JP2005227160A - Near field spectroscopic analyzer and spectroscopic analytical method used in combination with chromatograph - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an analyzer and an analytical method of high sensitivity used in combination with a chromatograph and a near field spectroscopic analyzer. <P>SOLUTION: This near field spectroscopic analyzer and analytical method used in combination with the chromatograph is provided with a chromatograph part and a near field spectroscopic analyzer part. In the analyzer and the analytical method, a sample is moved just to an under side of a probe in the near field spectroscopic analyzer part by moving a stage, to be analyzed, after the sample separated by the chromatograph part is mounted on the stage to be enriched and fixed by cooling or heating, and the analysis-finished sample is moved to another position by moving the stage, to be removed by heating. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a high-sensitivity analyzer and method that combine a chromatographic function and a near-field spectroscopic analysis function.

  Conventionally, GC-IR, LC-IR, etc., which are a combination of a gas or liquid chromatograph and an infrared spectroscopic analyzer, are known. Thereby, the component separated by the chromatograph can be analyzed by the infrared spectroscopic analyzer, and the chemical bonding state of the component sample can be obtained.

  However, considering the acceptance limits of chromatographic separation columns, detectors, etc., a very small amount of sample can be introduced into the chromatograph. Further, since the amount of a single component after separation is further small, detection by infrared spectroscopic analysis becomes difficult, and there is a problem that the sensitivity of the entire apparatus is very low.

  On the other hand, a near-field spectroscopic analyzer is known as a means for analyzing a micro area on a sample surface using a probe (probe) as described in Patent Document 1 (Japanese Patent Laid-Open No. 2001-27597). It is difficult to analyze with a very small amount of sample obtained from a chromatograph.

JP 2001-27597 A (Claims)

  It is an object of the present invention to provide a highly sensitive analyzer and analysis method using a chromatograph and a near-field spectroscopic analyzer in combination.

According to the present invention, the above object is an apparatus that includes a chromatograph unit and a near-field spectroscopic analyzer unit, and that analyzes a sample separated by the chromatograph unit using a near-field spectroscopic analyzer unit,
A sample guide tube branched from the component separation column in the chromatograph section,
A stage having a sample mounting portion for mounting a sample flowing out from the tip of the sample guide tube;
Stage moving means for moving the stage between a sample mounting position, a near-field spectroscopic analysis position, and an analyzed sample removal position;
Sample concentration fixing means for concentrating and fixing the sample on the stage by cooling or heating at the sample mounting position,
This is achieved by a chromatographic combined near-field spectroscopic analyzer comprising a sample removing means for removing the analyzed sample on the stage by heating at the analyzed sample removal position.

According to the present invention, there is further provided a chromatography combined near-field spectroscopic analysis method using the above-mentioned apparatus, comprising the following steps:
The process of loading the sample from the sample guide tube to the sample loading part of the stage,
A process of thickening and fixing the mounted sample by cooling or heating;
Moving the stage to move the concentrated and fixed sample on the sample mounting part to the near-field spectroscopic analysis position;
A step of performing near-field spectroscopic analysis of the sample,
Moving the stage to move the analyzed sample on the sample mounting section to the analyzed sample removal position;
Removing the analyzed sample by heating;
Are carried out in the above order, and a chromatography combined near-field spectroscopic analysis method is provided.

  The present invention has the following effects by combining a chromatograph and a near-field spectroscopic analyzer.

  Near-field spectroscopy is a method for analyzing the chemical bonding state of a sample surface with high spatial resolution below the wavelength of light. As shown in FIG. 1, when light L is introduced into, for example, an aperture probe P similar to a probe such as a scanning probe microscope (SPM), near-field light N is generated at an aperture T smaller than the wavelength. This is irradiated onto the surface of the sample S, and the reflected light R is detected by the detector D and subjected to spectral analysis. This enables spectroscopic analysis of a very small region smaller than the wavelength of the light L.

  In the present invention, by utilizing this characteristic of the near-field spectroscopic analysis method, a highly sensitive spectroscopic analysis of a small amount of sample separated by chromatography is realized.

