polarity of the voltage applied to the stainless steel rod 12 and the counter electrode 15. Any ion can be used for analysis, and for mass spectrometer @4. Although a detailed explanation of its configuration has been omitted, well-known types such as a magnetic field type, a quadrupole type, and a magnetic field type can be used. Furthermore, interface 2
It is also optional to heat this part to more effectively remove the mobile phase quenching solution. From the above, this invention makes it possible to continuously ionize components flowing from a liquid chromatograph, including small volatile samples and thermally unstable samples, without having to vaporize the sample for one analysis. A versatile liquid 0-r spike-ruff mass spectrometer can be realized.

[Brief explanation of drawings]

FIG. 1 is a structural diagram of an equipment according to the present invention, and FIG. 2 is a schematic vertical cross-sectional view of a main part of an embodiment of the present invention. In the figure, 1 is a liquid chromatograph, 2 is an interface, 3 is an ionization chamber, and 4 is a mass spectrometer. 5 is an inlet nozzle, 11 is a socket nozzle, 14 is a high-speed neutral atomic gun, 15 is a counter electrode, and 16 is a partition wall.

Claims (1)

[Claims] 1. An inlet nozzle with a nebulizing gas passage into which a pipe connected to the column outflow end of the liquid flow chart is inserted, and a rod with an inclined surface at the tip that protrudes into the ionization chamber is fitted into the other and the center A vacuum atomization interface is formed by facing a socket nozzle with a hole passing through the loft with a certain gap under vacuum, and the sample components flowing out to the sloped surface of the loft tip of the socket nozzle are irradiated with high-speed neutral atoms. A liquid chromatograph and a mass spectrometer are coupled through an ionization chamber equipped with a high-speed neutral atomic gun and a counter electrode, and sample components separated and flowing out from the liquid chromatograph are removed from the mobile phase solution through a vacuum atomization interface. A liquid chromatograph/mass spectrometer, characterized in that sample components are ionized by high-speed neutral atom beam irradiation in an ionization chamber, and generated ions are analyzed by a quality i-sweat analyzer.