  That is, according to the present invention, since the sample separated by the chromatograph is concentrated and fixed on the stage, the near-field spectroscopic analysis suitable for the analysis of the minute region is performed, so that the minute amount sample can be spectroscopically analyzed with high sensitivity.

  Furthermore, since the cycle of sample loading → analysis → removal → loading... Can be repeated at a high speed by moving the stage, highly sensitive continuous spectroscopic analysis can be performed for each separated component sample.

Embodiment 1
FIG. 2 shows a configuration example of a gas chromatograph combined near-field spectroscopic analyzer (hereinafter abbreviated as “GC spectroscope”) as an embodiment of the present invention.

  The illustrated GC spectrometer 100 includes a gas chromatograph unit 102 and a near-field spectroscopic analyzer unit 104.

  The gas chromatograph unit 102 includes a separation column (capillary column) Q and an analyzer A such as a mass spectrometer, and a sample inlet J receives a sample from the sample collector I. A sample guide tube B is branched in the middle of the piping from the column Q to the analyzer A, and a sample jet port F is opened at the tip thereof.

  The near-field spectroscopic analyzer 104 detects the light source E that generates the light L, the probe P that receives the light L from the rear end and generates the near-field light N at the tip T, and the reflected near-field light R. A device D is provided. As the light source E, for example, a wavelength variable laser can be used.

  The sample separated by the gas chromatograph 102 is mounted as a sample S from the sample outlet F to the sample mounting portion of the stage G that reciprocates horizontally (arrow M). A cooler C such as a Peltier element is disposed at the sample mounting position X1 so as to face the back surface of the stage G.

  The sample S from the gas chromatograph 102 is usually a mixed gas of an organic volatile vapor which is a substantial sample material and a carrier gas (He or the like). When the sample S is cooled (rapidly cooled) on the stage G by the cooler C, only the organic volatile vapor is concentrated in a minute region, and is condensed and adhered. The carrier gas is separated and removed during the condensation process. The cooling temperature is generally 0 ° C. or lower.

  When the sample S is concentrated and fixed at the mounting position X1 in this way, the stage G is moved to the left (arrow K1) to stop the sample S at the spectroscopic analysis position X2, and the sample S is probed by the near-field spectroscopic analyzer 104. Close to the tip T of P.

  Light L from the light source E is introduced into the probe P, and near-field light N is generated from the tip T. The reflected near-field light R from the sample S is detected by the detector D and subjected to spectral analysis.

  After the analysis, the stage G is moved to the right (arrow K2) to stop the sample S at the removal position X3 at the right end in the figure. Here, the sample S is heated and decomposed and removed by the heater H. The heating temperature is generally 500 ° C. or higher.

  Thereafter, the stage G is moved to the left (arrow X3) to return the sample mounting portion to the sample mounting position X1 directly below the sample ejection port F.

  By repeating the above cycle, the sample from the chromatograph 102 can be continuously spectroscopically analyzed.

  As the spectroscopic analysis of the present invention, vibrational spectroscopy including infrared light, visible light (such as Raman spectroscopy), and ultraviolet light can be applied.

[Embodiment 2]
FIG. 3 shows a configuration example of a liquid chromatograph combined near-field spectroscopic analyzer (hereinafter abbreviated as “LC spectroscope”) as another embodiment of the present invention.

  The illustrated LC spectrometer 110 includes a liquid chromatograph unit 112 and a near-field spectroscopic analyzer unit 114.

  The liquid chromatograph unit 112 includes a separation column Q and an analyzer A, and a sample inlet J receives a sample from the sample collector I. A sample guide tube B is branched in the middle of the piping from the column Q to the analyzer A, and a sample jet port F is opened at the tip thereof.

  The near-field spectroscopic analysis device 114 has the same configuration as the near-field spectroscopic analysis device 104 of the first embodiment shown in FIG. 2, and a near-field at the front end T that receives the light L from the light source E that generates the light L and the rear end. A probe P that generates light N and a detector D that detects reflected near-field light R are provided.

  The sample separated by the liquid chromatograph 112 is mounted as a sample S from the sample outlet F to the sample mounting portion of the stage G that reciprocates horizontally (arrow M). A heater H1 is disposed at the sample mounting position X1 so as to face the back surface of the stage G.

  The sample S from the liquid chromatograph 112 is usually a mixed solution of a high-boiling organic substance that is a substantial sample substance and a low-boiling organic solvent (THF, chloroform, etc.). When this sample S is heated on the stage G by the heater H1, the low boiling point organic solvent is volatilized and removed, and only the high boiling point organic substance is concentrated and adhered in a minute region and fixed. The heating temperature by the heater H1 is generally about 100 ° C.

  After the sample S is concentrated and fixed at the mounting position X1, the stage G is sequentially moved horizontally in the same manner as in the first embodiment, and then the mounting position X1 → <left shift K1> → analysis position X2. → <Right move K2> → Move to removal position X3. Here, the sample S is heated and decomposed and removed by the heater H2. The heating temperature by the heater H2 is generally 500 ° C. or higher.

  Thereafter, the stage G is returned to the sample mounting position X1 immediately below the sample outlet F by <left movement X3>.

  By repeating the above cycle, the sample from the liquid chromatograph 112 can be continuously spectroscopically analyzed.

  As the spectroscopic analysis of the present invention, vibrational spectroscopy including infrared light, visible light (such as Raman spectroscopy), and ultraviolet light can be applied.

  In both cases of Embodiments 1 and 2, the spectroscopic analysis spectrum shown in FIG. 4 (2) is obtained for the desired peak substance in the chromatogram shown in FIG. 4 (1). This also applies to the embodiments described below.

[Embodiment 3]
In the first and second embodiments, the stage G is moved back and forth, and the cycle of sample loading X1 → <left movement K1> → analysis X2 → <right movement K2> → sample removal X3 → <left movement K3> → sample loading X1. Execute. At this time, the period of the right movement K2 cannot be temporarily analyzed, and this analysis incapable period K2 is inefficient in that it must be larger than the other periods K1 and K3.

  In the present embodiment, as shown in FIG. 5, the stage G is rotationally moved to eliminate the above points and increase the efficiency. In the figure, each component given the same reference numeral as in FIGS. 2 and 3 corresponds to each component in the first and second embodiments.

  When the disk-shaped stage G is rotated in the direction of the arrow V, the sample mounting portion α on the stage G moves to the mounting position X1 → <forward movement K1> → analysis position X2 → <forward movement K2> → removal position X3 → < Since the forward movement K3> → mounting position, K2, and K3 are all in the forward direction, the unidirectional movement does not include the reverse movement period K2 in the first and second embodiments, and the above analysis impossible period can be minimized. , Improve efficiency. Along with this, the time resolution is also improved.

  A point to be considered in the present embodiment is the presence of centrifugal force accompanying the rotational motion V. The present invention aims to analyze samples supplied one after another from a chromatograph at high speed. For this purpose, it is necessary to speed up the rotational movement of the stage G that is responsible for moving the sample, and the centrifugal force also increases accordingly. Therefore, it is necessary to stably hold the sample S on the mounting portion against this.

  Therefore, as shown in FIG. 5, the jet outlet F of the sample guide tube B is arranged at a small angle θ with respect to the horizontal stage surface from the outer side to the inner side of the disk-shaped stage G. Thereby, the sample jet output from the jet outlet F can be effectively acted as a resistance against the centrifugal force toward the rotation center of the stage G.

[Embodiment 4]
In the embodiment shown in FIG. 6, as a measure against the centrifugal force when rotating the stage G as in the third embodiment, the stage G is cylindrical and can rotate around the vertical central axis U. A mounting portion for the sample S is provided at a corner portion formed by the inner peripheral surface and the bottom surface of the cylinder. Each component given the same reference numeral as in FIG. 5 corresponds to each component in the third embodiment.

  In the present embodiment, by mounting the sample S on the corner portion between the inner peripheral surface and the bottom surface of the cylindrical stage G, the sample S can be stably held on the mounting portion even when the stage G is stopped or at high speed rotation.

  In the present embodiment, the detector D is arranged inside the cylindrical stage G to ensure a proximity state with the sample S.

[Embodiment 5]
In the present embodiment, as shown in FIG. 7 as an example, the stage G has a drum shape with a horizontal rotation axis, and a smooth metal film Y is provided on the sample mounting surface. The sample S mounted on the metal film Y is irradiated with near-field light N from the tip F of the probe P of the near-field spectroscopic analyzer at a shallow irradiation angle φ. Each component given the same reference numeral as that in FIGS. 5 and 6 corresponds to each component in the third and fourth embodiments.

The irradiation angle φ of the near-field light N is for example 10 ° or less, by surface enhanced reflection strong electric field caused by the interference between the reflected near-field light R, the detection sensitivity can be increased to 10 ² times ^{to 105} times.

  In the example of FIG. 7, the stage G is shown as a drum that rotates about the horizontal axis, but it is not necessary to be limited to this. Even if the planar stage is reciprocally moved as in the first and second embodiments (FIGS. 2 and 3), a disk-like shape rotating around the vertical axis as in the third and fourth embodiments (FIGS. 5 and 6) Even if it is a form using a cylindrical stage, or it is another form, the same effect as this embodiment is acquired.

[Embodiment 6]
In Embodiments 1 and 2 (FIGS. 2 and 3), by providing a plurality of mounting portions for the sample S, combinatorial chemistry for analyzing a large number of samples at once is possible.

  FIG. 8 shows an example, and for each sample S mounted at a plurality of locations, near field spectroscopy analysis is performed immediately below the probe P after adding various reagents from the additive reagent outlet d. Each component given the same reference numeral as in FIGS. 2 and 3 corresponds to each component in the first and second embodiments.

  In the present embodiment, in addition to the configurations of the first and second embodiments, a slit Z that performs horizontal reciprocating motion (arrow m) in front of the surface of the sample outlet F is provided in addition to the provision of a plurality of sample mounting portions. The reciprocating motion m of the slit Z is synchronized with the reciprocating motion M of the stage G so that each component from the chromatograph can be clearly separated.

  Thereby, combinatorial chemistry can be realized in which a plurality of reagents can be added to each separated sample and the reaction state can be observed at any time.

[Embodiment 7]
In the present embodiment, in the configuration of the sixth embodiment, the probe P of the near-field spectroscopic analyzer is synchronized with the point where each sample mounting portion of the stage G is provided with the depression h and the position of the depression h due to the movement of the stage G. Improved the vertical vibration (arrow β). Each component given the same reference numeral as in FIG. 7 corresponds to each component in the sixth embodiment.

  By holding and mounting the sample S in the recess h, the holding of the sample S is stabilized on the stage G that reciprocates at high speed. However, in order to perform near-field spectroscopic analysis, it is necessary to bring the probe P close to the sample S in the recess h. For this purpose, the probe P is vibrated up and down as indicated by an arrow β, and this vertical vibration β is synchronized with the movement of the recess h by the movement M of the stage G. That is, the stage left-right movement M and the probe vertical movement β are synchronized with the timing so that the probe P is lowered into the depression h when the depression h is located immediately below the probe P.

  ADVANTAGE OF THE INVENTION According to this invention, the highly sensitive analyzer and analysis method which combined use of the chromatograph and a near field spectroscopic analyzer are implement | achieved.

FIG. 1 is a cross-sectional view showing the general principle of a near-field spectroscopic analyzer. FIG. 2 is a layout diagram showing a gas chromatograph combined near-field spectroscopic analyzer using a reciprocating plate stage according to Embodiment 1 of the present invention. FIG. 3 is a layout diagram showing a near-field spectroscopic analyzer combined with a liquid chromatograph using a reciprocating plate stage according to Embodiment 2 of the present invention. FIG. 4 is a graph schematically showing (1) a chromatogram obtained by the analyzer of the present invention and (2) a spectroscopic analysis spectrum for a substance having a desired peak. FIG. 5 is a (1) cross-sectional view, (2) perspective view, and (3) plan view showing a chromatographic combined near-field spectroscopic analyzer using a rotary motion disc stage according to Embodiment 3 of the present invention. FIG. 6 is a perspective view showing a chromatographic combined near-field spectrometer using a rotating cylindrical stage according to Embodiment 4 of the present invention. FIG. 7 is a cross-sectional view showing a chromatographic combined near-field spectrometer using a rotary drum stage according to Embodiment 5 of the present invention. FIG. 8 is a cross-sectional view showing a chromatographic combined near-field spectroscopic analyzer using a reciprocating multi-sample stage according to Embodiment 6 of the present invention. FIG. 9 is a cross-sectional view showing a chromatographic combined near-field spectroscopic analyzer using a reciprocating multi-sample hollow stage according to Embodiment 7 of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ... Near field spectroscopic analyzer combined with gas chromatograph 102 ... Gas chromatograph unit 104 ... Near field spectroscopic analyzer unit 110 ... Near field spectroscopic analyzer combined with liquid chromatograph 112 ... Liquid chromatograph unit 114 ... Near field spectroscopic analyzer unit Q ... Separation column A ... Analyzer J such as mass spectrometer ... Sample inlet I ... Sample collector B ... Sample guide tube F ... Sample outlet L ... Light E ... Light source T ... Tip P of probe P ... Near field spectroscopic analysis Probe N of the apparatus: Near-field light R: Reflected near-field light D: Detector M: Horizontal reciprocation S of stage G ... Sample C ... Coolers H, H1, H2 ... Heater G ... Stage X1 ... Sample mounting position X2 ... Near-field spectroscopic analysis position X3 ... Sample removal position K1 ... Direction of movement from mounting position X1 to analysis position X2 ... Direction of movement K from analysis position X2 to removal position X3 The orientation of ... moving to the mounting position X1 from the removal position X3

Claims (10)

A device comprising a chromatograph unit and a near-field spectroscopic analyzer unit, and analyzing a sample separated by the chromatograph unit by a near-field spectroscopic analyzer unit,
A sample guide tube branched from the component separation column in the chromatograph section,
A stage having a sample mounting portion for mounting a sample flowing out from the tip of the sample guide tube;
Stage moving means for moving the stage between a sample mounting position, a near-field spectroscopic analysis position, and an analyzed sample removal position;
Sample concentration fixing means for concentrating and fixing the sample on the stage by cooling or heating at the sample mounting position,
A chromatographic combined near-field spectroscopic analyzer comprising a sample removing means for removing the analyzed sample on the stage by heating at the analyzed sample removal position.   2. The apparatus according to claim 1, wherein the chromatograph is a gas chromatograph and the sample concentration fixing means is a cooler.   2. The apparatus according to claim 1, wherein the chromatograph is a liquid chromatograph and the sample concentration fixing means is a heater.   4. The apparatus according to claim 1, wherein the stage moving means is a reciprocating means.   The apparatus according to any one of claims 1 to 3, wherein the stage moving means is rotational movement means.   6. The stage according to claim 5, wherein the stage is cylindrical and rotatable around a vertical central axis, and the sample mounting portion is provided at a corner portion formed by an inner peripheral surface and a bottom surface of the cylinder. Device to do.   6. The apparatus according to claim 4, wherein the sample mounted on the smooth metal film provided on the sample mounting surface of the stage is irradiated with near-field light at a shallow angle.   6. The apparatus according to claim 4, wherein a plurality of sample mounting portions are provided on the stage.   9. The plurality of sample mounting portions according to claim 8, wherein the plurality of sample mounting portions are depressions dug into the stage, and the probe of the near-field spectroscopic analysis apparatus vibrates up and down in synchronization with the position of the depression due to the movement of the stage. A device characterized by. A chromatography combined near-field spectroscopic analysis method using the apparatus according to claim 1, wherein the following steps are performed:
The process of loading the sample from the sample guide tube to the sample loading part of the stage,
A process of thickening and fixing the mounted sample by cooling or heating;
Moving the stage to move the concentrated and fixed sample on the sample mounting part to the near-field spectroscopic analysis position;
A step of performing near-field spectroscopic analysis of the sample,
Moving the stage to move the analyzed sample on the sample mounting section to the analyzed sample removal position;
Removing the analyzed sample by heating;
Are carried out in the order described above.

Images